(19)
(11)EP 4 032 611 A1

(12)EUROPEAN PATENT APPLICATION
published in accordance with Art. 153(4) EPC

(43)Date of publication:
27.07.2022 Bulletin 2022/30

(21)Application number: 20874815.2

(22)Date of filing:  24.07.2020
(51)International Patent Classification (IPC): 
B01J 23/78(2006.01)
B01J 21/18(2006.01)
B01D 53/48(2006.01)
B01J 23/83(2006.01)
B01J 21/08(2006.01)
(52)Cooperative Patent Classification (CPC):
B01D 53/02; B01D 53/48; B01D 53/50; B01D 53/75; B01J 20/20; B01J 20/30; C01B 17/04; C01B 17/16; F23G 7/06; B01J 21/08; B01J 23/83; B01J 21/18; B01J 23/78
(86)International application number:
PCT/CN2020/104502
(87)International publication number:
WO 2021/068599 (15.04.2021 Gazette  2021/15)
(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR
Designated Extension States:
BA ME
Designated Validation States:
KH MA MD TN

(30)Priority: 11.10.2019 CN 201910962508

(71)Applicants:
  • China Petroleum & Chemical Corporation
    Beijing 100728 (CN)
  • Sinopec Qilu Company
    Zibo, Shandong 255400 (CN)

(72)Inventors:
  • XU, Cuicui
    Zibo, Shandong 255400 (CN)
  • LIU, Aihua
    Zibo, Shandong 255400 (CN)
  • HAN, Feng
    Zibo, Shandong 255400 (CN)
  • LIU, Jianli
    Zibo, Shandong 255400 (CN)
  • LIU, Zengrang
    Zibo, Shandong 255400 (CN)
  • TAO, Weidong
    Zibo, Shandong 255400 (CN)
  • CHANG, Wenzhi
    Zibo, Shandong 255400 (CN)
  • LYU, Caishan
    Zibo, Shandong 255400 (CN)

(74)Representative: Hoffmann Eitle 
Patent- und Rechtsanwälte PartmbB Arabellastraße 30
81925 München
81925 München (DE)

  


(54)COMPOSITE MATERIAL AND USE THEREOF IN DESULFURIZATION


(57) The present disclosure relates to the technical field of desulfurization, and discloses a composite material and the use thereof in desulfurization. The composite material contains activated carbon, alkali metal oxides, silicon oxides, iron oxides, and rare earth element oxides, wherein the weight ratio between the activated carbon, iron oxides and rare earth element oxides is 100 : (0.5-5) : (1-10), and the composite material satisfies a certain relationship. Also disclosed in the present disclosure is the use of the composite material in desulfurization. The composite material of the present disclosure, as an adsorbent, has a higher sulfur breakthrough capacity and desulfurization rate.




Description

TECHNICAL FIELD



[0001] The present disclosure relates to the technical field of desulfurization, in particular to a composite material and use thereof in desulfurization.

BACKGROUND



[0002] SO2 is the primary cause of acid rain; it can destroy the physiological function of plants, and slow down growth of crops and trees; when the human body inhales SO2 gas with a high concentration, which can impose a strong irritating effect on the respiratory tract of human. SO2 is regarded as the major pollutant in the atmosphere and has attracted wide attention of the populace. For example, SO2 emissions have been reported to cause 40% of the domestic land area in China to be harmed by acid rain, the annual economic loss reaches up to 110 billion yuan. Therefore, controlling pollution and reducing SO2 emissions are important tasks to perform the sustainable economic and social development of China.

[0003] SO2-containing exhaust gas will be generated in the exhaust gas of industrial heating furnaces, sulfur tail gas and catalytic cracking regenerative flue gas. Given that the environmental protection regulations in China are increasingly stringent, the task of reducing SO2 emission is extremely urgent. At present, the flue gas desulfurization technologies at home and abroad are divided into two major categories. The first category is a wet process, i.e., the exhaust gas is treated with some kind of liquid absorbent, emulsion absorbent or absorption solution; the second category is a dry process, i.e., the SO2 in the flue gas is removed by a sorbent, an absorbent or a catalyst in powder or granular form. The most representative and fastest growing technique of the wet process desulfurization technologies is alkaline washing desulfurization, such as the LABSORBTM technology commercially available from the DuPont BELCO Corporation. A lower emission of 50mg/m3 or less is achieved by the wet process desulfurization technology which subjects the flue gas to the alkaline washing, but the process brings about the new secondary pollutants, namely sodium sulfate-containing waste water, which is forbidden by the law and regulations to be directly discharged and its retreatment process requires a large amount of investment. The China Petroleum & Chemical Corporation (Sinopec) has completely banned the newly implemented the alkaline process desulfurization on the fume gas emitted by a variety of facilities. The dry process desulfurization has been gaining momentum in recent years due to its characteristics of simple operation, small investment on equipment, and not causing secondary pollution, and is regarded as the most promising desulfurization technology with vast application prospect. The research and development of dry process flue gas desulfurization technologies have attracted widespread attention at home and abroad in recent years. If a mature technology of dry process desulfurization can be used for removing sulfur dioxide in the flue gas, it would be desirable to meet requirements of the environmental protection regulations and safeguard the atmospheric environment while reducing the emission amount of SO2.

[0004] The core of the dry process desulfurization technology is the adsorbent. The molecular sieves and activated carbons are the key adsorbents used for the dry process adsorption desulfurization. Activated carbons are charcoals having strong adsorption capability, which are prepared by using coal, wood, fruit husks and the like as the raw materials, and subjecting to high temperature (300-400°C) carbonization, anoxic activation (920-960°C) and post-treatment. The specific features of hydrophobic, non-polar and thermally stable performance of the activated carbons per se enable them to be easily modified and activated during use, and the activated carbons have unique surface chemical property and void volume structure, which enhances their loading capacity and adsorptive property. Activated carbons have well-developed internal porosity, the adsorbable micro-pore surface area accounts for more than 95% of the total surface area, the activated carbon with a tremendous specific surface area can effectively adsorb sulfur-containing compounds such as SO2. The adsorption of SO2 by activated carbons is affected by the surface properties such as morphology, distribution of the pore size. The ordinary activated carbons have a small capacity of sulfur adsorption, a low desulfurization rate and a poor accuracy, they are usually modified to achieve more desirable desulfurization effects. Modifying the chemical property of the activated carbon surface to increase its adsorption rate and sulfur capacity is currently the main direction of research and development of the desulfurization with activated carbons.

[0005] CN102059094A discloses a preparation method of sulfur-removal activated carbon containing copper, the method relates to the technical field of removing the sulfur-containing compounds in the air, and intends to solve the problems of low desulfurization efficiency and high production cost of the traditional sulfur-removal activated carbon. The present disclosure provides a sorbent for simulating industrial flue gas desulfurization with a mixed gas of high purity SO2, H2S, air and water vapor. CN101954284A discloses an activated carbon desulfurization catalyst and a preparation method thereof. The provided catalyst is consisting of carrier activated carbon and an active ingredient metal oxide mixture, wherein the metal oxide mixture is the mixture of copper oxide, iron oxide, aluminum oxide, nickel oxide, manganese oxide, cobalt oxide and zinc oxide.

[0006] Although the aforementioned literatures have reported some sorbents for removing the sulfur-containing compounds and the corresponding desulfurization process, there are problems with low sulfur removal rates (the saturated sulfur capacity is typically within the range of 5-10%) and low sulfur breakthrough capacity of the desulfurizing agent during the practical applications. The limited adsorption capacity causes a large dosage of sorbents and the bulky purification plant, increases the capital cost of the equipment, and the frequent regeneration complicates the operation process.

SUMMARY



[0007] The object of the present disclosure is to overcome the problems in the prior art that a combination of desulfurization rate and sulfur breakthrough capacity cannot be obtained simultaneously, and provide a composite material and its use in desulfurization.

[0008] The inventors of the present disclosure have discovered that the activated carbon composite material, prepared by selecting the specific elements and blending and kneading the raw materials with a specific proportion and calcinating the mixture, can significantly improve the desulfurization rate and sulfur breakthrough capacity of the composite material. Therefore, in order to achieve the above objects, a first aspect of the present disclosure provides a composite material, comprising activated carbon, alkali metal oxides, silicon oxides, iron oxides, and rare earth element oxides, wherein the weight ratio between the activated carbon, iron oxides and rare earth element oxides is 100 : (0.5-5) : (1-10), and the composite material satisfies the following formula I: [0009]


in formula I:

M1 represents the weight content of activated carbon in the composite material;

M2 represents the weight content of alkali metal oxides in the composite material;

M3 represents the weight content of silicon oxides in the composite material;

M4 represents the weight content of iron oxides in the composite material;

M5 represents the weight content of oxides of rare earth elements other than cerium in the composite material.



[0009] A second aspect of the present disclosure provides a method of preparing a composite material, the method comprises the following steps:
  1. (1) Blending, kneading, molding, drying, and calcinating activated carbon, alkali metal precursor, silicon-containing binder, and optional pore-enlarging agent in the presence of a solvent to obtain the modified activated carbon;
  2. (2) Contacting a precursor of an auxiliary agent with the modified activated carbon to load the modified activated carbon with the auxiliary agent, wherein the precursor of the auxiliary agent comprises a precursor of iron and a precursor of a rare earth element, an used amount of the precursor of the auxiliary agent causes that a weight ratio of activated carbon, iron element and rare earth element in the composite material is 100: (0.5-5): (1-10);


[0010] Wherein the used amounts of the precursor of the alkali metal and the silicon-containing binder enable that the weight content of the activated carbon, alkali metal element, silicon element, iron element and rare earth element in the composite material satisfies Formula I, and the weights of the alkali metal element, silicon element, iron element and rare earth element are based on the oxides.

[0011] A third aspect of the present disclosure provides an use of the aforementioned composite material in adsorption desulfurization.

[0012] A fourth aspect of the present disclosure provides a system with a desulfurization function, the system comprises:

an oxidation unit for treating sulfur-containing gas and recovering sulfur;

a hydrogenation purification unit, which is connected with the oxidation unit for subjecting the oxidation tail gas from the oxidation unit to hydrogenation reduction and recovering hydrogen sulfide in the reduced product obtained from the hydrogenation reduction;

an incineration unit for incinerating the purified tail gas discharged from the hydrogenation purification unit;

an adsorption unit for adsorbing SO2 from the SO2-containing flue gas obtained by incineration, wherein the adsorbent used in the adsorption unit is the aforementioned composite material.



