(19)
(11)EP 3 501 640 A1

(12)EUROPEAN PATENT APPLICATION

(43)Date of publication:
26.06.2019 Bulletin 2019/26

(21)Application number: 18202985.0

(22)Date of filing:  26.10.2018
(51)International Patent Classification (IPC): 
B01J 27/185(2006.01)
B01J 27/182(2006.01)
B01J 23/889(2006.01)
B01J 37/02(2006.01)
C10J 3/02(2006.01)
B01J 27/187(2006.01)
B01J 27/043(2006.01)
B01J 37/28(2006.01)
B01J 37/08(2006.01)
B01J 35/10(2006.01)
(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: 20.12.2017 TW 10644822

(71)Applicant: Industrial Technology Research Institute
31040 Hsinchu (TW)

(72)Inventors:
  • KUO, Yen-Ting
    116 Taipei City (TW)
  • WAN, Hou-Peng
    333 Taoyuan City (TW)
  • CHEN, Ju-Shiou
    234 New Taipei City (TW)
  • JUCH, Ching-I
    310 Hsinchu County (TW)
  • HUNG, Wei-Chun
    238 New Taipei City (TW)
  • LIN, Uei-Ting
    220 New Taipei City (TW)

(74)Representative: Michalski Hüttermann & Partner Patentanwälte mbB 
Speditionstraße 21
40221 Düsseldorf
40221 Düsseldorf (DE)

  


(54)CATALYST, METHOD FOR PREPARING THE SAME, AND METHOD FOR PREPARING SYNGAS


(57) A catalyst, a method for preparing the catalyst, and a method for preparing a syngas are provided. The catalyst meets one of the following two conditions (1) and (2):
(1) 4wt%-6wt% of Si, 5wt.%-10wt.% of P, 25wt.%-35wt.% of Ca, 8wt.%-21wt.% of Fe, 36wt.%-41wt.% of O, and 0.1wt.%-5wt.% of Mg, Al, Mn, or a combination thereof, based on the weight of the catalyst; and
(2) 3wt%-6wt.% of Al, 6wt.%-8wt.% of Si, 12wt.%-16wt.% of P, 28wt.%-32wt.% of Ca, 38wt.%-50wt.% of O, and 0.1wt.%-3wt.% of Mg, S, K, Ti, Mn, Fe, or a combination thereof, based on the weight of the catalyst.
The catalyst is prepared by immersing steel slag into a solution of a phosphorus-containing compound. It is used in the preparation of syngas.


Description

TECHNICAL FIELD



[0001] The technical field relates to a catalyst, a method for preparing the same, and a method for preparing a syngas.

BACKGROUND



[0002] With rapid economic development, mankind is facing critical problems, including the depletion of petrochemical resources and pollution caused by non-renewable energy resources such as gasoline and coal. It is imperative to find other sources of energy that have the advantages of high energy density, environmental friendliness, and sustainable development. The generation of syngas from biomass gasification is of increasing interest with regard to the demands of alternative energy.

[0003] However, in the conventional process for fabricating syngas from biomass via a fluidized bed reactor, a large amount of byproduct (such as char, tar, and ash) is also obtained, resulting in a reduction of the efficiency of gasification. The presence of byproduct in syngas poses major technical obstacles in the gasification process as it may cause fouling and the plugging of downstream processes and equipment. Condensing tar can dramatically foul gas cleaning equipment, and liquid tar droplets that enter prime movers hamper the operation of these end-use applications of the syngas. If tar and condensed water are mixed, e.g., in conventional water-based gas cleaning systems, it may create a water treatment problem that is often costly and difficult to solve.

[0004] Therefore, the industry needs a novel catalyst to serve as the material for a fluidized bed and to inhibit the formation of the byproduct and enhance gasification efficiency.

SUMMARY



[0005] According to embodiments of the disclosure, the disclosure provides a catalyst, wherein the catalyst meets one of the following two conditions (1) and (2):
  1. (1) 4wt%-6wt% of Si, 5wt.%-10wt.% of P, 25wt.%-35wt.% of Ca, 8wt.%-21wt.% of Fe, 36wt.%-41wt.% of O, and 0.1wt.%-5wt.% of Mg, Al, Mn, or a combination thereof, based on the weight of the catalyst; and
  2. (2) 3wt%-6wt.% of Al, 6wt.%-8wt.% of Si, 12wt.%-16wt.% of P, 28wt.%-32wt.% of Ca, 38wt.%-50wt.% of O, and 0.1wt.%-3wt.% of Mg, S, K, Ti, Mn, Fe, or a combination thereof, based on the weight of the catalyst.


