(19)
(11)EP 2 970 790 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
06.05.2020 Bulletin 2020/19

(21)Application number: 14723168.2

(22)Date of filing:  13.03.2014
(51)Int. Cl.: 
C10G 50/00  (2006.01)
C10L 1/04  (2006.01)
C07C 1/10  (2006.01)
C10G 57/02  (2006.01)
C10G 9/36  (2006.01)
(86)International application number:
PCT/US2014/025928
(87)International publication number:
WO 2014/151528 (25.09.2014 Gazette  2014/39)

(54)

METHOD FOR CONVERSION OF CARBONACEOUS MATERIALS TO LIQUID FUEL

VERFAHREN ZUR UMWANDLUNG VON KOHLENSTOFFHALTIGEN STOFFEN IN FLÜSSIGBRENNSTOFF

PROCÉDÉ POUR LA CONVERSION DE MATIÈRES CARBONÉES EN CARBURANT LIQUIDE


(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

(30)Priority: 15.03.2013 US 201313815766

(43)Date of publication of application:
20.01.2016 Bulletin 2016/03

(73)Proprietor: Altex Technologies Corporation
Sunnyvale, California 94086 (US)

(72)Inventors:
  • LUX, Kenneth W.
    Newark, California 94560 (US)
  • NAMAZIAN, Mehdi
    Sunnyvale, California 94086 (US)
  • KELLY, John T.
    Saratoga, California 95070 (US)

(74)Representative: ZBM Patents - Zea, Barlocci & Markvardsen 
Rambla Catalunya, 123
08008 Barcelona
08008 Barcelona (ES)


(56)References cited: : 
WO-A2-2011/156892
US-A1- 2008 016 769
US-A- 5 639 937
  
  • REN T ET AL: "Olefins from conventional and heavy feedstocks: Energy use in steam cracking and alternative processes", ENERGY, PERGAMON PRESS, OXFORD, GB, vol. 31, no. 4, 1 March 2006 (2006-03-01), pages 425-451, XP024900096, ISSN: 0360-5442, DOI: 10.1016/J.ENERGY.2005.04.001 [retrieved on 2006-03-01]
  
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


Description

Field of the Invention



[0001] The present invention relates to conversion of carbonaceous material such as coal and biomass to a synthetic liquid that may be used as a fuel.

Background of the Invention



[0002] Conversion of non-petroleum feedstocks into liquid fuels, such as jet fuel, diesel fuel, or gasoline, has long been of interest due to the limited distribution of petroleum reserves and due to the possibility of producing liquid fuels from biomass and/or waste, which can reduce or eliminate lifecycle CO2 emissions for liquid fuels. Current technologies for converting carbonaceous material into liquid fuels tend to fall into two categories: 1) pyrolysis followed by hydrotreating; and 2) gasification followed by Fischer-Tropsch synthesis.

[0003] In the first category are processes in which the carbonaceous material is pyrolyzed by heating the feed to temperatures of 500-600°C in the absence of molecular oxygen. This results in the generation of solid and gaseous products. The solid product, called char and/or ash, is separated from the gaseous products. The gaseous products are cooled to room temperature to condense a portion of the gaseous products into a liquid that superficially resembles crude oil called pyrolysis oil, or when the carbonaceous material is biomass, bio-oil. The pyrolysis-oil is then further processed to produce a liquid fuel.

[0004] However, when the carbonaceous material contains oxygen - as is the case for materials such as coal, biomass, municipal solid waste, etc. - a significant amount of oxygen is incorporated into the molecules of which the pyrolysis oil is comprised. The oxygen in the pyrolysis oil is often manifested in functional groups such as hydroxyl and carboxylic-acid groups. The presence of these compounds in the pyrolysis oil results in a pyrolysis oil that has a low heating value, a very high acidity, and lacks stability. The low heating value reduces the value of the pyrolysis oil as a fuel or feedstock for producing fuel, the high acidity makes it incompatible with the existing petroleum infrastructure, and the instability results in excessive gum formation and increases in viscosity when stored at or above room temperature.

[0005] In order to address these issues with pyrolysis oil, it is often hydrotreated with hydrogen to remove the oxygen. This results in a pyrolysis oil that has acceptable properties at mass yields of up to 30% depending upon the feedstock and if the source of hydrogen is natural gas. However, the production of hydrogen requires additional equipment operating at high temperatures and pressures, and, in some cases, a source of water. These requirements increase the cost of producing a marketable product. Also, depending upon the source of the fuel used to produce the hydrogen, there may be an increase in fossil-fuel-derived CO2 emissions or a reduction in yield.