[0013] A fifth aspect of the present disclosure provides a method for desulfurization, the method comprises the following steps:
  1. (a) oxidizing the sulfur-containing gas to be treated and recovering the sulfur;
  2. (b) subjecting the oxidized tail gas to hydrogenation reduction and recovering hydrogen sulfide from the reduction product obtained from the hydrogenation reduction;
  3. (c) incinerating the tail gas obtained after the hydrogenation reduction;
  4. (d) contacting the incinerated SO2-containing flue gas with a sorbent to adsorb SO2, the sorbent is the aforementioned composite material.


[0014] The advantages of the present disclosure over the prior art are as follows:
  1. (1) The composite material prepared with the modified activated carbon of the present disclosure has a high saturated sulfur capacity and sulfur breakthrough capacity when the composite material is used as an adsorbent. The composite material has a specific surface area more than 550m2/g and a pore volume more than 0.35ml/g, which ensures that the composite material has desirable adsorbability, and a saturated sulfur capacity equal to or greater than 15%, a sulfur capacity (sulfur breakthrough capacity) more than 12% when the removal rate of SO2 is lowered to 99%, and a long total time used for reaching the sulfur breakthrough capacity.
  2. (2) The composite prepared with the modified activated carbon of the present disclosure has desired regeneration properties.
  3. (3) The composite prepared with the modified activated carbon of the present disclosure has a simple preparation process, and the preparation process does not bring about the secondary pollution.
  4. (4) The composite prepared with the modified activated carbon of the present disclosure can promote development of the dry process desulfurization techniques, and provide a clean, secondary pollution-free, environmentally friendly process for the treatment of sulfur-containing waste gas.

BRIEF DESCRITION OF THE DRAWINGS



[0015] 

Figure 1 illustrates a schematic structure diagram of a system according to a preferred embodiment of the present disclosure;

Figure 2 illustrates a schematic structure diagram of a system according to another preferred embodiment of the present disclosure.


DESCRIPTION OF REFERNCE SIGNS



[0016] 

11 Thermal reaction furnace

12 First stage condenser

13 Primary catalytic converter

14 Second stage condenser

15 Secondary catalytic converter

16 Third stage condenser

17 Liquid sulfur pool

21 Hydrogenation reactor

22 Hydrogenation tail gas cooler

23 Quench tower

24 Absorption tower

31 Incineration unit

41 First absorption tower

42 Second absorption tower

111 Tail gas reheater

222 Flue gas heat exchanger


DETAILED DESCRPITION



[0017] The terminals and any value of the ranges disclosed herein are not limited to the precise ranges or values, such ranges or values shall be comprehended as comprising the values adjacent to the ranges or values. As for numerical ranges, the endpoint values of the various ranges, the endpoint values and the individual point value of the various ranges, and the individual point values may be combined with one another to produce one or more new numerical ranges, which should be deemed have been specifically disclosed herein.

[0018] Unless otherwise specified in the present disclosure, the volume of gas is expressed with the volume under the standard temperature and pressure (STP, i.e., under the temperature of 0°C or 273K and a pressure of 1.01×105 Pa); the term "silicon-aluminum ratio" means the molar ratio between the silicon element and the aluminum element; the term "ppm or parts per million" is the unit of volume concentration; the pressure refers to the gauge pressure. The term "saturated sulfur capacity" means the maximum amount of sulfur that can be absorbed per unit weight of the desulfurizing agent, that is, the fresh adsorbent is continuously contacted with the sulfur-containing gas, the saturated sulfur capacity is exactly the weight percentage of the sulfur content adsorbed by the adsorbent relative to the adsorbent when the sulfur content of the sulfur-containing gas before the contact with the adsorbent is equal to the sulfur content of the sulfur-containing gas after the contact with the adsorbent. The term "sulfur breakthrough capacity" refers to the weight percentage of sulfur that can be absorbed by the adsorbent when the process purge degree index (removal rate is reduced to 99%) is ensured under the conditions consisting of a gas volume hourly space velocity of 1,750h-1 and a reaction temperature of 120°C.

[0019] The present disclosure provides a modified activated carbon, it is characterized in that the modified activated carbon comprises activated carbon, alkali metal oxides and silicon oxides, wherein a weight ratio between the activated carbon, the alkali metal oxides and the silicon oxides is 100: (0.2-3): (0.8-5).

[0020] According to the modified activated carbon of the present disclosure, the weight ratio between the activated carbon and the alkali metal oxides is preferably 100: (0.5-2), such as 100:0.5, 100:0.6, 100:1, 100:1.2, 100:1.5, 100:1.7, 100:1.8, 100:2, or any value between the above-mentioned numerical values.

[0021] According to the modified activated carbon of the present disclosure, the weight ratio between the activated carbon and the silicon oxides is preferably 100: (1-2.8), such as 100:1, 100:1.5, 100:1.6, 100:1.7, 100:2, 100:2.2, 100:2.5, 100:2.8, or any value between the above-mentioned numerical values.

[0022] According to the present disclosure, the alkali metal oxides may be oxides of the commonly used alkali metal with different valence states (e.g., lithium, sodium, potassium), especially the oxides obtained by subjecting a precursor of the commonly used alkali metal to the high temperature calcination. Preferably, the alkali metal oxides are K2O and/or Na2O.

[0023] According to the present disclosure, the silicon oxides may be the oxides of the commonly used silicon with different valence states, in particular the oxides obtained by subjecting a precursor of the commonly used silicon to the high temperature calcination. Preferably, the silicon oxide is SiO2.

[0024] According to preferred embodiments of the present disclosure, the modified activated carbon has a specific surface area equal to or larger than 600m2/g, more preferably of 650-750m2/g.

[0025] According to a preferred embodiment of the present disclosure, the modified activated carbon has a pore volume equal to or larger than 0.4ml/g, more preferably 0.4-0.45ml/g.

[0026] The present disclosure provides a method for preparing modified activated carbon, wherein the method comprises the following steps: blending and kneading, molding, drying, and calcinating activated carbon, alkali metal precursor, silicon-containing binder, and an optional pore-enlarging agent in the presence of a solvent; the used amounts of the activated carbon, the alkali metal precursor and the silicon-containing binder cause that the weight ratio between the activated carbon, the alkali metal precursor and the silicon-containing binder in the modified activated carbon is 100: (0.2-3): (0.8-5), wherein the weights of the alkali metal element and the silicon element are based on the oxides.

[0027] According to the method for preparing modified activated carbon of the present disclosure, the used amounts of the activated carbon and the alkali metal precursor cause that the weight ratio between the activated carbon and the alkali metal element in the modified activated carbon is preferably 100: (0.5-2).

[0028] According to the method for preparing modified activated carbon of the present disclosure, the used amounts of the activated carbon and the silicon-containing binder cause that the weight ratio between the activated carbon and the silicon element in the modified activated carbon is preferably 100: (1-2.8).

[0029] According to the method of preparing a modified activated carbon of the present disclosure, the activated carbon may be a variety of commonly used activated carbons, preferably the activated carbons have a specific surface area equal to or larger than 700m2/g, more preferably 700-1,000m2/g.

[0030] According to the method of preparing a modified activated carbon of the present disclosure, the alkali metal precursor is not specifically limited, the precursor may be various common alkali metal-containing water-soluble compounds, preferably, the alkali metal precursor is at least one of a bicarbonate salt of the alkali metal, a carbonate salt of the alkali metal, a nitrate salt of the alkali metal and a sulfate salt of the alkali metal, and more preferably, at least one of sodium bicarbonate, potassium bicarbonate, sodium carbonate and potassium carbonate.

[0031] The method for preparing a modified activated carbon of the present disclosure does not impose the particular requirement on the silicon-containing binder, it is preferably silica and/or silicate, more preferably silica sol and/or water glass. It is well-known among those skilled in the art that water glass generally means an aqueous solution of sodium silicate (Na2O.nSiO2), thus it can provide Si as a silicon-containing binder or provide Na as a precursor for alkali metals, in this case, the total used amount of water glass and a precursor for alkali metals (sodium) enables that the content of Na2O in the prepared product is within the above-mentioned range.

[0032] According to the method for preparing modified activated carbon of the present disclosure, the pore-enlarging agent is a selectively used substance, an use of the pore-enlarging agent can further increase the specific surface area of the modified activated carbon. The used amount of the pore-enlarging agent is not particularly defined, but preferably, the weight ratio of the activated carbon to the pore-enlarging agent is 100: (1-10).

[0033] According to the method for preparing modified activated carbon of the present disclosure, the pore-enlarging agent may be a variety of existing pore-enlarging agents, preferably, the pore-enlarging agent is a decomposable substance at a temperature of not higher than 450°C. More preferably, the pore-enlarging agent is at least one of sesbania powder, polyethylene glycol, cellulose, starch and citric acid.

[0034] The method for preparing modified activated carbon of the present disclosure does not impose a special requirement on the drying mode, but for the sake of further improving the properties of the obtained modified activated carbon, the drying process is performed by a multi-stage drying method. Preferably, the drying process is performed by initially drying at 40-80°C for 2-4h, and then drying at 100-160°C (preferably 110-130°C) for 4-6h.

[0035] The method for preparing modified activated carbon of the present disclosure does not impose special requirement on the calcination conditions, it is preferable that the calcination conditions comprise a calcination temperature within the range of 400-700°C, more preferably 450-600°C. Still preferably, the calcination conditions further comprise the calcination time within the range of 3-8h, more preferably 4-6h.

[0036] The method for preparing the modified activated carbon of the present disclosure does not impose a special requirement on the solvent, which may be a commonly used organic solvent and/or an inorganic solvent. However, it is preferable that the solvent is water. Those skilled in the art can control the dosage of the solvent according to the requirements of blending, kneading and molding, the relevant content will not be further described herein.

[0037] According to the method for preparing modified activated carbon of the present disclosure, the blending, kneading and molding may be performed in a conventional manner, for example, by means of a molding apparatus, such as a strip extruder.

[0038] The present disclosure also provides a modified activated carbon prepared with the aforementioned method.

[0039] According to an embodiment of the present disclosure, the present disclosure provides a composite material, wherein the composite material comprises activated carbon, alkali metal oxides, silicon oxides, iron oxides, and rare earth element oxides, wherein the weight ratio between the activated carbon, iron oxides and rare earth element oxides is 100 : (0.5-5) : (1-10), and the composite material satisfies the following formula I: [0077]



[0040] In formula I:

M1 represents the weight content of activated carbon in the composite material;

M2 represents the weight content of alkali metal oxides in the composite material;

M3 represents the weight content of silicon oxides in the composite material;

M4 represents the weight content of iron oxides in the composite material;

M5 represents the weight content of oxides of rare earth elements other than cerium in the composite material.