[0006] According to embodiments of the disclosure, the disclosure provides a method for preparing the aforementioned catalyst. The method includes immersing an industrial byproduct into a solution to obtain a mixture, wherein the solution includes a phosphorus-containing compound dissolved in a solvent, and wherein the phosphorus-containing compound includes phosphorus-containing inorganic acid, phosphorus-containing salt, phosphorus-containing ester, or a combination thereof. Next, the mixture is dried to remove the solvent, obtaining a solid. The solid is subjected to an annealing process to obtain the catalyst of the disclosure.

[0007] According to other embodiments of the disclosure, the disclosure also provides a method for preparing the syngas. The method includes disposing the catalyst into a reactor. Next, a carbon source is introduced into the reactor. A heating process is performed to convert the carbon source into a syngas by means of the catalyst.

[0008] A detailed description is given in the following embodiments with reference to the accompanying drawings.

DETAILED DESCRIPTION



[0009] According to embodiments of the disclosure, the disclosure provides a catalyst and a method for preparing the same, and a method for preparing a syngas. According to embodiments of the disclosure, the catalyst of the disclosure, for example, can be a silicon-phosphorus-calcium-containing composite oxide. The catalyst can further include aluminum, magnesium, sulfur, potassium, titanium, manganese, iron, or a combination thereof. Since the catalyst of the disclosure includes specific elements and amounts of the elements, the catalyst, serving as a material of fluidized bed disposed in the reactor, can inhibit the formation of the byproduct (such as tar) and enhance the conversion efficiency of hydrocarbon. In addition, the catalyst of the disclosure can be prepared from easily available and cheap industrial byproduct. Therefore, the cost for manufacturing syngas can be reduced.

[0010] According to embodiments of the disclosure, the disclosure provides a catalyst, wherein the catalyst meets one of the following two conditions (1) and (2):
  1. (1) 4wt%-6wt% of Si, 5wt.%-10wt.% of P, 25wt.%-35wt.% of Ca, 8wt.%-21wt.% of Fe, 36wt.%-41wt.% of O, and 0.1wt.%-5wt.% of Mg, Al, Mn, or a combination thereof, based on the weight of the catalyst; and (2) 3wt%-6wt.% of Al, 6wt.%-8wt.% of Si, 12wt.%-16wt.% of P, 28wt.%-32wt.% of Ca, 38wt.%-50wt.% of O, and 0.1wt.%-3wt.% of Mg, S, K, Ti, Mn, Fe, or a combination thereof, based on the weight of the catalyst.


[0011] According to embodiments of the disclosure, the elements (such as silicon, phosphorous, calcium, iron, aluminum, magnesium, potassium, titanium, and/or manganese) in the catalyst are present mainly in the form of oxide (such as silicon oxide, phosphorus pentoxide, calcium oxide, iron oxide, aluminum oxide, magnesium oxide, potassium oxide, titanium oxide, and/or manganese oxide). Therefore, the catalyst of the disclosure can be a composite oxide. According to embodiments of the disclosure, when the catalyst of the disclosure includes sulfur, the metal element of the catalyst can be present in the form of sulfide.

[0012] According to embodiments of the disclosure, when the catalyst of the disclosure meets condition (1), the ratio (W1/W2) of the weight of phosphorous (W1) to the total weight of silicon, calcium, and iron (W2) is from about 0.1 to 0.2 (such as 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, or 0.19), and/or the ratio (W1/W3) of the weight of phosphorous (W1) to the weight of oxygen (W3) is from about 0.1 to 0.27 (such as 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, or 0.26). When the ratio (W1/W2 or W1/W3) is too low, the electrons and holes of the catalyst are not apt to be spaced apart from each other to create an electric dipole moment. As a result, the gasification conversion efficiency of the catalyst is reduced. Conversely, when the ratio (W1/W2 or W1/W3) is too high, the electrons and holes of the catalyst are apt to be recombined due to the narrow depletion region on the catalyst surface. As a result, the gasification conversion efficiency of the catalyst is reduced.

