CN114805023B - Method for preparing olefin by using zero-emission coal - Google Patents
Method for preparing olefin by using zero-emission coal Download PDFInfo
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- CN114805023B CN114805023B CN202210314624.5A CN202210314624A CN114805023B CN 114805023 B CN114805023 B CN 114805023B CN 202210314624 A CN202210314624 A CN 202210314624A CN 114805023 B CN114805023 B CN 114805023B
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- C07—ORGANIC CHEMISTRY
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
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- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
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Abstract
The invention relates to the technical field of coal processing and conversion, and discloses a method for preparing olefin from zero-emission coal. According to the method provided by the invention, by introducing the step of reforming treatment, the byproducts and CO 2 in the production process are reformed, so that the comprehensive utilization of CO 2 generated in the process of preparing high-carbon (olefin) hydrocarbon from coal is realized, the diversification of products prepared from synthetic gas is realized, and the technical route of coal-based clean energy chemical industry is expanded. Meanwhile, the method has the advantages of simple process flow, making full use of each component in the coal gas, reducing the emission of greenhouse gases and the like, and realizing the coordinated development of economy, environment and energy.
Description
Technical Field
The invention relates to the technical field of coal processing and conversion, in particular to a method for preparing olefin from zero-emission coal.
Background
As an important organic raw material, the high-carbon alpha-olefin has the advantages of higher additional value, reduced harm, easy transportation and storage and the like, and has wide application range, so the technology development value of the high-carbon alpha-olefin is higher. In recent years, with the rapid development of the synthetic resin industry in China, the productivity of hexene-1 and octene-1 is obviously insufficient, so that the development of high-carbon alpha-olefin has become an important research direction in the petrochemical industry in China. The production method of high-carbon alpha-hydrocarbon olefin is mainly characterized by comprising a wax cracking process, a fatty alcohol dehydrogenation process, an ethylene oligomerization process, an alkane catalytic cracking process, a Fischer-Tropsch synthesis process and the like, wherein the ethylene oligomerization process uses triethylaluminum as a catalyst, and ethylene is subjected to compression, preheating, growth, replacement, separation and other processing flows to finally obtain the high-carbon alpha-hydrogen olefin product. The high-carbon alpha-hydrocarbon olefin produced by the ethylene oligomerization process has narrow polymerization degree distribution and high product quality, and is the most common process. The Fischer-Tropsch synthesis reaction has the characteristic of easily generating linear alpha olefins or primary alcohols, and the product contains alpha hydrocarbon olefins with various carbon numbers (odd and even), so that the defect that an ethylene method can only produce even alpha hydrocarbon olefins can be overcome, and the product has wider application and higher added value. At present, global petroleum resources are increasingly consumed, the problem of energy safety is more and more serious, and research and development of a new energy system are urgent. The synthesis gas chemical industry is a hotspot in the field of energy chemical industry at present, wherein synthesis gas is prepared through coal gasification, and then synthesis gas is subjected to catalytic hydrogenation to synthesize low-carbon alcohol, so that one of the problems of more research is achieved. However, these processes have the problem of underutilization of the synthesis gas, especially CO 2 generated during the process, resulting in excessive CO 2 being emitted and causing significant environmental damage.
Therefore, how to improve the yield of the high-carbon hydrocarbon from the coal, improve the utilization efficiency of the Fischer-Tropsch synthesis tail gas, realize low carbon emission, and find out that the method and the process for comprehensively utilizing the CO 2 resources have important environmental significance and industrial application value.
Disclosure of Invention
The invention aims to solve the problems that the high-efficiency utilization of synthetic gas cannot be realized in the process of preparing olefin from coal, the emission of CO 2 generated in the process is large, the utilization of C resources is insufficient and the like in the prior art, and provides a method for preparing olefin from coal with zero emission.
In order to achieve the above object, the present invention provides a method for producing olefins from coal with zero emission, comprising the steps of: preparing and purifying synthesis gas, fischer-Tropsch synthesis of high-carbon hydrocarbon, reforming methane and carbon dioxide, and synthesis of low-carbon alcohol;
The raw coal is subjected to the synthesis gas preparation and purification step to obtain pure synthesis gas and methane, the pure synthesis gas enters the high-carbon hydrocarbon Fischer-Tropsch synthesis step to obtain a liquid phase product containing high-carbon hydrocarbon and a gas phase product containing unreacted synthesis gas and CO 2, CO 2 in the gas phase product and methane obtained in the synthesis gas preparation and purification step enter the methane and carbon dioxide reforming step to obtain a reformed product, the reformed product is used as the raw gas and enters the low-carbon alcohol synthesis step, and purge gas generated in the low-carbon alcohol synthesis step is recycled in the low-carbon alcohol synthesis step.
Through the technical scheme, the invention can obtain the following beneficial effects:
(1) The invention fully utilizes the methane in the synthesis gas produced by pulverized coal pressurized gasification, and the methane and CO 2 produced in Fischer-Tropsch synthesis produce reformed synthesis gas (hydrogen-rich synthesis gas), thereby realizing the full utilization of CO 2, increasing the utilization of carbon resources and reducing carbon emission.