[0041] In the present disclosure, the content of the alkali metal oxides is calculated based on the monovalent metal oxide; the content of the silicon oxides is calculated based on SiO2; the content of the iron oxides is calculated based on Fe2O3; among the oxides of the rare earth elements, the content of the cerium oxide is based on CeO2, and the content of the oxide of the rare earth elements other than cerium is calculated based on the trivalent metal oxide.

[0042] According to this embodiment of the present disclosure, the composite material may be prepared by subjecting all the precursors to blending and mixing, molding, drying and calcination. In this embodiment, the composite has a specific surface area preferably equal to or larger than 560m2/g, more preferably within a range of 570-600m2/g. Preferably, the composite material has a pore volume equal to or larger than 0.38ml/g, more preferably 0.38-0.42ml/g. Preferably, the composite material has a saturated sulfur volume equal to or larger than 15%, more preferably 18-20%. Preferably, the composite material has a sulfur breakthrough capacity equal to or larger than 12%, more preferably 12-15%. Preferably, the pore volume of the pores having a pore size below 3nm accounts for 80% or more of the total pore volume of the composite material, more preferably, the pore volume of the pores having a pore size below 3nm accounts for 80-88% of the total pore volume of the composite material. Preferably, the pore volume of the pores having a pore size below 1nm accounts for 5-10% of the total pore volume of the composite material; the pore volume of the pores having a pore size within a range of 1-2nm accounts for 40-55% of the total pore volume; the pore volume of the pores having a pore size larger than 2nm and equal to or less than 3nm accounts for 25-35% of the total pore volume. The pore volume of the pores having a pore size larger than 3nm accounts for 12-20% of the total pore volume of the composite material.

[0043] According to another embodiment of the present disclosure, there is provided a composite material, it is characterized in that the composite material comprises modified activated carbon and an auxiliary agent supported on the modified activated carbon, wherein the modified activated carbon comprises activated carbon, alkali metal oxides and silicon oxides; the auxiliary agent comprises iron oxides and rare earth element oxides, a weight ratio between the activated carbon, iron oxides and rare earth element oxides is 100: (0.5-5): (1-10), and the composite material satisfies the following formula I: [0087]



[0044] In formula I:

M1 represents the weight content of activated carbon in the composite material;

M2 represents the weight content of alkali metal oxides in the composite material;

M3 represents the weight content of silicon oxides in the composite material;

M4 represents the weight content of iron oxides in the composite material;

M5 represents the weight content of oxides of rare earth elements other than cerium in the composite material.



[0045] According to the embodiment of the present disclosure, the modified activated carbon may be initially prepared, the auxiliary agent is then loaded on the modified activated carbon to prepare the composite material. In this embodiment, the composite has a specific surface area preferably equal to or larger than 550m2/g, more preferably within a range of 560-590m2/g. Preferably, the composite material has a pore volume equal to or larger than 0.35ml/g, more preferably 0.36-0.40ml/g. Preferably, the composite material has a saturated sulfur volume equal to or larger than 18%, more preferably 20-25%. Preferably, the composite material has a sulfur breakthrough capacity equal to or larger than 12%, more preferably 15.5-16%. Preferably, the pore volume of the pores having a pore size below 3nm accounts for 80% or more of the total pore volume of the composite material, more preferably, the pore volume of the pores having a pore size below 3nm accounts for 80-88% of the total pore volume of the composite material. Preferably, the pore volume of the pores having a pore size below 1nm accounts for 5-10% of the total pore volume of the composite material; the pore volume of the pores having a pore size within a range of 1-2nm accounts for 40-55% of the total pore volume; the pore volume of the pores having a pore size larger than 2nm and equal to or less than 3nm accounts for 25-35% of the total pore volume. The pore volume of the pores having a pore size larger than 3nm accounts for 12-20% of the total pore volume of the composite material.

[0046] According to the composite material of the present disclosure, the weight ratio between the activated carbon and the alkali metal oxides may be 100: (0.2-3), preferably 100: (0.5-2), such as 100:0.5, 100:0.6, 100:1, 100:1.2, 100:1.5, 100:1.7, 100:1.8, 100:2 or any value between the above-mentioned numerical values.

[0047] According to the composite material of the present disclosure, the weight ratio between the activated carbon and the silicon oxides may be 100: (0.8-5), preferably 100: (1-2.8), such as 100:1, 100:1.5, 100:1.6, 100:1.7, 100:2, 100:2.2, 100:2.5, 100:2.8 or any value between the above-mentioned numerical values.

[0048] According to the composite material of the present disclosure, the weight ratio between the activated carbon and the iron oxides is preferably 100: (1-2.2), such as 100:1, 100:1.5, 100:1.7, 100:2, 100:2.1, 100:2.2 or any value between the above-mentioned numerical values.

[0049] According to the composite material of the present disclosure, a weight ratio between the activated carbon and rare earth element oxides is preferably 100: (2-5), such as 100:2, 100:2.2, 100:2.5, 100:3, 100:3.5, 100:3.8, 100:4, 100:4.5, 100:5 or any value between the above-mentioned numerical values.

[0050] According to the composite material of the present disclosure, the alkali metal oxides may be oxides of the commonly used alkali metal with different valence states (e.g., lithium, sodium, potassium), especially the oxides obtained by subjecting a precursor of the commonly used alkali metal to the high temperature calcination. Preferably, the alkali metal oxides are K2O and/or Na2O.

[0051] According to the composite material of the present disclosure, the silicon oxides may be the oxides of the commonly used silicon with different valence states, in particular the oxides obtained by subjecting a precursor of the commonly used silicon to the high temperature calcination. Preferably, the silicon oxide is SiO2.

[0052] According to the composite material of the present disclosure, the iron oxides may be the oxides of the commonly used iron with different valence states, in particular the oxides obtained by subjecting a precursor of the commonly used iron to the high temperature calcination. Preferably, the iron oxide is Fe2O3.

[0053] According to the composite material of the present disclosure, rare earth element oxides may be oxides of the commonly used rare earth element of different valence, such as lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), yttrium (Y), and scandium (Sc), particularly the oxides obtained by subjecting a precursor of the commonly used rare earth element to the high temperature calcination. Preferably, the rare earth element oxides are CeO2 and/or La2O3. Further preferably, rare earth element oxides are CeO2 and La2O3, and the weight ratio of CeO2 to La2O3 is within a range of 1-3. The adsorption property of the composite material can be further improved by selecting the preferred rare earth element oxides.

[0054] According to preferred embodiments of the present disclosure, the modified activated carbon has a specific surface area equal to or larger than 600m2/g, more preferably of 650-750m2/g.

[0055] According to a preferred embodiment of the present disclosure, the modified activated carbon has a pore volume equal to or larger than 0.4ml/g, more preferably 0.4-0.45ml/g.

[0056] According to a preferred embodiment of the present disclosure, the modified activated carbon or composite material of the present disclosure does not contain a detectable amount of Y, Cu, Al, Ni, Mn, Co, Zn, Mg, V, Zr, Ti or Mo. More preferably, the modified activated carbon or composite material of the present disclosure is only composed of the aforementioned ingredients.

[0057] According to an embodiment, the present disclosure provides a method of preparing a composite, it is characterized in that the method comprises the following steps: blending and kneading, molding, drying and calcinating the activated carbon, alkali metal precursor, silicon-containing binder, iron precursor, rare earth element precursor, and optional pore-enlarging agent in the presence of a solvent, the used amounts cause that the weight ratio of the activated carbon, the iron precursor and the rare earth element precursor is 100: (0.5-5): (1-10), wherein the used amounts of the alkali metal precursor and the silicon-containing binder cause that the weight content of the activated carbon, the alkali metal, the silicon element, the iron element and the rare earth element in the composite material satisfies formula I, wherein the weights of the alkali metal element, the silicon element, the iron element, and the rare earth element are based on the oxides thereof. In the embodiment, the drying mode is preferably carried out by initially drying at 40-80°C for 2-4h, and subsequently drying at 100-160°C (more preferably 110-130°C) for 4-6h. Preferably, the calcination conditions comprise a calcination temperature within the range of 400-700°C, and more preferably 450-600°C. Preferably, the calcination conditions further comprise a calcination time of 3-8h, and more preferably 4-6h.

[0058] According to another embodiment of the present disclosure the present disclosure provides a method of preparing a composite material, it is characterized in that the method comprises the following steps:
  1. (1) Blending and kneading, molding, drying, and calcinating activated carbon, alkali metal precursor, silicon-containing binder, and optional pore-enlarging agent in the presence of a solvent to obtain the modified activated carbon;
  2. (2) Contacting a precursor of an auxiliary agent with the modified activated carbon to load the modified activated carbon with the auxiliary agent, wherein the precursor of the auxiliary agent comprises a precursor of iron and a precursor of a rare earth element, an used amount of the precursor of the auxiliary agent causes that a weight ratio of activated carbon, iron element and rare earth element in the composite material is 100: (0.5-5): (1-10);


[0059] Wherein the used amounts of the precursor of the alkali metal and the silicon-containing binder enable that the weight content of the activated carbon, alkali metal element, silicon element, iron element and rare earth element in the composite material satisfies Formula I, and the weights of the alkali metal element, silicon element, iron element and rare earth element are based on the oxides.

[0060] In step (1) of the embodiment, the drying mode is preferably performed by initially drying at 40-80°C for 2-4h, and then drying at 100-160°C (more preferably 110-130°C) for 4-6h. Preferably, the calcination conditions comprise a calcination temperature within the range of 400-700°C, more preferably 450-600°C. The calcination conditions further comprise the calcination time within the range of 3-8h, more preferably 4-6h.

[0061] In step (2) of the embodiment, the molecular sieve composite may be loaded with an auxiliary agent by adopting the conventional method, the mode of loading the modified activated carbon with an auxiliary agent is preferably that impregnating the modified activated carbon with a solution of a precursor containing the auxiliary agent by means of an equal volume impregnation, drying the impregnated product, and calcinating the dried product.

[0062] More preferably, the conditions of equal volume impregnation comprise a temperature within the range of 5-40°C, further preferably 20-30°C. More preferably, the conditions of equal volume impregnation further comprise a time within the range of 20min-3h, further preferably 0.5-1h.

[0063] More preferably, the conditions of drying the impregnated product include a temperature within the range of 80-160°C, more preferably 110-130°C. More preferably, the conditions of drying the impregnated product further comprise a time within the range of 2-10h, more preferably 4-6h.