[0006] In the second category are processes where the carbonaceous material is gasified at temperatures of 800-1000°C to produce synthesis gas (mainly CO and H2). Because gasification yields a composition close to equilibrium, the specific chemical makeup of the feed only affects the H:C and C:O ratios in the synthesis gas, thus making control of the composition of the final product straightforward. After removing contaminants from the hot gas, a Fischer-Tropsch (F-T) process is employed to link C1 compounds (e.g., CO, CH4, etc.) to produce a targeted hydrocarbon product such as synthetic JP-8 jet fuel. This makes a synthetic fuel that is very close to the desired product. However, this approach is very expensive due, in part, to both the catalytic F-T process, but also due to the complexities of hot-gas clean-up.

[0007] There is a continuing need for technologies that convert carbonaceous material to a synthetic fuel at a cost competitive with traditional petroleum-derived fuels. US 5,639,937 discloses a method for obtaining olefins by conversion of a solid carbonaceous material.

SUMMARY OF THE INVENTION



[0008] The invention is defined in the appended claims. In response to this need, novel processes are described that obviate the limitations and disadvantages of the current processes described above and converts carbonaceous material into intermediate gases that are used as building blocks for producing a liquid that may be used as a targeted fuel (e.g., jet fuel, gasoline). In the invention, the carbonaceous materials - such as coal, biomass, or waste - is fed to a first reaction scheme wherein the feed heated in the absence of molecular oxygen to produce a solid containing char and ash and volatile gases. In contrast to the prior art wherein the volatile gases are partially condensed to form pyrolysis oil, the volatile gases are fed directly to a second reaction scheme wherein a non-catalytic reactor converts a portion of the volatile gases into a mixture of light olefins, predominantly ethylene and propylene. This process, like gasification in the gasification/F-T processes, effectively normalizes the volatile gas feed by converting it into a gas stream that is relatively independent of the feed composition. In further embodiments, in a fashion similar to the linking of C1 compounds in F-T synthesis, the stream containing light olefins, which are reactive towards oligomerization using very inexpensive catalysts, are optionally first cleaned using standard gas-cleanup techniques and then fed to a third reaction scheme where they are linked together to produce hydrocarbons of the correct molecular weight for the targeted synthetic fuel. This use of light olefins as building blocks results in good control of the product composition as with a traditional gasification/F-T process. However, it also reduces cost by avoiding the need for hot-gas cleanup and F-T catalysts. In contrast to traditional pyrolysis, the main product can be used as a high-value liquid fuel. By combining inexpensive feedstock and the best aspects of pyrolysis processes (e.g., lower cost) and gasification/F-T processes (e.g., finer product control) with oligomerization of the light olefins produced, the process embodiments of the invention enable the production of synthetic fuel from carbonaceous material at a relatively low cost.

BRIEF DESCRIPTION OF THE DRAWINGS



[0009] 

Figure 1: Broad process diagram of an embodiment of the invention.

Figure 2: For an embodiment of the present invention, the effect of furnace temperature on outlet temperature and C2-C4 concentrations. Feed: lignite.

Figure 3: For an embodiment of the present invention, the effect of feed rate on C2-C4 concentrations. Open symbols: lignite, filled symbols: subbituminous coal.

Figure 4: For an embodiment of the present invention, the effect of outlet temperature on C2-C4 yields. Feed: lignite.

Figure 5: For an embodiment of the present invention, the effect of feed rate on hydrogen, ethylene, and acetylene concentrations. Open symbols: lignite, filled symbols: subbituminous coal.

Figure 6: For an embodiment of the present invention, the effect of the temperature of the second reaction scheme on C2-C4 concentrations. Feed: ligno-cellulosic biomass.


DETAILED DESCRIPTION OF EMBODIMENTS



[0010] As used herein, unless specified otherwise, any words of approximation such as without limitation, "about," "essentially," "substantially" and the like mean that the element so modified need not be exactly what is described but can vary from the description by as much as ±15% without exceeding the scope of this invention.

[0011] As used herein, any ranges presented are inclusive of the end-points. For example, "a temperature between 500 °C and 600 °C" or "a temperature from 500 °C to 600 °C" includes 500 °C and 600 °C, as well as any temperature in between.

[0012] As used herein, the use of "preferred," "preferably," "more preferred," and the like to modify an aspect of the invention refers to preferences as they existed at the time of filing of the patent application.

[0013] As used herein, including the claims, the phrase "deg C" refers to degrees Celsius.

[0014] As used herein, including the claims, "molecular oxygen" refers to the chemical compound comprised of two oxygen atoms (i.e., with chemical formula O2)

[0015] As used herein, including the claims, "atm" refers to atmospheres.

[0016] As used herein, including the claims, "sec" refers to second or seconds.

[0017] As used herein, including the claims, "e.g." is used to introduce a non-exclusive list of example items and is not intended, as used herein, including the claims, to list all possible items.

[0018] As used herein, including the claims, "wt%" refers to "weight percent."