(2) Compared with the existing hydrocarbon preparation technology by using the synthetic gas, the method provided by the invention can not only produce high-carbon (olefin) hydrocarbon and prepare the synthetic gas by reforming methane in the synthetic gas, but also produce low-carbon (olefin) hydrocarbon by using the synthetic gas prepared by reforming CO 2 and Fischer-Tropsch byproduct methane, thereby avoiding the emission of greenhouse gases, achieving the comprehensive utilization of CO 2, realizing the diversification of products prepared by the synthetic gas and expanding the technical route of coal-based clean energy chemical industry.
(3) The method provided by the invention makes full use of each component in the coal gas, has no greenhouse gas emission, saves energy, water and investment, has simple process flow and stable running operation, and realizes the coordinated development of economy, environment and energy.
Drawings
FIG. 1 is a schematic diagram of a process flow of zero emission coal-to-olefin.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The inventors of the present invention have found in the course of studies that by introducing a reforming treatment device/step in the course of coal-to-olefins, particularly high-carbon olefins, methane as a by-product and CO 2 generated in the production process can be reformed and the reformed product can be used for the production of low-carbon alcohols. Thereby realizing the recycling of byproducts and wastes in the process of preparing the high-carbon olefin by the coal, reducing the carbon emission, particularly the emission of CO 2, and realizing the production zero emission while improving the environmental protection value of the process.
Based on the above findings, the present invention provides a method for producing olefins from coal with zero emission, comprising the steps of: preparing and purifying synthesis gas, fischer-Tropsch synthesis of high-carbon hydrocarbon, reforming methane and carbon dioxide, and synthesis of low-carbon alcohol;
The raw coal is subjected to the synthesis gas preparation and purification step to obtain pure synthesis gas and methane, the pure synthesis gas enters the high-carbon hydrocarbon Fischer-Tropsch synthesis step to obtain a liquid phase product containing high-carbon hydrocarbon and a gas phase product containing unreacted synthesis gas and CO 2, CO 2 in the gas phase product and methane obtained in the synthesis gas preparation and purification step enter the methane and carbon dioxide reforming step to obtain a reformed product, the reformed product is used as the raw gas and enters the low-carbon alcohol synthesis step, and purge gas generated in the low-carbon alcohol synthesis step is recycled in the low-carbon alcohol synthesis step.
In the invention, the purge gas generated in the low-carbon alcohol synthesis step mainly comprises components such as H 2、CO、CO2、CH4、N2, and the like, the carbon dioxide reforming and the purge gas recycling are carried out by the method provided by the invention, N2 in the purge gas is directly discharged, and other components (such as H 2、CO、CO2、CH4, and the like) are recycled in the system (recycling herein comprises direct recycling or recycling after reforming). Preferably, the purge gas includes: h 2 -70 vol%, CO 5-10 vol%, CO 2 -5 vol%, CH 4 -3 vol% and N 2 -30 vol%.
In the present invention, there is no particular limitation on the specific operation and method in the synthesis gas preparation and purification step. According to a preferred embodiment of the invention, the synthesis gas preparation and purification step comprises the steps of mixing raw coal and O 2 for coal gasification, and sequentially carrying out alcohol washing and methane separation on the obtained raw coal gas after sulfur-tolerant shift to obtain pure synthesis gas and methane.
The inventor of the invention also discovers that the method provided by the invention can adopt the low-grade coal with high water content and high ash content as the raw material coal gasification, further process the obtained gas product, and realize the multi-stage co-production and the staged utilization of the coal.
Preferably, the raw coal is selected from low-grade coal dust with 15-30 wt% of moisture content, 9-25 wt% of ash content, 25-40 wt% of volatile content and 49-61 wt% of carbon content, and the grain size of the raw coal is preferably 5-50mm;
More preferably, the feed coal has a moisture content of 15 to 21 wt%, an ash content of 20 to 25 wt%, a volatile content of 32 to 37 wt%, a carbon content of 50 to 55 wt%, and a particle size of 25 to 50mm.
Preferably, the O 2 is provided by air.
Preferably, the coal gasification is performed by means of fixed bed gasification, fluidized bed gasification, entrained flow gasification and the like;
More preferably, the coal gasification conditions include a temperature of 1000-1500 ℃, a pressure of 4-6MPa, and a volume ratio of raw coal to O 2 of 1:1-5, preferably 1:2-3.
Because the low-quality coal has complex components, the coal gas pressurized gasification by the coal powder has low tapping temperature, and the components of the raw coal gas are also complex. In general, possible components in the raw gas include CO, H 2、CO2、CH4、H2 S, organic sulfur 、C2H4、C2H6、C3H8、C4H10、HCN、N2、Ar, and tar, fatty acids, monophenols, complex phenols, naphtha, oil, etc. Preferably, the raw gas contains 0.05-0.1% by volume of CH 4, 55-65% by volume of CO, 21-31% by volume of H 2 and 3-8% by volume of CO 2;
Preferably, the sulfur tolerant shift employs a Co-Mo catalyst. Preferably, a Co-Mo catalyst is used, wherein the carrier is at least one of active alumina, magnesia-alumina spinel and an aluminum-titanium-magnesium composite carrier.