[0013] According to embodiments of the disclosure, when the catalyst of the disclosure meets condition (2), the ratio (W1/W2) of the weight of P (W1) to the total weight of Si, Ca, and Fe (W2) is from about 0.3 to 0.4 (such as 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, or 0.39), and/or the ratio (W1/W3) of the weight of P (W1) to the weight of O (W3) is from about 0.3 to 0.4 (such as 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, or 0.39). When the ratio (W1/W2 or W1/W3) is too low, the electrons and holes of the catalyst are not apt to be spaced apart from each other to create an electric dipole moment, resulting in an inability to stabilize the free radical intermediate product during gasification. As a result, the gasification conversion efficiency of the catalyst is reduced. Conversely, when the ratio (W1/W2 or W1/W3) is too high, the electrons and holes of the catalyst are apt to be recombined due to the narrow depletion region on the catalyst surface, and as a result, the electric dipole moment cannot be created and the free radical intermediate product cannot be stabilized during gasification. As a result, the gasification conversion efficiency of the catalyst is reduced.

[0014] According to embodiments of the disclosure, the catalyst of the disclosure can have a specific surface area from about 10 m2/g to 100 m2/g (such as 20 m2/g, 30 m2/g, 40 m2/g, 50 m2/g, 60 m2/g, 70 m2/g, 80 m2/g, or 90 m2/g).

[0015] According to embodiments of the disclosure, the disclosure provides a method for preparing the catalyst. The catalyst can be prepared from subjecting easily available and cheap industrial byproducts (including elements such as iron, calcium, magnesium, silicon, and/or aluminum), modified by a phosphorous-containing solution, to an annealing process. According to embodiments of the disclosure, the method for preparing the catalyst includes the following steps. First, an industrial byproduct is immersed into a solution to obtain a mixture, wherein the solution includes a phosphorus-containing compound dissolved in a solvent. The phosphorus-containing compound can include phosphorus-containing inorganic acid, phosphorus-containing salt, phosphorus-containing ester, or a combination thereof. Next, the mixture is dried to remove solvent, obtaining a solid. Next, the solid is subjected to an annealing process, obtaining the catalyst of the disclosure.

[0016] It should be noted that, when replacing the phosphorus-containing compound with hydrochloric acid or sulfuric acid to modify the industrial byproduct, the syngas, prepared in the presence of the obtained catalyst, would include chloride-containing compound or sulfur-containing compound, resulting in air pollution. In addition, when replacing the phosphorus-containing compound with organic acid (such as formic acid, or acetic acid) to modify the industrial byproduct, the gasification conversion efficiency of the obtained catalyst cannot be effectively improved.

[0017] According to some embodiments of the disclosure, after immersing the industrial byproduct into the solution to obtain the mixture, the mixture can be divided into a first fraction (such a fraction with relatively low density) and a second fraction (such a fraction with relatively high density) through filtration, decantation, or magnetic sorting. The first fraction or the second fraction is then dried to remove the solvent, obtaining the solid. According to embodiments of the disclosure, the catalyst, prepared by subjecting the fraction with relatively high density of the mixture after drying to an annealing process, has a relatively large amount of iron and manganese.

[0018] According to embodiments of the disclosure, the industrial byproduct can be steel slag. In addition, according to embodiments of the disclosure, the industrial byproduct is free of nickel, and/or chromium. As a result, the obtained catalyst does not include nickel and/or chromium, thereby avoiding the generation of hazardous waste. Herein, the phrase "the industrial byproduct does not includes nickel (or chromium)" means that the amount of nickel (or chromium) in the catalyst is zero or not more than 0.01wt.%, based on the weight of the industrial byproduct.

[0019] According to embodiments of the disclosure, the industrial byproduct meets one of the following two conditions (1) and (2):
  1. (1) 5wt%-9wt% of Si, 0.1wt.%-2wt.% of P, 30wt.%-40wt.% of Ca, 12wt.%-25wt.% of Fe, 30wt.%-40wt.% of O, and 0.1wt.%-8wt.% of Mg, Al, Mn, or a combination thereof, based on the weight of the catalyst; and, based on the weight of the industrial byproduct; and (2) 5wt%-12wt.% of Al, 9wt.%-18wt.% of Si, 0.01wt.%-0.5wt.% of P, 30wt.%-38wt.% of Ca, 35wt.%-48wt.% of O, and 0.1wt.%-8wt.% of Mg, S, K, Ti, Mn, Fe, or a combination thereof, based on the weight of the industrial byproduct.