[0019] Embodiments of the present invention encompass the integration of two reaction schemes to convert carbonaceous material into a solid product of char and ash, a gaseous product containing light olefins, and liquid byproducts. Optionally, a third reaction scheme may be integrated. Thus, some embodiments include the further integration of a third reaction scheme to produce a liquid product, such as a targeted liquid fuel, from the olefins.

[0020] An embodiment of the invention is shown in Figure 1. The carbonaceous feedstock (e.g., coal, biomass, waste) is converted with a first reaction scheme to a gaseous component including condensable gases which includes hydrocarbons and a solid component including char and ash. The gaseous component is fed to a second reaction scheme where the condensable gases and the non-condensable gases that contain 2 or more carbon atoms are converted to reaction products including light olefins. Optionally, a portion of the reaction products of the second reaction scheme may be converted with a third reaction scheme to a liquid product, such as a product that is substantially a targeted liquid fuel.

[0021] A carbonaceous material is any material including carbon and hydrogen. It may include other elements such as without limitation oxygen, nitrogen, sulfur, etc. Non-limiting examples include coal, biomass, paper, cardboard, wood, wheat straw, switchgrass, and waste. In some embodiments, the carbonaceous material serving as the input to the first reaction scheme is a combination of different types of carbonaceous materials.

[0022] A liquid fuel is a liquid product that complies with the specifications for a targeted fuel, or a liquid product that may be used as a fuel. Non-limiting examples include gasoline, jet fuel (JP-5, JP-8), and diesel.

[0023] Condensable gases are those substances that exist as a liquid at 25 deg C and 1 atm pressure.

[0024] Non-condensable gases are those substances that do not exist as a liquid at 25 deg C and 1 atm pressure.

[0025] The first reaction scheme incorporates a non-catalytic reactor similar to a fast-pyrolysis reactor. In fast-pyrolysis reactors, a carbonaceous feedstock is heated in the absence of molecular oxygen to a high temperature, such as but not limited to, around 600 deg C, in a short time period, such as but not limited to, less than 1 second, and not less than 0.0001 sec. This converts the carbonaceous feedstock to a solid product containing char and ash and a gaseous product containing condensable gases and non-condensable gases. The gaseous component can be cooled to produce an oil-like liquid from the condensable hydrocarbons in the gaseous product called pyrolysis oil. In conventional processes, the gaseous component is cooled to produce pyrolysis oil.

[0026] The first reaction scheme is terminated prior to equilibrium to obtain the composition of condensable gases, non-condensable gases that contain 2 or more carbon atoms, or both.

[0027] In the present invention, the gaseous product is not cooled to produce pyrolysis oil. The gaseous product instead is fed directly to the second reaction scheme.

[0028] The second reaction scheme incorporates a non-catalytic reactor that is similar to the radiant section of a steam cracker. As used extensively in the ethylene industry, a steam cracker is fed a hydrocarbon gas (e.g., ethane) or hydrocarbon liquid (e.g., naphtha) and water. The convective section of a furnace preheats the feed and water to produce a gaseous feed to the radiant section of the furnace. Rapidly heating this mixture in the radiant section of the furnace to high temperatures, above around 600°C (such as 600 - 1000 deg C, preferably 700 - 1000 deg C, and more preferably 800 - 1000 deg C), and rapidly cooling the reaction products after a short residence time (e.g. < 5 sec, preferably < 1 sec, and more preferably < 0.1 sec, and optionally, not less than 0.000001 sec) results in the hydrocarbon gas or hydrocarbon liquid being converted to light olefins (e.g., C2-C4 olefins where the subscript after the "C" represents the number of carbons in the compound) as well as other byproducts including hydrogen, light alkanes, light alkynes, and aromatic compounds. A rapid cooling of the product gas freezes out polymerization reactions and minimizes the production of higher molecular-weight compounds. The high-molecular-weight byproducts that are formed are easily separated from the light olefins and recovered as pyrolysis oil and pyrolysis gasoline.

[0029] In the invention, the reactor in the second reaction scheme is similar only to the radiant section of a steam cracker and not include the convective section of a conventional steam cracker.

[0030] It is important to note that, to date, steam crackers have operated on gas and liquid feeds that contain negligible amounts of oxygen. They are specifically intended for and designed for production of ethylene and propylene from oxygen-free gas and oxygen-free liquid feeds. Using a steam cracker for the processing of feeds containing oxygen, particularly a solid feed containing oxygen, is not a conventional use. The embodiments of the present invention utilize conditions similar to those utilized in the radiant section of a traditional steam cracker to convert oxygenated feeds into light olefins. Importantly, this reaction scheme not only serves to produce light olefins, but also serves to convert oxygen-containing functional groups to CO and CO2. Therefore, this reaction scheme also utilizes a reactor similar to a traditional steam cracker as a means of not only producing light olefins, but also for simultaneously converting the oxygen in oxygenated feedstocks and excess carbon into a form that can be readily separated from the light olefins or that does not participate in the reactions used to produce the liquid-fuel product. This is an additional advantage of the embodiments of the present invention.