The catalyst for sulfur shift resistance in the present invention may be a commercially available catalyst having the above-mentioned characteristics, for example, SSK type catalyst of Denmark topline, K8-11 type catalyst of German BASF corporation, C113 type catalyst of Japanese XingKogyo Co., ltd, QDB-04 series sulfur shift resistance catalyst manufactured by Qingdao Union chemical industry Co., ltd, QCS-04 series sulfur shift resistance catalyst manufactured by Utility chemical industry Co., ltd, EB series sulfur shift resistance catalyst developed by Hubei chemical research institute, or the like. It is also possible to use catalysts having the abovementioned features, which are prepared by themselves according to the prior art.
More preferably, the sulfur shift resistant conditions include a temperature of 220-450 ℃, a pressure of 2-5MPa, and a volume space velocity of 1000-3000h -1 based on dry gas.
The inventor of the invention also found in the study that the sulfur-tolerant shift is carried out on part of the raw gas, and the shift-treated raw gas is mixed with the unchanged raw gas, so that the amount of CO 2 generated in the shift can be greatly reduced, the adjusting range of the synthesis gas H 2/CO entering the Fischer-Tropsch synthesis reactor can be enlarged, the production process can be adjusted more conveniently, and the emission of CO 2 can be reduced.
According to a preferred embodiment of the present invention, the step of sulfur shift resisting includes sulfur shift resisting part of the raw gas and alcohol washing the mixture of the residual raw gas not subjected to sulfur shift conversion and the shifted raw gas.
Preferably, the raw gas subjected to sulfur shift conversion accounts for 25-50% by volume, preferably 30-40% by volume of the total raw gas.
Except for CO, H 2 effective components, CH 4、N2, ar and hydrocarbon inert gases in raw gas components (such as the possible components), all the other components including CO 2 and sulfides are harmful impurities which need to be removed, and various harmful components such as hydrocarbons above CO 2、H2S、COS、C4H4S、HCN、NH3、H2O、C2 (including light oil, aromatic hydrocarbon, naphtha, olefin, colloid and the like) and other carbonyl compounds can be completely removed in the same device by generally adopting (low-temperature) alcohol cleaning.
In order to prevent the damage to the environment, equipment and personnel and improve the green production of the factory, preferably, the step of alcohol washing is performed by adopting a low-temperature methanol washing and/or polyethylene glycol dimethyl ether washing mode; .
More preferably, the conditions of the alcohol washing include a temperature of-33 ℃ to-55 ℃ and a pressure of 2-6MPa, and preferably the alcohol washing is such that H 2 S (volume fraction) content in the raw gas after the alcohol washing is 0.1ppm or less and CO 2 is 20ppm or less.
Preferably, the alcohol washing step further comprises the operation of recovering the washed H 2 S concentrated gas. Recovery of H 2 S concentrate gas may be carried out, for example, using a Claus sulfur recovery process.
Preferably, the methane separation is performed by cryogenic separation and/or adsorptive separation.
According to a preferred embodiment of the present invention, wherein the conditions of cryogenic separation comprise a temperature of-145 ℃ to-175 ℃ and a pressure of 3-8MPa.
Preferably, the conditions of the cryogenic separation comprise a temperature of-150 ℃ to-160 ℃ and a pressure of 4-5.5MPa
According to a preferred embodiment of the invention, the step of Fischer-Tropsch synthesis of higher hydrocarbons comprises the step of taking pure synthesis gas obtained in the step of synthesis gas preparation and purification as a raw material to carry out Fischer-Tropsch reaction, preferably the conditions of the Fischer-Tropsch reaction comprise a pressure of 2-4MPa, a temperature of 220-350 ℃, a molar ratio of H 2 to CO of 2-5:1 and a gas phase volume space velocity of 5000-50000H -1.
In the present invention, the Fischer-Tropsch reaction may employ any catalyst known in the art for use in Fischer-Tropsch reactions. In order to further improve the reaction efficiency and the carbon conversion, the catalyst used in the Fischer-Tropsch reaction is preferably a Fe-Mn-Cu-K catalyst or a Fe-Mn-Cu-K-M catalyst, wherein M is at least one of B, C, N, zn, ga and Sn. The Fe-Mn-Cu-K catalyst refers to a catalyst taking Fe, mn, cu, K as a catalyst active component, and a carrier with a characteristic of large specific surface area can be adopted as the carrier, such as nano-sheet Al 2O3 and the like. The Fe-Mn-Cu-K-M catalyst refers to a catalyst which takes Fe, mn, cu, K and M (the specific selection of M is as described above) as catalyst active components, and a carrier with a large specific surface area and slightly alkaline characteristic can be adopted as the carrier, for example, nano-sheet Al 2O3、MgO、TiO2 and the like.
In order to further increase the catalytic activity of the catalyst and thus the efficiency of the fischer-tropsch reaction and increase the conversion of carbon, more preferably, the weight ratio of Fe, mn, cu, K in the Fe-Mn-Cu-K catalyst may be 100:0.2-12:0.2-12:0.1-10. In the Fe-Mn-Cu-K-M catalyst, the weight ratio of Fe, mn, cu, K to M can be 100:0.2-12:0.2-12:0.1-10:3-40.