[0020] According to embodiments of the disclosure, the industrial byproduct meets condition (1) and the weight ratio of the phosphorus-containing compound to the industrial byproduct is from about 1:10 to 1:5 (such as 1:9, 1:8, 1:7, or 1:6). In addition, the industrial byproduct meets condition (2), and the weight ratio of the phosphorus-containing compound to the industrial byproduct is from about 1:5 to 1:2 (such as 1:4, or 1:3).

[0021] According to embodiments of the disclosure, the phosphorus-containing compound can be phosphorus-containing inorganic acid, such as phosphoric acid, phosphorous acid, hypophosphorous acid, or polyphosphoric acid.

[0022] According to embodiments of the disclosure, the phosphorus-containing compound can include phosphorous-containing salt, such as phosphate, phosphite, hypophosphite, or polyphosphate. For example, the phosphorus-containing salt can be phosphorous-containing potassium salt, phosphorous-containing aluminum salt, phosphorous-containing iron salt, phosphorous-containing magnesium salt, phosphorous-containing calcium salt, phosphorous-containing titanium salt, or phosphorous-containing manganese salt.

[0023] According to embodiments of the disclosure, the phosphorus-containing compound can be phosphorus-containing ester, such as phosphoric acid ester, phosphorous acid ester, hypophosphorous acid ester, or polyphosphoric acid ester. For example, the phosphorus-containing ester can be dimethyl phosphite, diethyl phosphite, dipropyl phosphite, diisopropyl phosphite, dibutyl phosphite, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, triisopropyl phosphite, tributyl phosphite, diphenyl phosphite, dibenzyl phosphite, trimethyl phosphate, triethyl phosphate, or triphenyl phosphate.

[0024] According to embodiments of the disclosure, the solvent can be water, tetrahydrofuran, isopropanol, methanol, ethanol, acetonitrile, dioxane, or acetone. According to embodiments of the disclosure, the solution (including the phosphorus-containing compound and the solvent) can have a solid content from about 50% to 85%. According to embodiments of the disclosure, when immersing the industrial byproduct into the solution, the solution covers the whole industrial byproduct. After being stirred completely, the mixture is obtained.

[0025] According to embodiments of the disclosure, the annealing process can be performed at a temperature from about 300°C to 800°C (such as 400°C, 500°C, 600°C, or 700°C). In addition, the annealing process can be performed for a period from 30 minutes to 6 hours (such as 1 hour, 2 hours, 3hours, 4 hours, or 5 hours).

[0026] According to embodiments of the disclosure, the disclosure provides a method for preparing the syngas. The method includes disposing the aforementioned catalyst into a reactor. Next, a carbon source is introduced into the reactor. Next, a heating process is performed to convert the carbon source into a syngas by means of the catalyst. According to embodiments of the disclosure, when converting the carbon source into a syngas by means of the catalyst, a carrier gas can be introduced into the reactor, wherein the carrier gas includes nitrogen gas or inert gas.

[0027] According to embodiments of the disclosure, before disposing the catalyst into the reactor, the catalyst can be subjected to a crushing and screening treatment. As a result, the catalyst has a particle size from about 50 µ m to 1,000 µ m, such as from 50 µ m to 700 µ m, or from 200 µ m to 1000 µ m.

[0028] According to embodiments of the disclosure, the reactor can be a fixed bed reactor, fluidized bed reactor, entrained bed reactor, or double-bed reactor. According to embodiments of the disclosure, the carbon source can be biomass, such as rice straw, sawdust, rice husk, or coal.

[0029] According to embodiments of the disclosure, the heating process temperature is performed at a temperature from 600°C to 1000°C (such as 600°C, 700°C, 800°C, or 900°C). According to embodiments of the disclosure, the weight ratio of the catalyst to the carbon source is from 1:1 to 5:1, such as: 1:2, 1: 3, or 1: 4.

[0030] According to embodiments of the disclosure, the syngas has a heating value from 3 MJ/Nm3 to 18 MJ/Nm3. For example, the syngas can include hydrogen gas (H2), carbon monoxide (CO), methane (CH4), or a combination thereof.

[0031] According to embodiments of the disclosure, the method for preparing a syngas by means of the catalyst of the disclosure, the gasification conversion efficiency of the method can be from about 25% to 58%, such as 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, or 59%. According to embodiments of the disclosure, the heating value of the syngas can be determined by the gas chromatograph with thermal conductivity detector (GC/TCD). The gasification conversion efficiency is determined by the following equation:



[0032] Below, exemplary embodiments will be described in detail so as to be easily realized by a person having ordinary knowledge in the art. The inventive concept may be embodied in various forms without being limited to the exemplary embodiments set forth herein. Descriptions of well-known parts are omitted for clarity.