[0031] In some embodiments, the first reaction scheme increases the H:C ratio of the input, by at least 5%, preferably at least 10%, and more preferably at least 20%, and the second reaction scheme decreases the O:C ratio of the input by at least 5%, preferably 10%, and more preferably 20%. In this manner, the embodiments of the invention increase the H:C ratio and reduce the O:C ratio without requiring the addition of hydrogen.

[0032] In some embodiments, the first and second reaction scheme are executed in separate pieces of equipment, and in other embodiments, the first and second reaction scheme are executed in one piece of equipment.

[0033] Optionally, at least a portion of the olefins, and optionally a portion of the gaseous byproducts from the second reaction scheme, are fed to a third reaction scheme. In some embodiments, light byproducts that may interfere with downstream reactions (e.g., H2S, COS, NH3). Thus in some embodiments, the light olefins and gaseous byproducts may be fed to traditional gas cleanup operations using traditional gas cleanup techniques. For example, the acid-gas components (e.g., CO2, COS, and H2S) and NH3 may be removed with an amine loop. In some embodiments, optionally after removal of acid-gas components and NH3, other non-condensable byproducts (e.g., CO, H2, CH4) are removed through a simple Joule-Thomson cryogenic cycle before the light-olefin stream is fed to the third reaction scheme, which may be an oligomerization reactor. Other gas clean-up techniques that are known in the art may be used. In some embodiments, there are no gas clean-up processes before at least a portion of the reaction products of the second reaction scheme are fed to the third reaction scheme. In some embodiments, compounds which are not olefins (e.g., CO, H2, CH4) pass through the third reaction scheme unchanged, or substantially unchanged.

[0034] The third reaction scheme may incorporate a catalytic reactor similar to a traditional oligomerization reactor. The production of liquids from oligomerization of light olefins is known to practitioners of the art. However, conventionally, this approach has been limited to processes utilizing light olefins derived from petroleum refining as the feedstock. As such, the feeds to traditional oligomerization reactors contain no oxygen, either as molecular oxygen or as oxygen atoms combined with carbon atoms (e.g. CO).

[0035] In some embodiments of the invention, the feed to the third reaction scheme may include oxygenated compounds (e.g. CO) or other compounds not generated in petroleum-refinery operations. The presence of these compounds may impact oligomerization-reactor performance and design as well as the choice of catalyst for use in the oligomerization reactor. Therefore, the integration of the third reaction scheme with the first and second reactions schemes involves more than the addition of a process using a conventional reactor operating at conventional reactor conditions to the end of the equipment train.

[0036] The third reaction scheme is selected based upon the choice of targeted liquid fuel. The reaction pressure, temperature, and space velocity, as well as the choice of catalyst will depend upon the targeted liquid fuel, and may be impacted by the choice of carbonaceous feed to the first reaction scheme. However, it is believed that the specifics of the third reaction scheme are relatively insensitive to the choice of carbonaceous feed to the first reaction scheme. The third reaction scheme is essentially an oligomerization reaction, and one of skill in the art would know be able to select the oligomerization reaction scheme based on what is known to one of skill in the art and the disclosure herein.

[0037] In some embodiments of the invention, the third reaction scheme utilizes an oligomerization reactor wherein the light olefins are oligomerized to form linear α-olefins with a carbon-number distribution that matches that of the targeted fuel. It should be noted that in the oligomerization reactor the linear α-olefins formed from oligomerization of the light olefins are further converted into cycloparaffins to stabilize the liquid fuel and match the key specifications for the fuel properties of interest.

[0038] In some embodiments, the liquid product that may be used as a fuel produced from the integration of the first, second, and third reaction schemes, is jet fuel including, but not limited to, JP-5 and JP-8. In some embodiments, the liquid fuel produced from the integration of the first, second, and third reaction schemes, is gasoline, and in still other embodiments the liquid fuel produced is diesel. In some embodiments, the liquid product of the integration of the first, second, and third reaction schemes, is at least 60 wt%, at least 65 wt%, or at least 70 wt% a liquid that may be used as a fuel, such as a targeted liquid fuel.

Example 1. Laboratory Tests of the Process with Lignite and Subbituminous Coal



[0039] One type of carbonaceous material that can be utilized as the feedstock for process embodiments of the invention is coal. Coal refers to a broad range of materials classified by rank, which is, in general, an indication of the geological age of the material. Of particular interest is the use of low-rank coal such as lignite and sub-bituminous coal. Importantly, these materials contain a considerable amount of oxygen. This oxygen can be in the form of water or it can be incorporated into the chemical structure of the coal.