[0064] More preferably, the conditions of calcinating the dried product comprise a calcination temperature within the range of 300-500°C, further preferably 350-450°C. More preferably, the conditions of calcinating the dried product further comprise a calcination time within the range of 2-10h, further preferably 3-5h.

[0065] According to the method of the present disclosure, the used amounts of the activated carbon and the alkali metal precursor cause that the weight ratio between the activated carbon and the alkali metal element in the composite material may be 100: (0.2-3), preferably 100: (0.5-2), such as 100:0.5, 100:0.6, 100:1, 100:1.2, 100:1.5, 100:1.7, 100:1.8, 100:2 or any value between the above-mentioned numerical values.

[0066] According to the method of the present disclosure, the used amounts of the activated carbon and the silicon-containing binder cause that the weight ratio between the activated carbon and the silicon element in the composite material can be 100: (0.8-5), preferably 100: (1-2.8), such as 100:1, 100:1.5, 100:1.6, 100:1.7, 100:2, 100:2.2, 100:2.5, 100:2.8 or any value between the above-mentioned numerical values.

[0067] According to the method of the present disclosure, the used amounts of the activated carbon and the iron precursor cause that the weight ratio between the activated carbon and the iron element in the composite material is preferably 100: (1-2.2), such as 100:1, 100:1.5, 100:1.7, 100:2, 100:2.1, 100:2.2, or any value between the above-mentioned numerical values.

[0068] According to the method of the present disclosure, the used amounts of the activated carbon and the rare earth element precursor cause that the weight ratio between the activated carbon and the rare earth element in the composite material is preferably 100: (2-5), such as 100:2, 100:2.2, 100:2.5, 100:3, 100:3.5, 100:3.8, 100:4, 100:4.5, 100:5, or any value between the above-mentioned numerical values.

[0069] According to the method of preparing a composite material of the present disclosure, the activated carbon may be a variety of commonly used activated carbons, preferably the activated carbons have a specific surface area equal to or larger than 700m2/g, more preferably 700-1,000m2/g.

[0070] The method for preparing a composite material of the present disclosure does not impose special limitation to the alkali metal precursor, the precursor may be various common alkali metal-containing water-soluble compounds, preferably, the alkali metal precursor is at least one of a bicarbonate of the alkali metal, a carbonate of the alkali metal, a nitrate of the alkali metal and a sulfate of the alkali metal, and more preferably, at least one of sodium bicarbonate, potassium bicarbonate, sodium carbonate and potassium carbonate.

[0071] The method for preparing a composite material of the present disclosure does not impose the particular requirement on the silicon-containing binder, it is preferably silica and/or silicate, more preferably silica sol and/or water glass. It is well-known among those skilled in the art that water glass generally means an aqueous solution of sodium silicate (Na2O·nSiO2), thus it can provide Si as a silicon-containing binder or provide Na as a precursor for alkali metals, in this case, the total used amount of water glass and a precursor for alkali metals (sodium) enables that the content of Na2O in the prepared product is within the above-mentioned range.

[0072] According to the method for preparing a composite material of the present disclosure, the pore-enlarging agent is a selectively used substance, an use of the pore-enlarging agent can further increase the specific surface area of the modified activated carbon. The used amount of the pore-enlarging agent is not particularly defined, but preferably, the weight ratio of the activated carbon to the pore-enlarging agent is 100: (1-10).

[0073] According to the method for preparing a composite material of the present disclosure, the pore-enlarging agent may be a variety of existing pore-enlarging agents, preferably, the pore-enlarging agent is a decomposable substance at a temperature of not higher than 450°C. More preferably, the pore-enlarging agent is at least one of sesbania powder, polyethylene glycol, cellulose, starch and citric acid.

[0074] According to the method of preparing a composite material of the present disclosure, the iron precursor may be a variety of commonly used iron-containing water-soluble compounds. Preferably, the iron precursor is a soluble iron salt, preferably ferric nitrate and/or ferric chloride.

[0075] According to the method of preparing a composite material of the present disclosure, the rare earth element precursor may be a variety of the existing water-soluble compounds containing a rare earth element, preferably, the rare earth element precursor is a soluble salt of a rare earth metal, more preferably a nitrate of a rare earth metal and/or a chloride of a rare earth metal.

[0076] Further preferably, the rare earth element precursor comprises a precursor of cerium and a precursor of lanthanum, and the used amounts of the precursor of cerium and the precursor of lanthanum cause that the weight ratio of the cerium element to the lanthanum element in the composite material is within a range of 1-3. As previously mentioned, the precursor of cerium is preferably cerium nitrate and/or cerium chloride; the precursor of lanthanum is preferably lanthanum nitrate and/or lanthanum chloride.

[0077] The method of preparing a composite material of the present disclosure does not impose a special requirement on the solvent, which may be a commonly used organic solvent and/or an inorganic solvent. However, it is preferable that the solvent is water. Those skilled in the art can control the dosage of the solvent according to the requirements of blending, kneading and molding, the relevant content will not be further described herein.

[0078] According to the method of preparing a composite material of the present disclosure, the blending, kneading and molding may be performed in a conventional manner, for example, by means of a molding apparatus, such as a strip extruder.

[0079] The present disclosure also provides a composite prepared with the aforementioned method.

[0080] The present disclosure further provides an use of the aforementioned modified activated carbon or composite material in adsorption desulfurization, particularly in adsorption desulfurization of the samples having a low sulfur content, such as the gas samples having a sulfur dioxide content no more than 0.2vol.% (i.e., 6,000mg/m3), e.g., the flue gas.

[0081] The present disclosure further provides a desulfurization method, the method comprises: contacting the sulfur-containing gas to be treated with the aforementioned composite material;
Alternatively, the method comprises: preparing a composite material according to the aforementioned method; then contacting the sulfur-containing gas with the produced composite material.

[0082] The desulfurization method according to the present disclosure is particularly suitable for removal of sulfur contained in samples having a relatively low sulfur content, therefore, the sulfur dioxide content of the sulfur-containing gas is preferably not greater than 0.2vol.%. On the other hand, when the sulfur dioxide content of the sulfur-containing gas is greater than 0.2vol.%, the method preferably further comprises a step of reducing the sulfur dioxide content of the sulfur-containing gas to below 0.2vol.% prior to contacting it with the composite material.

[0083] The desulfurization method of the present disclosure does not impose the special requirements on the contacting conditions, but the contacting conditions preferably include a temperature of 100-150°C. It is Preferable that the contacting conditions further include a gas volume hourly space velocity within a range of 1,500-2,000h-1.

[0084] According to the present disclosure, the composite material not only has desirable adsorbability, but also has excellent regeneration properties. Therefore, the method further comprises regenerating the composite material. The present disclosure does not impose the special requirements on the regeneration method, for example, the regeneration mode may be thermal regeneration and/or water wash regeneration. The composite material of the present disclosure may be subjected to the thermal regeneration and/or water wash regeneration under the conventional conditions.

[0085] More preferably, the thermal regeneration mode is carried out by a gas purge, the conditions of gas purge comprise a gas volume hourly space velocity within a range of 1,000-1,500h-1, a temperature of 150-250°C, and the purge gas is a non-reactive gas or an inert gas(e.g., nitrogen).

[0086] More preferably, the conditions of water wash regeneration comprise a liquid hourly space velocity within a range of 0.5-1.5 h-1 and a temperature of 25-40°C.

[0087] According to the desulfurization method of the present disclosure, the sulfur-containing gas is at least one of the heating furnace exhaust gas of the petroleum refining industry, sulfur tail gas and catalytic cracking regenerative flue gas.

[0088] The present disclosure also provides a system with a desulfurization function, wherein the system comprises:

an oxidation unit for treating sulfur-containing gas and recovering sulfur;

a hydrogenation purification unit, which is connected with the oxidation unit for subjecting the oxidation tail gas from the oxidation unit to hydrogenation reduction and recovering hydrogen sulfide in the reduced product obtained from the hydrogenation reduction;

an incineration unit for incinerating the purified tail gas discharged from the hydrogenation purification unit;

an adsorption unit for adsorbing SO2 from the SO2-containing flue gas obtained by incineration, wherein the adsorbent used in the adsorption unit is the aforementioned composite material



[0089] In accordance with the system of the present disclosure, in order to facilitate regeneration of the composite material in the adsorption unit, the adsorption unit comprises an inlet and an outlet of substance used for regeneration, thereby facilitating introduction of the substance used for regeneration (heat source or washing water) into the adsorption unit for regenerating the composite material. It is preferably that the adsorption unit is further connected with the oxidation unit, such that the SO2-containing regeneration gas obtained from regeneration is returned to the oxidation unit and subjected to retreatment.

[0090] In order to achieve continuous operation of the system according to the present disclosure, it is preferable that the adsorption unit comprises at least two adsorption towers (e.g., a first adsorption tower 41 and a second adsorption tower 42) for an alternate use to continuously adsorb SO2 in the SO2-containing flue gas obtained from the incineration. When the composite material is regenerated by means of the thermal regeneration, as shown in FIG. 1, the hot gas (e.g., hot nitrogen gas) may be introduced from the bottom of the adsorption tower, the produced regeneration gas is discharged from the top of the adsorption tower, an oxidation unit may be further introduced for performing retreatment. When the composite material is regenerated by means of the water wash regeneration, as shown in FIG. 2, the washing water may be introduced from the top of the adsorption tower, the produced regenerated dilute acid is discharged from the bottom of the adsorption tower, an oxidation unit may be further introduced for carrying out retreatment.

[0091] According to the system of the present disclosure, the oxidation unit may comprise a liquid sulfur pool 17 and a thermal reaction furnace 11, a first stage condenser 12 and a catalytic converter which are connected in sequence, wherein the liquid sulfur pool 17 is connected with the first stage condenser 12 and the catalytic converter so as to collect the cooled liquid sulfur. In order to recover sulfur in a more efficient manner, the oxidation unit preferably comprises a liquid sulfur pool 17 and a thermal reaction furnace 11, a first stage condenser 12, a primary catalytic converter 13, a second stage condenser 14, a secondary catalytic converter 15 and a third stage condenser 16 which are connected in sequence; the liquid sulfur pool 17 is connected with the first stage condenser 12, the second stage condenser 14 and the third stage condenser 16 respectively, so as to collect the cooled liquid sulfur.