Preferably, the step of Fischer-Tropsch synthesis of the high-carbon hydrocarbon further comprises the step of gas-liquid separation of the reaction product to obtain a liquid-phase product and a gas-phase product.
According to a preferred embodiment of the invention, wherein the liquid phase product comprises C8-C12 alpha-olefins and naphtha, preferably wherein the content of alpha-olefins is in the range of 35 to 75 mole% (preferably the remainder is naphtha).
According to a preferred embodiment of the invention, wherein the gas phase product comprises CH 4 and/or CO 2.
Preferably, the process further comprises the operation of decarbonating the gaseous product to obtain recovered synthesis gas and CO 2, preferably recycling the recovered synthesis gas to the fischer-tropsch reaction.
In the present invention, the purpose of the decarburization treatment is to remove CO 2 and the like from the gas-phase product, and the specific decarburization treatment method and conditions are not particularly limited as long as the purpose can be achieved. Preferably, the decarbonization treatment mode comprises liquid absorption and/or molecular sieve absorption, preferably liquid absorption, more preferably K 2CO3 aqueous solution and/or Na 2CO3 aqueous solution for decarbonization. The concentration of solute in the aqueous solution may be 240g/L to 290g/L, preferably 245g/L to 280g/L. For better control of the CO 2 outlet content, V 2O5, preferably V 2O5, may be added to the aqueous solution in an amount such that the total vanadium concentration in the solution is greater than 20g/L, wherein the vanadium concentration at valence 5 is greater than 20g/L.
According to a preferred embodiment of the present invention, the methane and carbon dioxide reforming step comprises reforming CO 2 obtained in the higher hydrocarbon fischer-tropsch synthesis step with methane separated in the synthesis gas production and purification step to obtain a reformate.
Preferably, the catalyst used in the reforming treatment comprises a main active component, a secondary active component and a carrier, wherein the main active component is Co, preferably the content of the main active component is 0.05 to 30 weight percent of the total mass of the catalyst, the secondary active component comprises at least one of Th, ni, ce, mo, mg, pa, pt, ru, rh and Ir, preferably the content of the secondary active component is 0.01 to 20 weight percent of the total mass of the catalyst, and the carrier comprises at least one of a carbon carrier, an inorganic oxide and a molecular sieve.
More preferably, the weight ratio of the primary active component to the secondary active component is 0.1-2:1. preferably 1-2:1.
Preferably, the reforming treatment conditions include a pressure of 0-5MPa, a temperature of 450-850 ℃, and a gas phase volume space velocity of 5000-50000h -1.
More preferably, the conditions of the reforming treatment include a reactor pressure of 1-4MPa, a temperature of 600-700 ℃, and a gas phase volume space velocity of 20000-40000h -1.
According to a preferred embodiment of the present invention, wherein the reformate comprises at least one of CO, H 2、CO2、CH4 and H 2 O.
Preferably, the method further comprises subjecting the reformate to a dehydration treatment, resulting in a dehydrated reformate, preferably a cooled dehydration treatment.
More preferably, the dehydrated reformate contains no more than 0.01 mole% of H 2 O, preferably 0.001 to 0.005 mole%, no more than 8 mole% of CH 4 and no more than 12 mole% of CO 2.
More preferably, the molar ratio of CO to H 2 in the dehydrated reformate is 1:0.5-1.5. When the molar ratio of CO to H 2 in the dehydrated reforming product is not in the range, the method can adjust the molar ratio to the range by introducing CO or H 2 from an external source, and then introducing the mixture into a low-carbon alcohol synthesis unit to synthesize the low-carbon alcohol.
According to a preferred embodiment of the present invention, the lower alcohol synthesis step comprises subjecting at least part of the reformate obtained in the reforming step of methane and carbon dioxide (mainly CO and H 2 in the reformate, i.e. reformed synthesis gas) to lower alcohol synthesis and separating the synthesis product to obtain a crude lower alcohol and a separated synthesis gas. By "lower alcohol" is meant an alcohol having no more than 4C atoms, such as methanol, ethanol, propanol, n-butanol, and the like.
In the present invention, when a partially reformed synthesis gas is used to enter the lower alcohol synthesis step, the remainder of the reformed synthesis gas may be returned to the Fischer-Tropsch synthesis step for use as a feed gas. The invention is not particularly limited with respect to the proportion of lower alcohols going to the lower alcohol synthesis and Fischer-Tropsch synthesis steps. Those skilled in the art can adjust and select the materials according to actual needs and production conditions. For example, can be adjusted according to the market price of the product. At most the whole reformed synthesis gas may be passed to a lower alcohol synthesis or fischer-tropsch synthesis step.
Preferably, the conditions for synthesizing the lower alcohol include: the temperature is 250-290 ℃, the pressure is 2-6MPa, and the airspeed is 10000-30000h -1.
In the present invention, the specific catalyst selected for the synthesis of the lower alcohol is not particularly limited. Those skilled in the art can select a suitable catalyst by themselves according to the kind of the desired lower alcohol, restrictions of equipment and conditions, and the like. The catalyst may be a self-prepared catalyst according to the prior art or may be a commercially available related product.