[0040] An experimental apparatus that integrated first and second reaction schemes, in this example a pyrolyzer and a cracking furnace, was used to test an embodiment of the invention with lignite and subbituminous coal. The first two reaction schemes were integrated as this arrangement avoids condensation and re-vaporization of the condensable gases, from the first reaction scheme. The pyrolyzer was operated in such a manner that the feed was heated to a reaction temperature of 350-550 °C in 1-10 sec. Higher heating rates would produce higher yields of condensable gases, and hence better overall yield. Operating at moderate heating rates enabled testing the first two reaction schemes under conditions that would yield conservative results for yields. Lignite and sub-bituminous coal were fed to this apparatus. The results of these tests are presented in Figure 2 through Figure 5.

[0041] Figure 2 shows the effect of the temperature of the furnace used to provide the heat required by the second reaction scheme on the outlet temperature of this reaction scheme (i.e., the temperature of the reaction products). This test was carried out with lignite as the feed. Higher furnace temperatures lead to higher outlet temperatures and lower C2-C4 concentrations as more H2 and CH4 are produced at higher temperatures.

[0042] Figure 3 shows the effect of feed rate on the C2-C4 concentrations. Data for lignite are shown as open symbols. Data for subbituminous coal are shown as filled symbols. The data for lignite show that higher feed rates lead to slightly lower concentrations. The data for subbituminous coal shows higher yields than for lignite, consistent with the higher hydrocarbon yield from pyrolysis of subbituminous coal as compared to lignite as reported in the literature.

[0043] Figure 4 shows the concentrations of C2-C4 compounds as a function of outlet temperature for lignite. Consistent with the data shown in Figure 2, the concentrations of C2-C4 compounds decrease with increasing outlet temperature. Also shown in Figure 4 is the design target for the concentration of C2-C4 compounds as determined by process-flow simulations of a complete liquid-fuel-production plant using a process embodiment of the present invention.

[0044] Figure 5 shows the concentrations of hydrogen, ethylene, and acetylene as a function of feed rate for lignite (open symbols) and the concentrations of hydrogen, ethylene, and acetylene for subbituminous coal at one particular feed rate. At higher feed rates, the concentration of ethylene decreases while the concentration of hydrogen increases.

[0045] The data shown in Figure 2 through Figure 5 demonstrate that the first two reaction schemes can be combined to produce light olefins that can be utilized by the third reaction scheme to produce a liquid fuel.

[0046] To test the conversion of the light-olefin-containing stream from the second reaction scheme to JP-8, a liquid fuel, tests were conducted with bottled gas representing a typical gas composition of the light-olefin-containing stream after gas clean up. The tests were performed using a proprietary catalyst developed by and available for license from Pennsylvania State University. The best operating conditions and the effect of impurities, such as H2S, on the process were also determined.

[0047] In this test of one of the embodiments of the invention, the process was able to produce a liquid hydrocarbon fuel with a boiling point less than 320°C with a yield of more than 80%. The results demonstrated that the test product of the third reaction scheme is similar to JP-8. This is borne out by a comparison of the properties of the synthetic JP-8 (test product) to a typical sample of JP-8 as shown in Table 1. It can be seen that an embodiment of the invention is able to produce a synthetic JP-8 from coal, a carbonaceous material.
Table 1. Properties of the Test Product and JP-8.
FuelProductJP-8
Density (g/mL) 0.8052 (25°C) 0.77-0.84
D2887 Distillation    
 10% Recovered 135°C < 186°C
 Final Boiling Point 290°C < 330°C
Cloud point (°C) -44.5 -47
Carbon content (wt %) 85.8 -
Hydrogen content (wt %) 13.4 >13.4
Sulfur (ppm) 2.3 1000
Olefins (%) <1% 0.5
Aromatic compounds (%) 22% <25%

Example 2. Laboratory Tests of the Process with Ligno-Cellulosic Biomass



[0048] The production of gasoline from ligno-cellulosic biomass was tested using a proprietary catalyst developed by and available for license from Pennsylvania State University. The results demonstrated that production of olefins from lingo-cellulosic biomass is feasible and that a liquid product similar to gasoline can be obtained through oligomerization. Figure 6 illustrates that the variation in the C2 - C4 compounds with the temperature of the second reaction scheme and for various carbonaceous starting materials. Increasing the reaction temperature of the second reaction scheme generally results in a reduction in the C2-C4 compounds, which is consistent with the results in Example 1 (c.f. Figure 3 and Figure 4). It should be noted that by changing the catalyst or reactor operating pressure or reactor operating temperature, liquids with different molecular weights can be produced making the process extremely flexible and able to create jet fuel (eg. JP-8 and JP-5) or gasoline.

Economic Feasibility



[0049] In order to construct a full-scale plant, both the feasibility and scalability of the process needs to be shown. Laboratory tests have shown embodiments of the invention are technically feasible based on laboratory-scale tests and analyses.