Preparation of catalyst:


Example 1 :



[0033] First, 100 parts by weight of Slag powder (1) (manufactured by China Himent Corporation) (components analyzed by X-ray fluorescence spectrometer (XRF) were shown in Table 1) was immersed in a solution, wherein the solution included 1.47 parts by weight of phosphoric acid and 20 parts by weight of water. After stirring at room temperature for 4 hours, the fraction with relatively low density (suspending fraction) of the solution was divided from the fraction with relatively high density (settling fraction) of the solution by magnetic sorting. Next, the fraction with relatively high density was dried at 105°C to remove water, obtaining a solid. Next, the solid was subjected to an annealing process at 400°C for 3 hours, obtaining Catalyst (1). Catalyst (1) was analyzed by X-ray fluorescence spectrometer (XRF). The results are shown in Table 1.

Example 2:



[0034] Example 2 was performed in the same manner as Example 1 except that the amount of phosphoric acid was increased from 1.47 parts by weight to 14.7 parts by weight. After stirring at room temperature for 4 hours, the fraction with relatively low density (suspending fraction) of the solution was divided from the fraction with relatively high density (settling fraction) of the solution by magnetic sorting. Next, the fraction with relatively high density was dried at 105°C to remove water, obtaining a solid. Next, the solid was subjected to an annealing process at 400°C for 3 hours, obtaining Catalyst (2). Catalyst (2) was analyzed by X-ray fluorescence spectrometer (XRF). The results are shown in Table 1.

Example 3:



[0035] Example 3 was performed in the same manner as Example 1 except that the fraction with relatively high density (settling fraction) of the solution was replaced with the fraction with relatively low density (suspending fraction) of the solution. Next, the fraction with relatively low density was dried at 105°C to remove water, obtaining a solid. Next, the solid was subjected to an annealing process at 400°C for 3 hours, obtaining Catalyst (3). Catalyst (3) was analyzed by X-ray fluorescence spectrometer (XRF). The results are shown in Table 1.

Example 4:



[0036] Example 4 was performed in the same manner as Example 1 except that the amount of phosphoric acid was increased from 1.47 parts by weight to 25 parts by weight. After stirring at room temperature for 4 hours, the fraction with relatively low density (suspending fraction) of the solution was divided from the fraction with relatively high density (settling fraction) of the solution by magnetic sorting. Next, the fraction with relatively high density was dried at 105°C to remove water, obtaining a solid. Next, the solid was subjected to an annealing process at 400°C for 3 hours, obtaining Catalyst (4). Catalyst (4) was analyzed by X-ray fluorescence spectrometer (XRF). The results are shown in Table 1.

Example 5:



[0037] Example 5 was performed in the same manner as Example 1 except that the amount of phosphoric acid was increased from 1.47 parts by weight to 40 parts by weight. After stirring at room temperature for 4 hours, the fraction with relatively low density (suspending fraction) of the solution was divided from the fraction with relatively high density (settling fraction) of the solution by magnetic sorting. Next, the fraction with relatively high density was dried at 105°C to remove water, obtaining a solid. Next, the solid was subjected to an annealing process at 400°C for 3 hours, obtaining Catalyst (5). Catalyst (5) was analyzed by X-ray fluorescence spectrometer (XRF). The results are shown in Table 1.
Table 1
 Elemental analysis
Mg (wt.%)Al (wt.%)Si (wt.%)P (wt.%)Ca (wt.%)Mn (wt.%)Fe (wt.%)O (wt.%)
Slag powder (1) 3.62 1.54 6.01 1.09 36.16 1.58 15.31 34.69
Catalyst (1) 2.41 1.64 6.25 1.77 33.02 1.72 17.79 35.4
Catalyst (2) 1.7 1.48 4.77 5.59 27.44 1.93 20.63 36.46
Catalyst (3) 1.56 1.28 4.78 9.24 34.79 1.02 8.99 38.34
Catalyst (4) 1.21 1.22 4.0 10.8 29.51 1.34 12.97 38.95
Catalyst (5) 0.79 0.62 1.92 14.26 25.04 1.49 15.95 39.93

Example 6:



[0038] First, 100 parts by weight of Slag powder (2) (manufactured by China Himent Corporation) (components analyzed by X-ray fluorescence spectrometer (XRF) were shown in Table 2) was immersed in a solution, wherein the solution included 1.47 parts by weight of phosphoric acid and 20 parts by weight of water. After stirring at room temperature for 4 hours, the fraction with relatively low density (suspending fraction) of the solution was divided from the fraction with relatively high density (settling fraction) of the solution by magnetic sorting. Next, the fraction with relatively high density was dried at 105°C to remove water, obtaining a solid. Next, the solid was subjected to an annealing process at 400°C for 3 hours, obtaining Catalyst (6). Catalyst (6) was analyzed by X-ray fluorescence spectrometer (XRF). The results are shown in Table 2.

Example 7:



[0039] Example 7 was performed in the same manner as Example 6 except that the amount of phosphoric acid was increased from 1.47 parts by weight to 14.7 parts by weight. After stirring at room temperature for 4 hours, the fraction with relatively low density (suspending fraction) of the solution was divided from the fraction with relatively high density (settling fraction) of the solution by magnetic sorting. Next, the fraction with relatively high density was dried at 105°C to remove water, obtaining a solid. Next, the solid was subjected to an annealing process at 400°C for 3 hours, obtaining Catalyst (7). Catalyst (7) was analyzed by X-ray fluorescence spectrometer (XRF). The results are shown in Table 2.

Example 8:



[0040] Example 8 was performed in the same manner as Example 6 except that the amount of phosphoric acid was increased from 1.47 parts by weight to 25 parts by weight. After stirring at room temperature for 4 hours, the fraction with relatively low density (suspending fraction) of the solution was divided from the fraction with relatively high density (settling fraction) of the solution by magnetic sorting. Next, the fraction with relatively high density was dried at 105°C to remove water, obtaining a solid. Next, the solid was subjected to an annealing process at 400°C for 3 hours, obtaining Catalyst (8). Catalyst (8) was analyzed by X-ray fluorescence spectrometer (XRF). The results are shown in Table 2.

Example 9:



[0041] Example 9 was performed in the same manner as Example 6 except that the amount of phosphoric acid was increased from 1.47 parts by weight to 40 parts by weight. After stirring at room temperature for 4 hours, the fraction with relatively low density (suspending fraction) of the solution was divided from the fraction with relatively high density (settling fraction) of the solution by magnetic sorting. Next, the fraction with relatively high density was dried at 105°C to remove water, obtaining a solid. Next, the solid was subjected to an annealing process at 400°C for 3 hours, obtaining Catalyst (9). Catalyst (9) was analyzed by X-ray fluorescence spectrometer (XRF). The results are shown in Table 2.
Table 2
 Elemental analysis
Mg (wt. %)Al (wt.%)Si (wt.%)P (wt.%)S (wt.%)K (wt.%)Ca (wt.%)Ti (wt.%)Mn (wt.%)Fe (wt.%)O (wt.%)
Slag powder (2) 3.58 7.24 13.93 0.04 0.6 0.36 33.24 0.32 0.46 0.09 40.14
Catalyst (6) 1.9 4.68 10.22 1.36 0.41 0.41 41.61 0.53 0.49 0.61 37.78
Catalyst (7) 1.05 4.54 8.84 10.67 0.22 0.33 30.71 0.52 0.28 0.49 42.35
Catalyst (8) 0.41 3.98 6.5 14.63 0.11 0.22 29.94 0.34 0.23 0.4 43.24
Catalyst (9) 0.63 5.32 7.4 13.27 0.13 0.28 28.9 0.41 0.21 0.26 43.19

Comparative Example 1:



[0042] First, 100 parts by weight of Slag powder (1) (manufactured by China Himent Corporation) (components analyzed by X-ray fluorescence spectrometer (XRF) were shown in Table 1) was immersed in a solution, wherein the solution included 0.6 parts by weight of formic acid and 20 parts by weight of water. After stirring at room temperature for 4 hours, the fraction with relatively low density (suspending fraction) of the solution was divided from the fraction with relatively high density (settling fraction) of the solution by magnetic sorting. Next, the fraction with relatively high density was dried at 105°C to remove water, obtaining a solid. Next, the solid was subjected to an annealing process at 400°C for 3 hours, obtaining Catalyst (10).