According to a preferred embodiment of the present invention, when the lower alcohol is methanol, the catalyst can be selected from Zn-Cr-K catalyst of Snam company, moS2-M-K catalyst of DOW chemical company, modified Cu-Zn-Al catalyst of Denmark TOPSOE, etc. as catalyst for synthesizing low-carbon alcohol.
Preferably, the separation mode comprises normal pressure rectification or reduced pressure rectification, preferably the normal pressure rectification condition comprises a temperature of 80-150 ℃, preferably the reduced pressure rectification condition comprises a temperature of 80-150 ℃ and a pressure of-0.5 to 0.7MPa.
More preferably, the conditions of the atmospheric rectification include a temperature of 90-130 ℃ and a pressure of 0.1-0.5MPa.
More preferably, the conditions of the reduced pressure rectification include a temperature of 80-145 ℃ and a pressure of-0.5 to 0.2MPa.
According to a preferred embodiment of the present invention, wherein the crude lower alcohol comprises at least one of C1-C6 lower alcohol, C1-C6 lower aldehyde, C1-C3 organic acid and water. Preferably, the content of the lower alcohol is 65 to 95 mol%. More preferably, the content of the lower alcohol is 85 to 92 mol%.
Preferably, the method further comprises the operation of refining the crude lower alcohol to obtain a refined lower alcohol, preferably having a lower alcohol content of 99 mol% or more. The refining mode can be any existing refining mode for alcohol products in the field, and the specific operation and conditions of the refining mode are not particularly limited, so long as the content of the low-carbon alcohol in the obtained refined low-carbon alcohol meets the requirements.
More preferably, the process further comprises recycling the separated synthesis gas (as feed gas) to the step of lower alcohol synthesis.
The present invention will be described in detail by examples. It should be understood that the following examples are illustrative only and are not intended to limit the invention.
The bituminous coal used in the examples below was from Ningdong mining area with a moisture content of about 17.81.+ -. 0.5 wt.%, ash content of about 23.28.+ -. 0.1 wt.%, volatile content of about 36.14.+ -. 0.5 wt.%, carbon content of about 51.06.+ -. 0.5 wt.%, and particle size of about 40 mm.+ -. 5mm. Unless specifically stated, reagents were purchased from regular chemical suppliers and were pure analytically.
In the examples below, ppm is volume fraction unit, for example 1ppm refers to "parts per million by volume", unless specifically stated otherwise.
Example 1
Referring to the process flow in fig. 1, the bituminous coal is used as a raw material to carry out the cascade production of high-carbon olefin and low-carbon olefin:
(1) Preparation and purification of purified synthesis gas
Oxygen is introduced into bituminous coal, and the bituminous coal is subjected to a pulverized coal pressurized gasification technology (gasification pressure is 4.5MPa and gasification temperature is 1200 ℃) to prepare coarse coal gas, wherein the volume percentage of the coarse coal gas is CO: H 2:CO2:CH4:H2 S=48.29:24.31:14.26:12.96:0.18, 67 volume percent of coarse coal gas is subjected to sulfur-resistant transformation under the catalysis of a Qingdao communication QDB-04 catalyst at 250 ℃, the calculated volume airspeed of dry gas is 4000H -1, the water/gas mole ratio after transformation is 0.35, and the transformed coarse coal gas and the other 33 volume percent of unconverted coarse coal gas are mixed and then sent to a low-temperature methanol washing unit.
After the raw gas enters a low-temperature methanol washing unit, the raw gas is absorbed by low-temperature methanol at the temperature of-40 ℃ and the pressure of 3.5MPa, so that H 2 S is reduced to 0.1ppm, CO 2 is less than 20ppm, and H 2 S concentrated gas subjected to low-temperature methanol washing is sent to sulfur recovery;
The crude gas after low-temperature methanol washing enters methane for cryogenic separation, and the methane in the crude gas is separated by adopting mixed refrigerant of Kang Taisi and Boclaweiqi company at the temperature of-161 ℃ and the pressure of 4.4MPa, wherein the purity of the methane is as follows: the volume fraction of methane is more than or equal to 98 percent, the sulfur content is less than or equal to 0.1ppm, the volume fraction of CO 2 is less than or equal to 1.0 percent, and the pure synthetic gas meeting the synthesis of low-carbon alcohol is prepared after the cryogenic separation of methane from the raw gas.
(2) Fischer-Tropsch synthesis, product separation and tail gas decarbonization
The synthesis gas is subjected to Fischer-Tropsch synthesis reaction in a slurry bed reactor, and the adopted catalyst is a Fe-Mn-Cu-K catalyst (SiO 2 is used as a carrier, and the weight ratio of active components Fe to Cu to K to Mn to SiO 2 is 100:5:3:8:25). The reaction conditions include: the reaction pressure was 2.6MPa, the reaction temperature was 280℃and the hydrogen to carbon molar ratio (calculated as H 2/CO) was 3.0, the volume space velocity was 30000H -1. After the product is cooled and separated, the heavy hydrocarbon removes the olefin separation unit to separate the high-carbon alpha-olefin, and the mass ratio of the high-carbon alpha-olefin to the heavy hydrocarbon is 43.7%. The light hydrocarbon is removed the low temperature oil washing unit and is separated CO 2 through decarbonization unit after removing the organic matter, decarbonization unit adopts the mode of liquid absorption to decarbonize, and the absorption liquid that specifically adopts is 245g/L concentration potassium carbonate aqueous solution (containing V 2O5, pentavalent vanadium content is 22 g/L). The rest CO and H 2 are recycled to the Fischer-Tropsch reactor, and the CO 2 is subjected to methane removal and reforming to generate hydrogen-rich synthetic gas.