[0092] According to the system of the present disclosure, the hydrogenation purification unit may comprise a hydrogenation reactor 21, a hydrogenation tail gas cooler 22, a quench tower 23 and an absorption tower 24 which are connected in sequence. The oxidation tail gas discharged from the oxidation unit is subjected to hydrogenation reduction in the hydrogenation reactor 21, and then cooled in the hydrogenation tail gas cooler 22 and the quench tower 23, and subsequently entered into the absorption tower 24 to absorb hydrogen sulfide in the reduction product.

[0093] According to the system of the present disclosure, the incineration unit may be an incinerator and/or a catalytic incineration reactor.

[0094] According to the system of the present disclosure, the oxidation unit, the hydrogenation purification unit and the incineration unit are used for reducing the content of sulfur in a sulfur-containing gas, which is mainly composed of hydrogen sulfide, the adsorption unit provided with an adsorbent material is used for further reducing the content of sulfur dioxide.

[0095] The present disclosure also provides a method of desulfurization, the method comprises the following steps:
  1. (a) Oxidizing the sulfur-containing gas to be treated and recovering the sulfur;
  2. (b) Subjecting the oxidized tail gas to hydrogenation reduction and recovering hydrogen sulfide from the reduction product obtained from the hydrogenation reduction;
  3. (c) Incinerating the tail gas obtained after the hydrogenation reduction;
  4. (d) Contacting the incinerated SO2-containing flue gas with a sorbent to adsorb SO2, the sorbent is the aforementioned composite material.


[0096] The present disclosure does not impose special requirements on the conditions of contact in step (d), but preferably, the conditions of contact comprise a temperature within the range of 100-150°C. Preferably, the conditions of contact further comprise a gas volume hourly space velocity within the range of 1,500-2,000h-1.

[0097] In accordance with the present disclosure, the composite material not only has desirable adsorbability, but also has excellent regeneration property. Therefore, the method further comprises regenerating the adsorbent. The present disclosure does not impose the special requirements on the regeneration method, for example, the regeneration mode may be thermal regeneration and/or water wash regeneration. The composite material of the present disclosure may be subjected to the thermal regeneration and/or water wash regeneration under the conventional conditions. In order to further ensure zero emission of sulfur, the method also comprises regenerating the adsorbent, and returning the SO2-containing regeneration gas obtained from the regeneration process to step (a) and subjecting to retreatment.

[0098] More preferably, the thermal regeneration mode is carried out by a gas purge, the conditions of gas purge comprise a gas volume hourly space velocity within a range of 1,000-1,500h-1, a temperature of 150-250°C, and the purge gas is a non-reactive gas or an inert gas (e.g., nitrogen).

[0099] More preferably, the conditions of water wash regeneration comprise a liquid hourly space velocity within a range of 0.5-1.5 h-1 and a temperature of 25-40°C.

[0100] Those skilled in the art can select the time of regeneration, as long as the sulfur capacity of the regenerated composite material is recovered to 95% or more of the composite material at its initial condition.

[0101] The present disclosure does not impose special requirement on the oxidation process in step (a), as long as the sulfur-containing gas is subjected to the Claus reaction to obtain sulfur. For example, the oxidation process may comprise the following steps: the sulfur-containing gas is successively subjected to combustion, first stage cooling and catalytic reaction.

[0102] Preferably, the conditions of combustion comprise a temperature within the range of 900-1,400°C and a residence time of 2-3 seconds. In the present disclosure, the term "residence time" refers to the residence time of the sulfur-containing gas in the combustion vessel, i.e. the time for the sulfur-containing gas to pass through the combustion furnace, namely the reaction time of the gas.

[0103] Preferably, the conditions of the first stage cooling cause that a temperature of the cooled gas is within a range of 120-180°C.

[0104] Preferably, the conditions of catalytic reaction comprise: the catalyst is an aluminium oxide-based catalyst and/or a titanium oxide-based catalyst, the gas volume hourly space velocity is within a range of 500-1,000 h-1, and the temperature is within the range of 200-350°C.

[0105] More preferably, the mode of catalytic reactions comprises the primary catalytic reaction, the second stage cooling, the secondary catalytic reaction and the third stage cooling which are carried out in sequence. Further preferably, the conditions for the primary catalytic reaction comprise that the catalyst is an aluminium oxide-based catalyst and/or a titanium oxide-based catalyst, the gas volume hourly space velocity is within a range of 600-800 h-1, and the temperature is within the range of 290-330°C. Further preferably, the conditions for the second stage cooling cause that the temperature of the cooled gas is within a range of 130-160°C. Further preferably, the conditions for the secondary catalytic reaction comprise that the catalyst is an aluminium oxide-based catalyst, the gas volume hourly space velocity is within a range of 600-800h-1, and the temperature is within the range of 220-250°C. Further preferably, the conditions for the third stage cooling cause that the temperature of the cooled gas is within a range of 130-160°C.

[0106] In the present disclosure, the aluminium oxide-based catalyst is composed of Al2O3 as the main ingredient, and has a specific surface area equal to or larger than 350m2/g, a pore volume equal to or larger than 0.45ml/g, the catalyst is commercially available, for example, the catalyst is LS-02 catalyst purchased from the Shandong Qilu Keli Chemical Institute Co., Ltd. The titanium oxide-based catalyst is composed of TiO2 as the main ingredient, and has a specific surface area equal to or larger than 180m2/g, a pore volume equal to or larger than 0.3ml/g, the catalyst is commercially available, for example, the catalyst is LS-981 catalyst purchased from the Shandong Qilu Keli Chemical Institute Co., Ltd.

[0107] According to the present disclosure, the conditions for the hydrogenation reduction in step (b) may comprise that the hydrogenation catalyst is a Co-Mo-based tail gas hydrogenation catalyst, the gas volume hourly space velocity is within the range of 500-1,000h-1, and the temperature is within the range of 220-350°C. Preferably, the mode of recovering the hydrogen sulfide in the reduction product obtained from the hydrogen reduction is as follows: lowering the temperature of the reduction product obtained by the hydrogen reduction to 30-40°C, and using an amine liquid to absorb the hydrogen sulfide in the product after lowering the temperature. The concentration of amine in the amine liquid may be 20-50wt.%. The amine in the amine liquid may be various alcohol amine based desulfurizers, wherein a composite type MethyldiethanolaMine (MDEA) is preferred. The amine liquid may be KMKTS-15 high efficiency desulfurizer commercially available from the Zibo Kaimeike Trade Co., Ltd.

[0108] In the present disclosure, the Co-Mo based tail gas hydrogenation catalyst may be a low temperature hydrogenation catalyst for Claus tail gas, which uses the modified Al2O3 as the carrier, and is composed of active metal ingredients such as cobalt and molybdenum, it has a specific surface area equal to or larger than 200m2/g, and is commercially available, for example, the catalyst is the LSH-02 catalyst purchased from the Shandong Qilu Keli Chemical Institute Co., Ltd. The Co-Mo based tail gas hydrogenation catalyst can also be a specific catalyst for Claus tail gas hydrogenation, which uses the modified Al2O3 as the carrier, and is composed of active metal ingredients such as cobalt and molybdenum, it has a specific surface area equal to or larger than 300m2/g, and is commercially available, for example, the catalyst is the LS-951T catalyst purchased from the Shandong Qilu Keli Chemical Institute Co., Ltd.

[0109] According to the present disclosure, the conditions of incineration in the step (c) may comprise a temperature within the range of 600-800°C and a residence time of 2-3 seconds.

[0110] According to the present disclosure, the incineration in step (c) may be performed with the conventional incineration mode. Preferably, the incineration mode is catalytic incineration. The conditions of the catalytic incineration comprise that the catalyst is a catalytic incineration catalyst containing iron and vanadium, the temperature is within a range of 250-350°C, the gas volume hourly space velocity is within a range of 500-1,000h-1. The specific composition of the catalytic incineration catalyst containing iron and vanadium comprise: Fe2O3 2-8 wt.%, V2O5 1-4 wt.%, and the balance is white carbon black.

[0111] According to the present disclosure, the content of CO2 in the sulfur-containing gas is 3-5%, the content of SO2 is 20-1,000ppm by volume, the content of NOx is 20-150ppm by volume, the content of O2 is 3-5%, the content of H2O is 3-10wt.%.

[0112] According to the present disclosure, the method is implemented in the aforementioned system.

Examples



[0113] The present disclosure will be described in detail with reference to examples. In the following examples:

The activated carbon is purchased from the Suzhou Tan Xuan Feng Activated Carbon, Co., Ltd.;

The alkaline silica sol is commercially available from the Qingdao Zhongneng Silicon Chemical Co., Ltd.;

The polyethylene glycol has a weight average molecular weight within the range of 1,900-2,200, is purchased from Wuxi Yatai United Chemical Co., Ltd.;

The sesbania powder has a weight average molecular weight of 206,000, is purchased from the Lankao County Plant Glue Factory in Henan Province.

Starch has a weight average molecular weight of 55,000, is commercially available from Shandong Hengren Industry and Trade Co., Ltd.

Cellulose is Aqualon hydroxyethylcellulose manufactured by the Ashland Specialty Chemicals Incorporation in the United states of America, it has a weight average of 380,000;

The water glass has a SiO2 content of 26.5wt.%, it is purchased from the Bengbu Jingcheng Chemical Co., Ltd.;

The extruding machine has a model number ZYDJ-30, the manufacture is Zibo Yuecheng Machinery Co., Ltd.;

The method of measuring the elemental composition is X-ray fluorescence method, the specific detection process is in compliance with the National Standard GB/T 30905-2014 of China, the method is used in conjunction with X-ray photoelectron energy spectrum analysis to determine the valence state of the elements; the content of activated carbon is obtained by the combustion method;

The detection methods of pore volume fraction, specific surface area and pore volume are performed with reference to the National Standard GB/T6609.35-2009 of China.


Example 1



[0114] The example served to illustrate the composite material (or adsorbent) of the present disclosure and the preparation method thereof.

[0115] 925g of coconut shell activated carbon having a specific surface area of 906m2/g, 32.67g of sodium bicarbonate having a purity of 99wt.%, and 28g of polyethylene glycol having a purity of 99wt.% were taken, the three compounds were uniformly blended to form the material A.

[0116] 66.67g of alkaline silica sol (with the SiO2 content of 30 wt.%) was weighted, the silica sol was dissolved in 360g of deionized water, the mixture was stirred uniformly and formulated into a binder.

[0117] The binder was added to the material A and was extruded on a strip extruder to obtain the strip-shaped materials having a size of ϕ 3-5mm ×10mm, which was initially subjected to drying at 60°C for 3 hours and then subjected to drying at 120°C for 5 hours, and then subjected to calcination at 550°C for 4 hours, in order to produce a modified activated carbon (or adsorbent carrier), the specific surface area and pore volume of the modified activated carbon were measured, the results were described in Table 4.