Comparative Example 2:



[0043] Comparative Example 2 was performed in the same manner as Comparative Example 1 except that the amount of formic acid was increased from 0.6 parts by weight to 4.4 parts by weight. After stirring at room temperature for 4 hours, the fraction with relatively low density (suspending fraction) of the solution was divided from the fraction with relatively high density (settling fraction) of the solution by magnetic sorting. Next, the fraction with relatively high density was dried at 105°C to remove water, obtaining a solid. Next, the solid was subjected to an annealing process at 400°C for 3 hours, obtaining Catalyst (11).

Preparation of syngas:



[0044] A fixed bed gasification reactor with a radio frequency heating device was provided. The mixture of the catalyst sample and willow wood chips was disposed on the reactor tray of the fixed bed gasification reactor, wherein the weight ratio of the catalyst to the willow wood chips was 4:1. Next, the carrier gas (N2, with a flow rate from 80 mL/min to 200 mL/min) was introduced into the fixed bed gasification reactor. Next, the reactor was rapidly heated to 850°C by the radio frequency heating device, and the obtained syngas was collected via the outlet port. The heating value of the syngas was determined by the gas chromatograph with thermal conductivity detector (GC/TCD), and then the gasification conversion efficiency of the catalyst sample was measured via the heating value of the obtained syngas. Herein, Slag powder (1), a quartz sand (available from Sigma-Aldrich), and Catalysts (1)-(11) individually served as the catalyst sample of the aforementioned preparation of syngas. The results are shown in Table 3.
Table 3
 modificationgasification conversion efficiency (J.%)
Slag powder (1) - 44.3
quartz sand - 23.8
Catalyst (1) Slag powder (1)/1.47wt.% of phosphoric acid /the fraction with relatively high density 28.1
Catalyst (2) Slag powder (1)/14.7wt.% of phosphoric acid /the fraction with relatively high density 56.5
Catalyst (3) Slag powder (1)/14.7wt.% of phosphoric acid /the fraction with relatively low density 49.1
Catalyst (4) Slag powder (1)/25wt.% of phosphoric acid /the fraction with relatively high density 26.0
Catalyst (5) Slag powder (1)/40wt.% of phosphoric acid /the fraction with relatively high density 25.5
Catalyst (6) Slag powder (2)/1.47wt.%of phosphoric acid /the fraction with relatively high density 26.4
Catalyst (7) Slag powder (2)/14.7wt.%of phosphoric acid /the fraction with relatively high density 31.0
Catalyst (8) Slag powder (2)/25wt.%of phosphoric acid /the fraction with relatively high density 48.9
Catalyst (9) Slag powder (2)/40wt%of phosphoric acid /the fraction with relatively high density 47.9
Catalyst (10) Slag powder (1)/0.6wt%of formic acid /the fraction with relatively high density 36.8
Catalyst (11) Slag powder (1)/4.4wt.% of formic acid /the fraction with relatively high density 29.2


[0045] As shown in Table 3, the gasification conversion efficiency of Catalyst (2) as disclosed in Example 2 was more than two times of the gasification conversion efficiency of the quartz sand (the material of the conventional fluidized bed reactor). Therefore, since the catalyst of the disclosure includes specific elements and amounts of the elements, the catalyst, serving as a material of fluidized bed disposed in the reactor, can inhibit the formation of the byproduct and enhance the conversion efficiency of hydrocarbon.

[0046] It will be clear that various modifications and variations can be made to the disclosed methods and materials. It is intended that the specification and examples be considered as exemplary only, with the true scope of the disclosure being indicated by the following claims.


Claims

1. A catalyst, which meets one of two conditions (1) and (2) as follows:

(1) 4wt%-6wt% of Si, 5wt.%-10wt.% of P, 25wt.%-35wt.% of Ca, 8wt.%-21wt.% of Fe, 36wt.%-41wt.% of O, and 0.1wt.%-5wt.% of Mg, Al, Mn, or a combination thereof, based on the weight of the catalyst; and

(2) 3wt%-6wt.% of Al, 6wt.%-8wt.% of Si, 12wt.%-16wt.% of P, 28wt.%-32wt.% of Ca, 38wt.%-50wt.% of O, and 0.1wt.%-3wt.% of Mg, S, K, Ti, Mn, Fe, or a combination thereof, based on the weight of the catalyst.