(3) Methane, CO 2 reforming
Methane separated from the raw gas and CO 2 separated in the Fischer-Tropsch synthesis process are mixed and then enter a reforming reactor, and reforming treatment conditions comprise: CH 4/CO2 volume ratio is 1.5, reactor pressure is 1MPa, and temperature is 600 ℃. The catalyst used was a Co-based catalyst (the support was Al 2O3 obtained by calcining pseudo-boehmite having a particle size of 10-120 μm at 400℃for 4 hours, the main active component was Co, the minor active component was Ce, and the weight ratio of the main active component to the minor active component was 1.5:1). The molar components of the product at the outlet of the reactor after cooling and dehydration are CO: H 2:CO2:CH4 =50.3:44.8:4.8:0.07, and 70% of the synthetic gas is subjected to further separation of moisture by deep cooling and then is subjected to synthesis of methanol units and 30% of the synthetic gas is subjected to Fischer-Tropsch synthesis units.
(4) Methanol synthesis
The synthesis gas after the cryogenic separation enters a methanol synthesizer, and methanol is synthesized under the conditions that the reaction pressure is 4.0MPa, the reaction temperature is 300 ℃, the hydrogen-carbon molar ratio (calculated by H 2/CO) is 3.0 and the volume airspeed is 25000H -1 by adopting a Zn-Cr-K catalyst of Italy Snam company;
The CO and H 2 of the purge gas after PSA separation of the synthesized low-carbon alcohol are recycled to the methanol synthesis reactor, the product after the methanol synthesis reactor enters a normal pressure methanol rectifying tower, and is separated under the conditions of 75 ℃ at the top of the tower, 150 ℃ at the bottom of the tower, normal pressure (1.01 MPa) and 2.3 reflux ratio, wherein the mole ratio of the separated product is 85% of methanol, 13.5% of water and 0.5% of fusel (the fusel mainly comprises ethanol, propanol and n-butanol).
Example 2
Referring to the process flow in fig. 1, the bituminous coal is used as a raw material to carry out the cascade production of high-carbon olefin and low-carbon olefin:
(1) Preparation and purification of purified synthesis gas
The method is characterized in that bituminous coal is used as a raw material, oxygen is introduced into the raw material, the raw material is prepared into raw gas through a pulverized coal pressurized gasification technology (gasification pressure is 4.5MPa and gasification temperature is 1200 ℃), the volume percentage of the raw gas is CO: H 2:CO2:CH4:H2 S=48.29:24.31:14.26:12.96:0.18, the raw gas is subjected to sulfur-resistant transformation under the condition that the temperature of the raw gas is 250 ℃,3.5MPa and Qingda communication QDB-04 type catalyst, the calculated volume airspeed of dry gas is 4000H -1, the water/gas mole ratio after transformation is 0.35, and the raw gas is mixed with other 33% of unconverted raw gas and then sent into a low-temperature methanol washing unit.
The mixed crude gas enters a low-temperature methanol washing unit, H 2 S is reduced to 0.1ppm by low-temperature methanol washing under the temperature of-40 ℃ and the pressure of 3.5MPa, CO 2 is less than 20ppm, and the H 2 S concentrated gas subjected to low-temperature methanol washing is sent to sulfur recovery.
(2) Methane separation
The crude gas after low-temperature methanol washing enters methane for cryogenic separation, and the methane in the crude gas is separated by adopting mixed refrigerant of Kang Taisi and Boclaweiqi company at the temperature of-161 ℃ and the pressure of 4.4MPa, wherein the purity of the methane is as follows: the volume fraction of methane is more than or equal to 98 percent, the sulfur content is less than or equal to 0.1ppm, the volume fraction of CO 2 is less than or equal to 1.0 percent, and the pure synthetic gas meeting the synthesis of low-carbon alcohol is prepared after the cryogenic separation of methane from the raw gas.
(3) Fischer-Tropsch synthesis, product separation and tail gas decarbonization
The synthesis gas is subjected to Fischer-Tropsch synthesis reaction in a slurry bed reactor, and the adopted catalyst is a Fe-Mn-Cu-K-B catalyst (the carrier is Al 2O3, and the weight ratio of active components Fe to Mn to Cu to K to B to Al 2O3 is 100:5:6:2:1.5:25). The reaction conditions include: the reaction pressure was 2.7MPa, the reaction temperature was 270 ℃, the hydrogen to carbon molar ratio (calculated as H 2/CO) was 2.5, and the volume space velocity was 25000H -1. After the product is cooled and separated, the heavy hydrocarbon removes the olefin and separates the high-carbon alpha-olefin, the high-carbon alpha-olefin accounts for 45.6% of the mass ratio of the heavy hydrocarbon. The light hydrocarbon is removed the low temperature oil washing unit and is separated CO 2 through decarbonization unit after removing the organic matter, decarbonization unit adopts the mode of liquid absorption to decarbonize, and the absorption liquid that specifically adopts is 245g/L concentration potassium carbonate aqueous solution (containing V 2O5, pentavalent vanadium content is 22 g/L). The rest CO and H 2 are recycled to the Fischer-Tropsch reactor, and the CO 2 is subjected to methane removal and reforming to generate hydrogen-rich synthetic gas.