[0118] 45.43g ferric nitrate (Fe(NO3)3), 26.58glanthanum nitrate hexahydrate (La(NO3)3·6H2O), 50.45g cerium nitrate hexahydrate (Ce(NO3)3·6H2O) were dissolved in deionized water, the mixture was stirred uniformly to form a stable solution, the impregnation solution of the auxiliary agent is obtained according to the metered volume of the added amount of the adsorbent carrier, the adsorbent carrier was impregnated at 25°C according to an equal volume impregnation method, the impregnation time was 1h, the impregnated material was subjected to drying at 120°C for 6 hours, and calcination at 400°C for 4 hours, the adsorbent was prepared, the elemental composition (in wt.%) of the adsorbent was measured, the measurement results were shown in Table 2, the measurement results of the specific surface area and pore volume of the adsorbent were shown in Table 4.

Examples 2-11



[0119] The adsorbents were prepared according to the same steps and conditions of Example 1, except that the composition, preparation conditions or concentration of the impregnation solution were modified, the specific preparation conditions were illustrated in Table 1. The contents of respective metal oxides and activated carbon (in wt.%) of the finally produced adsorbent products were shown in Table 2, the measurement results of the specific surface area and other parameters were illustrated in Table 4.
Table 1
No. of ExamplesBinderPore-enlarging agentPrecursor of alkali metalDrying of carriersCalcination of carriersImpregnationDrying after impregnationCalcination after impregnati on
Example 2 Silicon sol Polyethylene glycol Sodium bicarbonate 60°C, 3h 120°C, 5h 550°C, 4h 25°C, 1h 120°C, 6h 400°C, 4h
Example 3 Silicon sol Polyethylene glycol Sodium bicarbonate 60°C, 3h 120°C, 5h 550°C, 4h 25°C, 1h 120°C, 6h 400°C, 4h
Example 4 Silicon sol Polyethylene glycol Sodium bicarbonate 60°C, 3h 120°C, 5h 550°C, 4h 25°C, 1h 120°C, 6h 400°C, 4h
Example 5 Silicon sol Polyethylene glycol Sodium bicarbonate 60°C, 3h 120°C, 5h 550°C, 4h 25°C, 1h 120°C, 6h 400°C, 4h
Example 6 Silicon sol Polyethylene glycol Sodium bicarbonate 60°C, 3h 120°C, 5h 550°C, 4h 25°C, 1h 120°C, 6h 400°C, 4h
Example 7 Silicon sol Polyethylene glycol Sodium bicarbonate 60°C, 3h 120°C, 5h 550°C, 4h 25°C, 1h 120°C, 6h 400°C, 4h
Example 8 Water glass Sesbania powder Sodium bicarbonate 80°C, 2h 160°C, 4h 600°C, 3h 35°C, 40min 140°C, 3h 450°C, 2h
Example 9 Water glass Stare h Sodium carbonate 40°C, 7h 100°C, 6h 450°C, 6h 30°C, 1h 110°C, 6h 380°C, 4h
Example 10 Silicon sol Citric acid Sodium carbonate 50°C, 3h 130°C, 4h 500°C, 5h 20°C, 1.5h 80°C, 10h 350°C, 8h
Example 11 Silicon sol Sesba nia powder Potassium bicarbonate 70°C, 2.5h 110°C, 5h 480°C, 5.5h 10°C, 2h 130°C, 4h 420°C, 3h
Table 2
No. of ExamplesNa2OSiO2Fe2O3CeO2La2O3Activated carbonWhether formula I is satisfied
Example 1 1 2 1.5 2 1 92.5 Yes
Example 2 1 2 1 1 1 94 Yes
Example 3 1 2 2 3 1 91 Yes
Example 4 1 1 1.5 2 2 92.5 Yes
Example 5 0.5 2 1.5 2.5 1 92.5 Yes
Example 6 1.5 2.5 1.5 1.5 1.5 91.5 Yes
Example 7 1 1.5 1.5 2 1.5 92.5 Yes
Example 8 1 1 1.5 3 3 90.5 Yes
Example 9 0.5 2 1.5 0.5 1 94.5 Yes
Example 10 (K2O) 1 2 2.5 2 1 91.5 Yes
Example 11 (K2O) 1 2 0.5 2 1 93.5 Yes

Example 12



[0120] The coconut shell activated carbon with a specific surface area of 906m2/g, sodium bicarbonate with a purity of 99wt.%, polyethylene glycol with a purity of 99wt.%, alkaline silica sol (with the SiO2 content of 30 wt.%), iron nitrate, lanthanum nitrate hexahydrate, cerium nitrate hexahydrate and deionized water were mixed; relative to 100g of activated carbon, the used amount of polyethylene glycol was 2g, the used amount of deionized water was 12g; the used amount of other ingredients caused that the weight ratio among the activated carbon, alkali metal elements, silicon element, iron element and rare earth elements in the produced adsorbent was the same as that in Example 1. The produced mixture was extruded and molded on a strip extruder to obtain the strip-shaped materials having a size of 3-5mm×10mm, the materials were initially subjected to drying at 60°C for 3 hours and then subjected to drying at 120°C for 5 hours, and subsequently subjected to calcination at 550°C for 4 hours, such that the adsorbent was produced. The measurement results of the specific surface area of the adsorbent were shown in Table 4.

Example 13



[0121] The coconut shell activated carbon with a specific surface area of 906m2/g, sodium bicarbonate with a purity of 99wt.%, polyethylene glycol with a purity of 99wt.%, alkaline silica sol (with the SiO2 content of 30 wt.%), iron nitrate, lanthanum nitrate hexahydrate, cerium nitrate hexahydrate and deionized water were mixed; relative to 100g of activated carbon, the used amount of polyethylene glycol was 5g, the used amount of deionized water was 12g, the used amount of other ingredients caused that the weight ratio among the activated carbon, alkali metal elements, silicon element, iron element and rare earth elements in the produced adsorbent was the same as in Example 5. The produced mixture was extruded and molded on a strip extruder to obtain the strip-shaped materials having a size of 3-5mm×10mm, the materials were initially subjected to drying at 65°C for 3 hours and then subjected to drying at 110°C for 5 hours, and subsequently subjected to calcination at 530°C for 4 hours, such that the adsorbent was produced. The measurement results of the specific surface area of the adsorbent were shown in Table 4.

Example 14



[0122] The adsorbent was prepared according to the same steps and conditions of Example 1, except that the polyethylene glycol was replaced with an equal weight of cellulose.

Comparative Examples 1-6



[0123] The adsorbents were prepared according to the same steps and conditions of Example 1, except that the concentration of the impregnation solution was modified, such that the contents of the individual metal oxide and activated carbon (in wt.%) of the finally produced adsorbent products were shown in Table 3, the measurement results of the specific surface area and other parameters were shown in Table 4.
Table 3
NumbersNa2OSiO2Fe2O3CeO2La2O3Activated carbonWhether formula I is satisfied
Comparative Example 1 1 2 0 2 1 94 No
Comparative Example 2 1 2 3.5 0 1.5 92 No
Comparative Example 3 1 1 2 3 0 93 No
Comparative Example 4 1 2 1.5 0 0 95.5 Yes
Comparative Example 5 1.5 0 1.5 1.5 1.5 94 No
Comparative Example 6 0 1.5 1.5 2 1.5 93.5 No

Comparative Examples 7-9



[0124] The adsorbents were prepared according to the same steps and conditions of Example 1, except that the iron nitrate was replaced with equal weights of copper nitrate, manganese nitrate and zinc nitrate (calculated based on metal oxides), respectively.

Comparative Example 10



[0125] The adsorbent was prepared according to the same steps and conditions of Example 1, except that the lanthanum nitrate hexahydrate and the cerium nitrate hexahydrate were replaced with equal weight of nickel nitrate (calculated based on metal oxides).

Comparative Example 11



[0126] The adsorbent was prepared according to the same steps and conditions of Example 1, except that the alkaline silica sol was replaced with an equal weight of concentrated sulfuric acid (98 wt.%).

Test example 1



[0127] The adsorption activity evaluation was performed on the adsorbents prepared in the Examples and the Comparative Examples:
The reaction vessel of the micro-reactor was made of stainless steel tubes with an inner diameter of 20mm, the reaction vessel was placed in an incubator. The loading amount of the adsorbent was 10ml, the upper part of the reaction vessel was filled with quartz sand having the same particle size as the adsorbent, the two substances were subjected to mixing and pre-heating. The contents of SO2 in the inlet and outlet gases of the reaction vessel were analyzed by using a morphological sulfur chromatograph produced by the Agilent Technologies China Co., Ltd.

[0128] The operating conditions of chromatograph were as follows:

chromatography column: Agilent 7890B

Detector: Antek 7090 (SCD)

Chromatography column: stainless steel column with a length of 30m, an internal diameter of 0.32mm, a liquid membrane thickness of 4 µm; and a liquid membrane specification PDMS-1

Column temperature: 250°C

Detector temperature: 950°C

Gasification chamber temperature: 275°C

Flow rate of the carrier gas (N2): 90ml/min;

Injection quantity: 1 µL



[0129] The composition of the inlet gas by volume was as follows: CO2 3vol.%, SO2 0.03vol.% (900mg/m3), H2O 3vol.%, the balance was N2, the gas volume hourly space velocity was 1,750H-1, and the reaction temperature was 120°C.

[0130] The removal rate η SO2 of SO2 for the sorbent was calculated according to the following formula:




[0131] Wherein N0 and N1 represented the volumetric concentration of SO2 at the inlet and outlet, respectively.

[0132] The sulfur capacity was calculated according to the following formula:



[0133] Wherein Msulfur represents the weight of sulfur adsorbed by activated carbon and Mcatalyst represents the weight of the adsorbent used for adsorbing sulfur; the saturated sulfur capacity refers to the maximum amount of sulfur that can be absorbed by an unit weight of the desulfurizing agent, that is, the fresh adsorbent was continuously contacted with the sulfur-containing gas, when the sulfur content of sulfur-containing gas before its contact with the adsorbent is equal to the sulfur content of sulfur-containing gas after its contact with the adsorbent, the percentage of the sulfur content adsorbed by the adsorbent relative to the adsorbent was exactly the saturated sulfur capacity.