[0050] A Class 4 economic analysis of the process of an embodiment of the invention at a scale of 100,000 BPSD was conducted. A similar analysis of the process converting lingo-cellulosic biomass to gasoline was also conducted for a smaller scale plant for a similar embodiment of the invention. The results of these analyses were compared to the DOE design cases for several CTL (Coal To Liquid), BTL (Biomass to Liquid), and CBTL (Coal and Biomass to Liquid) processes. While the economic assumptions vary from case to case, the process economics data of the embodiment of the invention compares rather favorably to the DOE design cases when similar economic variable are included. The capital cost for an embodiment of the invention is less than DOE design cases. Including operating and financing costs result in embodiments of the invention producing fuel at a lower price than the DOE design cases.


Claims

1. A process for obtaining reaction products comprising olefins comprising:

converting a solid carbonaceous material with a first reaction scheme to a gaseous component comprising condensable gases and non-condensable gases and a solid component comprising char and ash, wherein a temperature of the first reaction scheme is in the range of 350 to 600 deg C, and a residence time of the first reaction scheme is less than 5 sec, and at least 0.0001 sec; and

converting at least a portion of the condensable gases and at least a portion of the non-condensable gases that contain 2 or more carbon atoms with a second reaction scheme to reaction products comprising olefins, wherein a temperature of second reaction scheme is in the range of 600 to 1000 deg C and a residence time of the second reaction scheme is less than 5 sec and at least 0.000001 sec;

wherein the portion of the condensable gases and the portion of the non-condensable gases that contain 2 or more carbon atoms are directly fed from the first reaction scheme to the second reaction scheme without being cooled;

the first reaction scheme is pyrolysis performed in the absence of a catalyst;

the second reaction scheme is similar to the reaction occurring only in the radiant section of a steam cracker, and is performed in the absence of a catalyst, and in the presence of steam and in the absence of molecular oxygen; and

wherein hydrogen is not added during the process.


 
2. The process of claim 1, further comprising separating the solid component from the gaseous component.
 
3. The process of claim 1, wherein the condensable gases and the non-condensable gases that contain 2 or more carbon atoms that are fed to the second reaction scheme comprise at least 0.1 wt% oxygen on a dry basis, and not more than 95 wt%.
 
4. The process of claim 1, further comprising converting at least a portion of the reaction products from the second reaction scheme to a liquid product with a third reaction scheme wherein the liquid product is at least 60% by weight a liquid fuel.
 
5. The process of claim 4, wherein the third reaction scheme is performed in the presence of a catalyst.
 
6. The process of claim 5, wherein the third reaction scheme is oligomerization.
 
7. The process of claim 6, further comprising, prior to being fed to the third reaction scheme, cleaning the gaseous reaction products of the second reaction scheme to remove species that poison catalysts.
 
8. The process of claim 1, wherein the reaction product of the second reaction scheme comprises non-condensable gases, and the non-condensable gases, free of CH4, CO, CO2, COS, H2, H2S, NH3, and H2O, comprise at least 50 wt% olefins.
 
9. The process of claim 1, wherein

the temperature of the first reaction scheme is in the range of 450 to 600 deg C, and

the temperature of the second reaction scheme is in the range of 700 to 1000 deg C.


 
10. The process of claim 1, wherein the condensable gases and the non-condensable gases that contain 2 or more carbon atoms that are fed to the second reaction scheme comprise at least 1 wt% oxygen on a dry basis, and not more than 95 wt%.
 
11. The process claim 4, wherein the feed to the third reaction scheme comprises oxygenated compounds.
 
12. The process of claim 1, wherein the reaction products of the second reaction scheme comprise non-condensable gases, and the non-condensable gases, free of CH4, CO, CO2, COS, H2, H2S, NH3, and H2O, comprise at least 35 wt% olefins.
 
13. The process of claim 6, wherein no gas clean-up processes are performed before at least a portion of the reaction products of the second reaction are fed to the third reaction scheme.
 
14. The process of claim 1, wherein first reaction scheme and second reaction scheme are executed in one piece of equipment.
 
15. The process of claim 1, wherein the non-condensable gases of the reaction products of the second reaction scheme, free of CH4, CO, CO2, COS, H2, H2S, NH3, and H2O, comprise at least 25 wt% olefins.
 


Ansprüche

1. Ein Verfahren zur Herstellung von Reaktionsprodukten umfassend Olefine umfassend:

das Umwandeln von einem festen kohlenstoffhaltigen Material mit einem ersten Reaktionsschema in einen gasförmigen Bestandteil umfassend kondensierbare Gase und nicht-kondensierbare Gase und einen festen Bestandteil umfassend Holzkohle und Asche, wobei eine Temperatur des ersten Reaktionsschemas im Bereich von 350 bis 600 Grad Celsius liegt und eine Verweildauer des ersten Reaktionsschemas weniger als 5 Sekunden, und mindestens 0,0001 Sekunde, beträgt; und