(4) Methane, CO 2 reforming
Methane separated from the raw gas and CO 2 separated in the Fischer-Tropsch synthesis process are mixed and then enter a reforming reactor, and reforming treatment conditions comprise: CH 4/CO2 volume ratio is 1, reactor pressure is 0.5MPa, and temperature is 650 ℃. The catalyst used was a Co-based catalyst (the carrier was SiO 2 obtained by calcining a silica powder having a particle size of 10-120 μm at 600℃for 4 hours, the main active component was Co, the minor active component was Mg, and the weight ratio of the main active component to the minor active component was 1:1). The molar components of the product at the outlet of the reactor after cooling and dehydration are CO: H 2:CO2:CH4 =46.3:48.8:4.1:0.14, and 70% of the synthetic gas is subjected to further separation of moisture by cryogenic cooling and then is subjected to synthesis of a methanol unit and 30% of the synthetic gas is subjected to Fischer-Tropsch synthesis unit.
(5) Synthesis of methanol
The synthesis gas after cryogenic separation enters a methanol synthesizer, and methanol is synthesized under the conditions that the reaction pressure is 5.0MPa, the reaction pressure is 260 ℃ and the hydrogen-carbon molar ratio (calculated by H 2/CO) is 2.2 and the volume airspeed is 30000H -1 by adopting a modified Zn-Zn-Al catalyst of Denmark TOPSOE company;
The CO and H 2 of the purge gas after PSA separation of the synthesized low-carbon alcohol are recycled to the methanol synthesis reactor, the product after the methanol synthesis reactor enters a normal pressure methanol rectifying tower, and is separated under the conditions of 75 ℃ at the top of the tower, 150 ℃ at the bottom of the tower, normal pressure and 2.0 reflux ratio, wherein the mole ratio of the main components in the separated crude methanol product is 88.9% of methanol, 10.5% of water and 0.6% of fusel (the fusel mainly comprises ethanol, propanol and n-butanol).
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (40)
1. A method for zero emission of coal olefins, the method comprising the steps of: preparing and purifying synthesis gas, fischer-Tropsch synthesis of high-carbon hydrocarbon, reforming methane and carbon dioxide, and synthesis of low-carbon alcohol;
The method comprises the steps of preparing and purifying raw coal by using synthesis gas to obtain pure synthesis gas and methane, wherein the pure synthesis gas enters a high-carbon hydrocarbon Fischer-Tropsch synthesis step to obtain a liquid phase product containing high-carbon hydrocarbon and a gas phase product containing unreacted synthesis gas and CO 2, CO 2 in the gas phase product and methane obtained in the synthesis gas preparation and purification step enter a methane and carbon dioxide reforming step to obtain a reformed product, the reformed product is used as raw gas to enter a low-carbon alcohol synthesis step, purge gas generated in the low-carbon alcohol synthesis step is recycled in the low-carbon alcohol synthesis step, and optionally part of the reformed synthesis gas is returned to the Fischer-Tropsch synthesis step to be used as raw gas;
The synthetic gas preparation and purification step comprises the steps of mixing raw material coal and O 2 for coal gasification, and sequentially carrying out alcohol washing and methane separation on the obtained raw gas after sulfur-tolerant conversion to obtain pure synthetic gas and methane;
The coal gasification conditions comprise the temperature of 1000-1500 ℃ and the pressure of 4-6MPa, and the volume ratio of raw material coal to O 2 is 1:2-3;
The crude gas contains 0.05-0.1 volume percent of CH 4, 55-65 volume percent of CO, 21-31 volume percent of H 2 and 3-8 volume percent of CO 2;
the step of sulfur-tolerant shift comprises the steps of performing sulfur-tolerant shift on part of the raw gas, and performing alcohol washing on a mixture of the residual raw gas which is not subjected to sulfur removal shift and the converted raw gas;
the sulfur-tolerant shift crude gas accounts for 25-50% by volume of the total crude gas;
The methane and carbon dioxide reforming step comprises the steps of reforming CO 2 obtained in the high-carbon hydrocarbon Fischer-Tropsch synthesis step and methane separated in the synthesis gas preparation and purification step to obtain a reformate;
The catalyst used in the reforming treatment comprises a main active component, a secondary active component and a carrier, wherein the main active component is Co, the secondary active component is at least one of Th, ni, ce, mo, mg, pa, pt, ru, rh and Ir, and the carrier is at least one of a carbon carrier, an inorganic oxide and a molecular sieve;
The content of the main active component accounts for 0.05-30% of the total mass of the catalyst;
the content of the secondary active component accounts for 0.01-20 wt% of the total mass of the catalyst;
The reforming treatment conditions comprise reactor pressure of 0.5-5MPa, temperature of 450-850 ℃, and gas phase volume space velocity of 5000-50000h -1;
The raw coal is selected from inferior coal powder with 15-30 wt% of moisture content, 9-25 wt% of ash content, 28-37 wt% of volatile content and 49-61 wt% of carbon content;
The Fischer-Tropsch reaction conditions comprise pressure of 2-4MPa, temperature of 220-350 ℃, molar ratio of H 2 to CO of 2-5:1, and gas phase volume space velocity of 5000-50000H -1;
The catalyst adopted in the Fischer-Tropsch reaction is a Fe-Mn-Cu-K catalyst or a Fe-Mn-Cu-K-M catalyst, wherein M is at least one of B, C, N, zn, ga and Sn;
the weight ratio of Fe, mn, cu, K in the Fe-Mn-Cu-K catalyst is 100:0.2-12:0.2-12:0.1 to 10, wherein in the Fe-Mn-Cu-K-M catalyst, the weight ratio of Fe, mn, cu, K to M is 100:0.2-12:0.2-12:0.1-10:3-40;
The liquid phase product comprises C8-C12 alpha-olefins and naphtha, wherein the content of the alpha-olefins is 35-75 mol%.