 
2. The catalyst as claimed in claim 1, wherein the catalyst meets condition (1), and the ratio (W1/W2) of the weight of P (W1) to the total weight of Si, Ca, and Fe (W2) is from 0.1 to 0.2; and/or wherein the catalyst meets condition (1), and the ratio (W1/W3) of the weight of P (W1) to the weight of O (W3) is from 0.1 to 0.27.
 
3. The catalyst as claimed in claim 1 or 2, wherein the catalyst meets condition (2), and the ratio (W1/W2) of the weight of P (W1) to the total weight of Si, Ca, and Fe (W2) is from 0.3 to 0.4; and/or wherein the catalyst meets condition (2), and the ratio (W1/W3) of the weight of P (W1) to the weight of O (W3) is from 0.3 to 0.4.
 
4. The catalyst as claimed in any of claims 1-3, wherein the catalyst has a specific surface area from 10 m2/g to 100 m2/g.
 
5. A method for fabricating a catalyst, comprising:

immersing an industrial byproduct into a solution to obtain a mixture, wherein the solution comprises a phosphorus-containing compound dissolved in a solvent, wherein the phosphorus-containing compound comprises phosphorus-containing inorganic acid, phosphorus-containing salt, phosphorus-containing ester, or a combination thereof;

drying the mixture to remove the solvent, obtaining a solid; and

subjecting the solid to an annealing process to obtain the catalyst as claimed in any of claims 1 to 4.


 
6. The method as claimed in claim 5, wherein the industrial byproduct is steel slag, wherein the industrial byproduct is free of Ni, wherein the industrial byproduct is free of Cr.
 
7. The method as claimed in claim 5 or 6, wherein the industrial byproduct meets one of the following two conditions (1) and (2):

(1) 5wt%-9wt% of Si, 0.1wt.%-2wt.% of P, 30wt.%-40wt.% of Ca, 12wt.%-25wt.% of Fe, 30wt.%-40wt.% of O, and 0.1wt.%-8wt.% of Mg, Al, Mn, or a combination thereof, based on the weight of the catalyst; and, based on the weight of the industrial byproduct; and

(2) 5wt%-12wt.% of Al, 9wt.%-18wt.% of Si, 0.01wt.%-0.5wt.% of P, 30wt.%-38wt.% of Ca, 35wt.%-48wt.% of O, and 0.1wt.%-8wt.% of Mg, S, K, Ti, Mn, Fe, or a combination thereof, based on the weight of the industrial byproduct.


 
8. The method as claimed in claim 7, wherein the industrial byproduct meets condition (1), and the weight ratio of the phosphorus-containing compound to the industrial byproduct is from 1:10 to 1:5.
 
9. The method as claimed in claim 7 or 8, wherein the industrial byproduct meets condition (2), and the weight ratio of the phosphorus-containing compound to the industrial byproduct is 1:5 to 1:2.
 
10. The method as claimed in any of claims 5-9, wherein the phosphorus-containing inorganic acid is phosphoric acid, phosphorous acid, hypophosphorous acid, or polyphosphoric acid, wherein the phosphorus-containing salt is phosphate, phosphite, hypophosphite, or polyphosphate, and/or, wherein the phosphorus-containing ester is phosphoric acid ester, phosphorous acid ester, hypophosphorous acid ester, or polyphosphoric acid ester.
 
11. The method as claimed in any of claims 5-10, wherein the solvent is water, tetrahydrofuran, isopropanol, methanol, ethanol, acetonitrile, dioxane, or acetone.
 
12. The method as claimed in any of claims 5-11, wherein the annealing process is performed at a temperature from 300°C to 800°C and/or performed for a period from 30 minutes to 6 hours.
 
13. The method as claimed in any of claims 5-12, after immersing the industrial byproduct into the solution to obtain the mixture, further comprising:

dividing the mixture into a first fraction and a second fraction through filtration, decantation, or magnetic sorting; and

drying the first fraction or the second fraction to remove the solvent, obtaining the solid.


 
14. A method for preparing a syngas, comprising:

disposing the catalyst as claimed in any of claims 1 to 4 into a reactor;

introducing a carbon source into the reactor; and

performing a heating process to convert the carbon source into a syngas by means of the catalyst.


 
15. The method as claimed in claim 14, wherein the heating process is performed at a temperature from 600°C to 1000°C, wherein the weight ratio of the catalyst to the carbon source is from 1:1 to 5:1, and/or wherein the syngas comprises H2, CO, CH4, or a combination thereof.
 





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