das Umwandeln von mindestens einem Teil der kondensierbaren Gase und mindestens einem Teil der nicht-kondensierbaren Gase, welche 2 oder mehr Kohlenstoffatome enthalten, mit einem zweiten Reaktionsschema in Reaktionsprodukte umfassend Olefine, wobei eine Temperatur des zweiten Reaktionsschemas im Bereich von 600 bis 1000 Grad Celsius liegt und eine Verweildauer des zweiten Reaktionsschemas weniger als 5 Sekunden und mindestens 0,000001 Sekunde beträgt;

wobei der Teil der kondensierbaren Gase und der Teil der nicht-kondensierbaren Gase, welche 2 oder mehr Kohlenstoffatome enthalten unmittelbar von dem ersten Reaktionsschema dem zweiten Reaktionsschema zugeführt werden, ohne abgekühlt zu werden;

das erste Reaktionsschema Pyrolyse ist, die in Abwesenheit von einem Katalysator durchgeführt wird;

das zweite Reaktionsschema der Reaktion ähnlich ist, die nur in der Strahlungszone eines Steamcrackers stattfindet und in Abwesenheit von einem Katalysator und in Gegenwart von Dampf und in Abwesenheit von molekularer Sauerstoff durchgeführt wird; und

wobei kein Wasserstoff während des Verfahrens hinzugegeben wird.


 
2. Das Verfahren des Anspruchs 1, weiterhin umfassend das Abtrennen des festen Bestandteils von dem gasförmigen Bestandteil.
 
3. Das Verfahren des Anspruchs 1, wobei die kondensierbaren Gase und die nicht-kondensierbaren Gase, welche 2 oder mehr Kohlenstoffatome enthalten, die dem zweiten Reaktionsschema zugeführt werden, mindestens 0,1 Gew.-% Sauerstoff, auf die Trockenmasse bezogen, und nicht mehr als 95 Gew.-% umfassen.
 
4. Das Verfahren des Anspruchs 1, weiterhin umfassend das Umwandeln von mindestens einem Teil der Reaktionsprodukte von dem zweiten Reaktionsschema in ein flüssiges Produkt mit einem dritten Reaktionsschema, wobei das flüssige Produkt zu mindestens 60 Gew.-% ein flüssiger Brennstoff ist.
 
5. Das Verfahren des Anspruchs 4, wobei das dritte Reaktionsschema in Gegenwart eines Katalysators durchgeführt wird.
 
6. Das Verfahren des Anspruchs 5, wobei das dritte Reaktionsschema Oligomerisation ist.
 
7. Das Verfahren des Anspruchs 6, weiterhin umfassend das Reinigen von den gasförmigen Reaktionsprodukten des zweiten Reaktionsschemas, bevor sie dem dritten Reaktionsschema zugeführt werden, um Spezies zu entfernen, die Katalysatoren vergiften.
 
8. Das Verfahren des Anspruchs 1, wobei das Reaktionsprodukt von dem zweiten Reaktionsschema nicht-kondensierbare Gase enthält und die nicht-kondensierbaren Gase, frei von CH4, CO, CO2, COS, H2, H2S, NH3, und H2O mindestens 50 Gew.-% Olefine enthalten.
 
9. Das Verfahren des Anspruchs 1, wobei

die Temperatur des ersten Reaktionsschemas im Bereich von 450 bis 600 Grad Celsius liegt, und

die Temperatur des zweiten Reaktionsschemas im Bereich von 700 bis 1000 Grad Celsius liegt.


 
10. Das Verfahren des Anspruchs 1, wobei die kondensierbaren Gase und die nicht-kondensierbaren Gase, welche 2 oder mehr Kohlenstoffatome enthalten, die dem zweiten Reaktionsschema zugeführt werden, mindestens 1 Gew.-% Sauerstoff, auf die Trockenmasse bezogen, und nicht mehr als 95 Gew.-% umfassen.
 
11. Das Verfahren des Anspruchs 4, wobei die Zuführung dem dritten Reaktionsschema sauerstoffhaltige Verbindungen umfasst.
 
12. Das Verfahren des Anspruchs 1, wobei die Reaktionsprodukte von dem zweiten Reaktionsschema nicht-kondensierbare Gase enthalten und die nicht-kondensierbaren Gasen, frei von CH4, CO, CO2, COS, H2, H2S, NH3, und H2O, mindestens 35 Gew.-% Olefine enthalten.
 
13. Das Verfahren des Anspruchs 6, wobei keine Gasreinigungsverfahren durchgeführt werden, bevor mindestens ein Teil von den Reaktionsprodukten der zweiten Reaktion dem dritten Reaktionsschema zugeführt werden.
 
14. Das Verfahren des Anspruchs 1, wobei das erste Reaktionsschema und das zweite Reaktionsschema in einem Ausrüstungsgegenstand ausgeführt werden.
 
15. Das Verfahren des Anspruchs 1, wobei die nicht-kondensierbaren Gase der Reaktionsprodukte von dem zweiten Reaktionsschema, frei von CH4, CO, CO2, COS, H2, H2S, NH3, und H2O, mindestens 25 Gew.-% Olefine enthalten.
 