[0134] Sulfur breakthrough capacity: referred to the weight percent of sulfur that can be adsorbed by the sorbent at certain conditions of use while ensuring the cleanness indicator of the process. In other words, when the sulfur content in the processed gas at an outlet is greater than the purification degree indicator of the process, the entire spent catalyst was immediately removed, the sulfur capacity measured by the samples on average was denoted as the sulfur breakthrough capacity. In the present disclosure, it was deemed to reach the sulfur breakthrough capacity when the SO2 removal rate was reduced to 99%, that, the sulfur breakthrough capacity in the present disclosure referred to the sulfur capacity of the sorbent when the SO2 removal rate was reduced to 99%, the total time of the sorbent in use before achieving the sulfur breakthrough capacity was defined as the time length of adsorption.

[0135] The analysis results were shown in Table 4.
Table 4
 CarriersAdsorbentAdsorption time, hSaturated sulfur capacity, %Sulfur breakthrough capacity, %
Specific surface area, m2/gPore volume, ml/gSpecific surface area, m2/gPore volume, ml/gPore distribution
Percentage of the pore volume of the pores having a pore size below 3nm, %Percentage of the pore volume of the pores having a pore size below lnm, %Percentage of the pore volume of the pores having a pore size within 1-2nm, %
Example 1 678 0.42 572 0.38 87.5 7.5 54.5 142 23.8 15.9
Example 2 692 0.43 580 0.38 86.2 7.2 52.9 138 21.5 15.6
Example 3 665 0.42 562 0.37 87.3 8.8 53.2 140 22.8 15.8
Example 4 670 0.40 582 0.36 85.5 6.7 51.7 137 22.6 15.7
Example 5 659 0.42 569 0.38 87.1 8.1 49.8 136 21.8 15.6
Example 6 681 0.44 581 0.39 86.4 7.9 48.6 138 22.6 15.7
Example 7 652 0.42 558 0.37 85.8 9.2 49.5 139 23.3 15.7
Example 8 648 0.43 578 0.37 81.2 6.5 46.2 112 18.8 12.5
Example 9 669 0.41 588 0.36 80.8 5.9 41.8 110 18.6 12.3
Example 10 652 0.42 568 0.37 84.5 6.5 51.2 128 20.5 14.5
Example 11 663 0.43 572 0.38 85.0 6.8 50.6 122 19.8 14.2
Example 12 - - 591 0.4 82.4 7 47.9 118 19.3 13.1
Example 13 - - 585 0.38 83.1 7.2 48.2 132 20.2 13.5
Example 14 632 0.38 545 0.34 81.5 8.8 44.2 95 14.2 10.1
Comparative Example 1 670 0.43 598 0.4 82.5 12.5 40.2 82 13.5 9.5
Comparative Example 2 672 0.42 610 0.38 78.9 12.5 38.5 86 13.9 9.1
Comparative Example 3 665 0.43 578 0.37 80.8 11.2 37.9 82 14.0 9.4
Comparative Example 4 675 0.42 572 0.37 77.5 9.8 35.9 78 13.4 9.2
Comparative Example 5 651 0.38 545 0.33 81.5 11.5 38.1 102 15.2 10.8
Comparative Example 6 658 0.4 552 0.36 82.1 9.7 37.3 99 14.9 10.2
Comparative Example 7 668 0.42 570 0.38 79.5 12.7 36.2 93 11.9 9.5
Comparative Example 8 671 0.43 559 0.37 77.6 13.5 34.5 78 10.2 8.9
Comparative Example 9 669 0.41 561 0.36 75.8 12.9 35.7 92 12.1 9.2
Comparative Example 10 658 0.43 559 0.38 80.5 15.1 32.5 72 10.9 8.5
Comparative Example 11 662 0.4 562 0.36 78.5 10.2 37.8 93 12.8 9.2
Coconut shell activated carbon - - - - -     45 6.8 5.2


[0136] As can be seen from the results of Table 4, the composite material of the present disclosure had a relatively high saturated sulfur capacity and sulfur breakthrough capacity.

Test example 2



[0137] The adsorbents prepared in Example 1 and Comparative Example 1 were subjected to SO2 removal test (the specific method was the same as that in the Test example 1), when the adsorption of SO2 by the adsorbent had a breakthrough and reached the sulfur breakthrough capacity of the adsorbent, the adsorption of SO2-containing gas was stopped, the regeneration performance of the adsorbent was examined by switching to an introduction of nitrogen gas. The regeneration conditions were that the gas volume hourly space velocity was 1,200h-1, the temperature was 200°C, nitrogen gas was used as the purge gas, and the regeneration time was 6h. The SO2 removal test was carried out by using the regenerated adsorbent, and the adsorbent was subjected to regeneration when the sulfur breakthrough capacity was reached, the adsorbent was continuously regenerated for 5 times. The results of the sulfur breakthrough capacity of the adsorbent in regard to SO2 following each time of regeneration were shown in Table 5.
Table 5
Number of regenerationSulfur breakthrough capacity, %
Example 1Comparative Example 1
1 15.8 9
2 15.8 8.8
3 15.7 8.2
4 15.7 7.5
5 15.7 6.9


[0138] The data in Table 5 demonstrated that the sulfur breakthrough capacity of the adsorbent of the present disclosure remains substantially unchanged, and the composite material of the present disclosure exhibited excellent regeneration performance. The further experiments proved that the regeneration performance of the adsorbents obtained in Examples 2-7 was similar to that of Example 1 (the results were not shown).

Test example 3



[0139] Desulfurization was performed by using the system of the present disclosure, as shown in FIG. 1, the system comprises:

an oxidation unit for treating the sulfur-containing gas and recovering the sulfur, comprising a liquid sulfur pool 17 and a thermal reaction furnace 11, a first stage condenser 12, a primary catalytic converter 13, a second stage condenser 14, a secondary catalytic converter 15 and a third stage condenser 16 which were connected in sequence; the liquid sulfur pool 17 was connected with the first stage condenser 12, the second stage condenser 14 and the third stage condenser 16 respectively, so as to collect the cooled liquid sulfur.

a hydrogenation purification unit, connected with the oxidation unit, for subjecting the oxidation tail gas discharged from the oxidation unit to hydrogenation reduction and recovering hydrogen sulfide in the reduced product obtained from the hydrogenation reduction; the hydrogenation purification unit comprising a hydrogenation reactor 21, a hydrogenation tail gas cooler 22, a quench tower 23 and an absorption tower 24 which were connected in sequence;

an incineration unit 31 for incinerating the purified tail gas discharged from the hydrogenation purification unit;

an adsorption unit for adsorbing SO2 in the SO2-containing flue gas obtained from incineration, the adsorbent used in the adsorption unit was the composite material prepared in the present disclosure, the adsorption unit comprising a first adsorption tower 41 and a second adsorption tower 42, which can be alternately used to achieve continuous adsorption;

a heat exchange unit including a tail gas reheater 111 and a flue gas heat exchanger 222, wherein the tail gas reheater 111 was disposed between the oxidation unit and the hydrogenation purification unit for heating the oxidized tail gas discharged from the oxidation unit, and the flue gas heat exchanger 222 was disposed between the incineration unit and the adsorption unit for lowering temperature of the flue gas generated by the incineration.



[0140] The steps of desulfurization were as follows (the specific operating conditions were shown in Table 6):
  1. (a) Treatment of sulfur-containing gas and recovery of sulfur in an oxidation unit.

    The acid gas containing 85 vol.% hydrogen sulfide (further containing CO2 in an amount of 10 vol.%, hydrocarbon in an amount of 2 vol.%, NH3 in an amount of 3 vol.%) in the thermal reaction unit was partially combusted in the thermal reaction furnace 11 to converting hydrogen sulfide into sulfur dioxide: the reaction was performed at high temperatures, the hydrogen sulfide and the sulfur dioxide performed the Claus reaction to produce elemental sulfur and process gas, the elemental sulfur was cooled by the first stage condenser 12 and delivered to the liquid sulfur pool 17 to produce the liquid sulfur;

    The process gas was passed sequentially into the primary catalytic converter 13, the second stage condenser 14, the secondary catalytic converter 15 and the third stage condenser 16 of the catalytic reaction unit. After subjecting to the Claus catalytic conversion, the elemental sulfur passed through the second stage condenser 14 and the third stage condenser 16 and entered the liquid sulfur pool 17; the reacted Claus tail gas was transported into the tail gas purification unit.

  2. (b) The oxidized tail gas was subjected to hydrogenation reduction and the hydrogen sulfide in the reduction product obtained from the hydrogenation reduction was recovered in the hydrogenation purification unit.
    The Claus tail gas was heated by a tail gas reheater 111 to 236°C and entered the hydrogenation reactor 21, where the sulfur-containing compounds were subjected to hydrogenation and converted to hydrogen sulfide by the action of a hydrogenation catalyst in the hydrogenation reactor 21, the hydrogen sulfide was cooled by a hydrogenation tail gas cooler 22 and a quench tower 23, and entered an absorption tower 24 with an amine solution (high-efficiency desulfurizer with a model name KMKTS-15, purchased from the Zibo Kaimeike Trade Co., Ltd.), the hydrogen sulfide in the tail gas was absorbed to produce the purified tail gas.
  3. (c) The tail gas after the hydrogenation reduction was incinerated in an incineration unit.
    The purified tail gas was introduced into an incineration unit (incinerator) 31 for incineration, producing the SO2-containing flue gas, which was introduced into an adsorption unit.
  4. (d) Contacting the SO2-containing flue gas obtained from the incineration with an adsorbent in an adsorption unit to adsorb SO2
    The flue gas was subjected to a heat exchange with a flue gas heat exchanger 222 and its temperature was decreased to 145°C, the cooled flue gas entered a first absorption tower 41, which was in the adsorbed state. After the SO2 in the flue gas was adsorbed, the flue gas was discharged via a chimney, and the SO2 emission control target of the flue gas was 20mg/m3. In the initial stage of operation, SO2 was not detected in the purified flue gas. After an operation for 650h, the SO2 was present in the flue gas at a low concentration of 1 mg/m3. After continuous operation for 780h, the concentration of SO2 in the flue gas reached 8mg/m3. Following the continuous operation for 900h, the concentration of SO2 in the flue gas reached 20mg/m3. The first absorption tower 41 was switched off, and the second absorption tower 42 was switched on so as to adsorb the incineration tail gas. At the same time, the first absorption tower 41 was subjected to the thermal regeneration by introducing the hot nitrogen gas, the regeneration process produced a regeneration gas containing SO2. The regeneration gas was introduced into the primary catalytic converter 13 and subjected to retreatment. The regeneration time was 100h (relative to the sorbent with a volume of 20m3). When the concentration of SO2 in the flue gas exhausted from the second absorption tower 42 reached 20mg/m3, the regenerated first absorption tower 41 was switched on so as to adsorb the regeneration gas. Finally, the SO2 emission concentration in the sulfur recovery device can be controlled to be less than 20mg/m3 by controlling the adsorption accuracy of 20mg/m3, such that the requirements of reducing the concentration of SO2 in the flue gas to less than 50mg/m3 imposed by the most stringent environmental protection regulations at present was satisfied. Furthermore, the regeneration mode was simple, and the whole treatment process was continuous and clean.