Revendications

1. Un procédé d'obtention de produits de réaction comprenant des oléfines comprenant :

convertir un matériau carboné solide avec un premier schéma réactionnel en un composant gazeux comprenant des gaz condensables et des gaz non condensables et un composant solide comprenant du résidu charbonneux et des cendres, dans lequel une température du premier schéma réactionnel est dans l'intervalle de 350 à 600 degrés Celsius, et un temps de résidence du premier schéma réactionnel est inférieur à 5 secondes, et d'au moins 0,0001 seconde ; et

convertir au moins une partie des gaz condensables et au moins une partie des gaz non condensables qui contiennent 2 ou plus atomes de carbone avec un second schéma réactionnel en des produits de réaction comprenant des oléfines, dans lequel une température du second schéma réactionnel est dans l'intervalle de 600 à 1000 degrés Celsius et un temps de résidence du second schéma réactionnel est inférieur à 5 secondes et d'au moins 0,000001 seconde ;

dans lequel la partie des gaz condensables et la partie des gaz non condensables qui contiennent 2 ou plus atomes de carbone sont alimentées directement du premier schéma réactionnel au second schéma réactionnel sans être refroidies ;

le premier schéma réactionnel est de la pyrolyse effectuée en absence de catalyseur ;

le second schéma réactionnel est similaire à la réaction qui se produit seulement dans la section radiante d'un vapocraqueur et est effectué en absence d'un catalyseur et en présence de vapeur et en absence d'oxygène moléculaire ; et

dans lequel on n'ajoute pas d'hydrogène pendant le procédé.


 
2. Le procédé de la revendication 1, comprenant en outre séparer le composant solide du composant gazeux.
 
3. Le procédé de la revendication 1, dans lequel les gaz condensables et les gaz non condensables qui contiennent 2 ou plus atomes de carbone qui sont alimentés au second schéma réactionnel comprennent au moins 0,1 % en poids d'oxygène, sur base sèche, et non plus de 95 % en poids.
 
4. Le procédé de la revendication 1, comprenant en outre convertir au moins une partie des produits de réaction du second schéma réactionnel en un produit liquide avec un troisième schéma réactionnel dans lequel le produit liquide constitue au moins 60 % en poids d'un combustible liquide.
 
5. Le procédé de la revendication 4, dans lequel le troisième schéma réactionnel est effectué en présence d'un catalyseur.
 
6. Le procédé de la revendication 5, dans lequel le troisième schéma réactionnel est une oligomérisation.
 
7. Le procédé de la revendication 6, comprenant en outre, nettoyer les produits de réaction gazeux du second schéma réactionnel, avant de les alimenter au troisième schéma réactionnel, afin d'enlever des espèces qui empoisonnent le catalyseur.
 
8. Le procédé de la revendication 1, dans lequel le produit de réaction du second schéma réactionnel comprend des gaz non condensables et les gaz non condensables, exempts de CH4, CO, CO2, COS, H2, H2S, NH3 et H2O, comprennent au moins 50 % en poids d'oléfines.
 
9. Le procédé de la revendication 1, dans lequel

la température du premier schéma réactionnel est dans l'intervalle de 450 à 600 degrés Celsius, et

la température du second schéma réactionnel est dans l'intervalle de 700 à 1000 degrés Celsius.


 
10. Le procédé de la revendication 1, dans lequel les gaz condensables et les gaz non condensables qui contiennent 2 ou plus atomes de carbone qui sont alimentés au second schéma réactionnel comprennent au moins 1 % en poids d'oxygène, sur base sèche, et non plus de 95 % en poids.
 
11. Le procédé de la revendication 4, dans lequel l'alimentation au troisième schéma réactionnel comprend des composés oxygénés.
 
12. Le procédé de la revendication 1, dans lequel les produits de réaction du second schéma réactionnel comprennent des gaz non condensables et les gaz non condensables, exempts de CH4, CO, CO2, COS, H2, H2S, NH3 et H2O, comprennent au moins 35 % en poids d'oléfines.
 
13. Le procédé de la revendication 6, dans lequel on n'effectue pas de procédés de nettoyage de gaz avant d'alimenter au moins une partie des produits de réaction de la seconde réaction au troisième schéma réactionnel.
 
14. Le procédé de la revendication 1, dans lequel le premier schéma réactionnel et le second schéma réactionnel sont effectués dans une unité d'équipement.
 
15. Le procédé de la revendication 1, dans lequel les gaz non condensables et les produits de réaction du second schéma réactionnel, exempts de CH4, CO, CO2, COS, H2, H2S, NH3 et H2O, comprennent au moins 25 % en poids d'oléfines.
 




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REFERENCES CITED IN THE DESCRIPTION



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Patent documents cited in the description