Test example 4



[0141] The desulfurization of acid gas was performed according to the same system and method as those of the Test example 3, except that the incinerator of the incineration unit was replaced with the catalytic incineration reactor, and the regeneration mode was water wash regeneration, as shown in FIG. 2, the water wash regeneration mode was as follows: the washing water was introduced into the first adsorption tower 41 for carrying out the adsorbent regeneration, which brought forth the regenerated dilute acid, the regenerated dilute acid was introduced into the thermal reaction furnace 11 and subjected to retreatment. The regeneration time was 140h. The specific operating conditions for each step were shown in Table 6.
Table 6
 Operating conditionTest example 3Test example 4
Oxidation unit Thermal reaction furnace The temperature was 1,250°C The temperature was 900°C
The residence time was 2s The residence time was 3s
The volume content of sulfur-containing compounds in the process gas at an outlet of the first stage condenser H2S: 7.56%, SO2: 3.78%, organic sulfur: 0.5% H2S: 7.38%, SO2: 3.61%, organic sulfur: 0.6%
Primary catalytic converter Catalyst: aluminium oxide-based catalyst (purchased from Shandong Qilu Keli Chemical institute Co., Ltd., with a brand number LS-02) The gas volume hourly space velocity was 800h-1 The temperature was 306°C Catalyst: titanium oxide-based catalyst (purchased from Shandong Qilu Keli Chemical Institute Co., Ltd., with a brand number LS-981) The gas volume hourly space velocity was 600h-1 The temperature was 290°C
Second stage condenser The outlet temperature was 153°C The outlet temperature was 130°C
Secondary catalytic converter Catalyst: aluminium oxide-based catalyst (purchased from Shandong Qilu Keli Chemical institute Co., Ltd., with a brand number LS-02) The gas volume hourly space velocity was 800h-1 The temperature was 246°C Catalyst: aluminium oxide-based catalyst (purchased from Shandong Qilu Keli Chemical Institute Co., Ltd., with a brand number LS-02) The gas volume hourly space velocity was 600h-1 The temperature was 220°C
Third stage condenser The outlet temperature was 145°C The outlet temperature was 145°C
Volume content of the sulfur-containing compounds in the tail gas H2S: 1.28%, SO2: 0.51%, organic sulfur: 0.05% H2S: 1.52%, SO2: 0.75%, organic sulfur: 0.04%
Hydrogenation purification unit Hydrogenation reactor Catalyst: Co-Mo based tail gas hydrogenation catalyst (purchased from Shandong Qilu Keli Chemical Institute Co., Ltd., with a brand number LSH-02) The gas volume hourly space velocity was 500h-1 The temperature was 236°C Catalyst: Co-Mo based tail gas hydrogenation catalyst (purchased from Shandong Qilu Keli Chemical Institute Co., Ltd., with a brand number LS-951T) The gas volume hourly space velocity was 1,000h-1 The temperature was 350°C
Hydrogenation tail gas cooler The outlet temperature was 145°C The outlet temperature was 155°C
Quench tower The outlet temperature was 38°C The outlet temperature was 32°C
Absorption tower Concentration of the amine solution was 38 wt.% The temperature was 38°C Concentration of the amine solution was 42 wt.% The temperature was 35°C
Volume content of the sulfur-containing compounds in the tail gas H2S: 82ppm, COS: 16ppm, no other sulfur-containing compound was detected H2S: 85ppm, COS: 28ppm, no other sulfur-containing compound was detected
Incineration unit Incinerator The temperature was 700°C, the residence time was 2.5s -
Catalytic incineration reactor - Catalyst: a catalytic incineration catalyst containing iron and vanadium (purchased from Shandong Qilu Keli Chemical Institute Co., Ltd., with a brand number LS-941), the temperature was 300°C, the gas volume hourly space velocity was 800h-1
The SO2 content in the generated flue gas 256mg/m3 305mg/m3
Adsorption unit   Adsorbent: Example 1 The temperature was 150°C The gas volume hourly space velocity was 2,000h-1 The concentration of SO2 in flue gas reached 20mg/m3 when the operation time was 900h Adsorbent: Example 1 The temperature was 100°C gas volume hourly space velocity was 1,500h-1 The concentration of SO2 in flue gas reached 20mg/m3 when the operation time was 820h
Regeneration Thermal regeneration The gas volume hourly space velocity was 1,200h-1 The temperature was 200°C -
Water wash regeneration - The liquid hourly space velocity (LHSV) was 1h-1, the temperature was 26°C

Test example 5



[0142] The desulfurization of acid gas was performed according to the same system and method as those of the Test example 3, except that the temperature of the adsorption unit was 80°C and the gas volume hourly space velocity was 1,000h-1. The concentration of SO2 in the flue gas reached 20mg/m3 after an operation time of 720h.

[0143] The above content describes in detail the preferred embodiments of the present disclosure, but the present disclosure is not limited thereto. A variety of simple modifications can be made in regard to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, including a combination of individual technical features in any other suitable manner, such simple modifications and combinations thereof shall also be regarded as the content disclosed by the present disclosure, each of them falls into the protection scope of the present disclosure.


Claims

1. A composite material, comprising activated carbon, alkali metal oxides, silicon oxides, iron oxides, and rare earth element oxides, wherein the weight ratio between the activated carbon, iron oxides and rare earth element oxides is 100 : (0.5-5) : (1-10), and the composite material satisfies the following formula I:

in formula I:

M1 represents the weight content of activated carbon in the composite material;

M2 represents the weight content of alkali metal oxides in the composite material;

M3 represents the weight content of silicon oxides in the composite material;

M4 represents the weight content of iron oxides in the composite material;

M5 represents the weight content of oxides of rare earth elements other than cerium in the composite material.


 
2. The composite material of claim 1, wherein the pore volume of the pores having a pore size below 3nm accounts for 80% or more of the total pore volume of the composite material.
 
3. The composite material of claim 1, wherein the pore volume of the pores having a pore size below 3nm accounts for 80-88% of the total pore volume of the composite material.
 
4. The composite material of claim 1 or 2, wherein the pore volume of the pores having a pore size below 1nm accounts for 5-10% of the total pore volume of the composite material; the pore volume of the pores having a pore size within a range of 1-2nm accounts for 40-55% of the total pore volume; the pore volume of the pores having a pore size larger than 2nm and equal to or less than 3nm accounts for 25-35% of the total pore volume.
 
5. The composite material of any one of claims 1 to 4, wherein a weight ratio between the activated carbon, alkali metal oxides, silicon oxides, iron oxides, and rare earth element oxides is 100: (0.2-3): (0.8-5): (0.5-5): (1-10), preferably 100: (0.5-2): (1-2.8): (1-2.2): (2-5).
 
6. The composite material of any one of claims 1 to 5, wherein the alkali metal oxide is K2O and/or Na2O, the silicon oxide is SiO2, the iron oxide is Fe2O3, and the rare earth element oxide is CeO2 and/or La2O3.
 
7. The composite material of any one of claims 1 to 6, wherein the rare earth element oxides are CeO2 and La2O3, and the weight ratio of CeO2 and La2O3 is within a range of 1-3.
 
8. The composite material of any one of claims 1 to 7, wherein the composite material has a specific surface area larger than or equal to 550m2/g, a pore volume larger than or equal to 0.35ml/g, a saturated sulfur volume larger than or equal to 15%, and a sulfur breakthrough capacity larger than or equal to 12%.
 
9. The composite material of any one of claims 1 to 8, wherein the composite material has a specific surface area within a range of 560-590m2/g, a pore volume within a range of 0.36-0.4ml/g, a saturated sulfur volume within a range of 20-25%, and a sulfur breakthrough capacity within a range of 15.5-16%.
 
10. The composite material of any one of claims 1 to 9, wherein the composite material does not contain a detectable amount of Y, Cu, Al, Ni, Mn, Co, Zn, Mg, V, Zr, Ti or Mo.
 
11. Use of the composite material of any one of claims 1 to 10 in adsorption desulfurization.
 
12. A system with a desulfurization function, wherein the system comprises:

an oxidation unit for treating sulfur-containing gas and recovering sulfur;

a hydrogenation purification unit, which is connected with the oxidation unit for subjecting the oxidation tail gas from the oxidation unit to hydrogenation reduction and recovering hydrogen sulfide in the reduced product obtained from the hydrogenation reduction;

an incineration unit for incinerating the purified tail gas discharged from the hydrogenation purification unit;

an adsorption unit for adsorbing SO2 from the SO2-containing flue gas obtained by incineration,

wherein the adsorbent used in the adsorption unit is the composite material of any one of claims 1 to 10.


 
13. The system of claim 12, wherein the adsorption unit further comprises an inlet and an outlet of substance used for regeneration, for introducing the substance used for regeneration into the adsorption unit for regenerating the adsorbent, and the adsorption unit is further connected with the oxidation unit, such that the SO2-containing regeneration gas obtained from regeneration is returned to the oxidation unit and subjected to retreatment.
 
14. A method for desulfurization, wherein the method comprises the following steps:

(a) oxidizing the sulfur-containing gas to be treated and recovering the sulfur;

(b) subjecting the oxidized tail gas to hydrogenation reduction and recovering hydrogen sulfide from the reduction product obtained from the hydrogenation reduction;

(c) incinerating the tail gas obtained after the hydrogenation reduction;

(d) contacting the incinerated SO2-containing flue gas with a sorbent to adsorb SO2, the sorbent is the composite material of any one of claims 1 to 10.


 
15. The method of claim 14, wherein the conditions of the contacting in step (d) comprise a temperature within a range of 100-150°C and a gas volume hourly space velocity within a range of 1,500-2,000h-1;

and/or, the method further comprises regenerating the sorbent, and returning the regenerated SO2-containing regeneration gas to step (a) for subjecting to retreatment;

and/or, the method is implemented in the system of claim 12 or 13.


 




Drawing










Search report










Cited references

REFERENCES CITED IN THE DESCRIPTION



This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description