2. The method according to claim 1, wherein the feed coal has a particle size of 5-50 μm.
3. The method of claim 1 or 2, the O 2 being provided by air.
4. The method of claim 1 or 2, wherein the coal gasification is performed by at least one of fixed bed gasification, fluidized bed gasification, and entrained flow gasification.
5. The method of claim 1, wherein the sulfur tolerant shift employs a Co-Mo catalyst.
6. The method of claim 5, wherein a Co-Mo catalyst is employed wherein the support is at least one of activated alumina, magnesium aluminate spinel, and aluminum titanium magnesium composite support.
7. The method according to claim 1, wherein the step of alcohol washing is performed by means of low temperature methanol washing and/or polyethylene glycol dimethyl ether washing.
8. The method of claim 7, wherein the low temperature methanol wash temperature is from-30 ℃ to-50 ℃.
9. The method of claim 1, 6, 7 or 8, wherein the methane separation is performed by cryogenic separation and/or adsorptive separation.
10. The method of claim 4, wherein the methane separation is performed by cryogenic separation and/or adsorptive separation.
11. The method of claim 1, wherein the sulfur shift resistant conditions include a temperature of 220-450 ℃, a pressure of 2-5MPa, and a volume space velocity of 1000-3000h -1 on a raw gas basis.
12. The method of claim 1, 6, 7, 8 or 11, wherein the conditions of the alcohol wash comprise a temperature of-33 ℃ to-55 ℃ and a pressure of 2-6MPa.
13. The method of claim 4, wherein the conditions of the alcohol washing include a temperature of-33 ℃ to-55 ℃ and a pressure of 2-6MPa.
14. The method of claim 12, wherein the alcohol washing results in an H 2 S content in the raw gas after alcohol washing of less than 0.1ppm and a CO 2 content of less than 20 ppm.
15. The method of claim 9, wherein the cryogenic separation conditions comprise a temperature of-145 ℃ to-175 ℃ and a pressure of 3-8MPa.
16. The method of claim 1, wherein the alcohol washing step further comprises recovering washed H 2 S concentrate.
17. The method of claim 1, wherein the step of fischer-tropsch synthesis of higher hydrocarbons comprises fischer-tropsch reacting pure synthesis gas produced in the synthesis gas preparation and purification step as a feedstock.
18. The method of claim 1, wherein the step of fischer-tropsch synthesis of higher hydrocarbons further comprises gas-liquid separation of the reaction products to obtain a liquid phase product and a gaseous phase product.
19. The method of claim 1, the gas phase product comprising CH 4 and/or CO 2.
20. The process of claim 1, 18 or 19, wherein the process further comprises decarbonizing the gas phase product to obtain recovered synthesis gas and CO 2.
21. The process of claim 20, wherein the recovered synthesis gas is recycled to the fischer-tropsch reaction.
22. The method of claim 20, wherein the decarbonation treatment comprises liquid absorption and/or molecular sieve adsorption.
23. The method of claim 22, wherein the decarbonizing treatment is liquid absorption.
24. The method of claim 23, wherein the liquid absorption is performed by using K 2CO3 aqueous solution and/or Na 2CO3 aqueous solution.
25. The method of claim 1, wherein the reformate comprises at least one of CO, H 2、CO2、CH4, and H 2 O.
26. The method of claim 25, further comprising subjecting the reformate to a dehydration treatment to obtain a dehydrated reformate.
27. The method of claim 26, wherein the dewatering is a chilled dewatering process.
28. The method of claim 26 or 27, wherein the dehydrated reformate contains no more than 0.01 mol% H 2 O, no more than 8 mol% CH 4, and no more than 12 mol% CO 2.
29. The method of claim 28, wherein the molar ratio of CO to H 2 in the dehydrated reformate is 1:0.5-1.5.
30. The method according to claim 29, wherein the content of H 2 O in the dehydrated reformate is 0.001 to 0.005 mol%,
31. The method of claim 1, wherein the lower alcohol synthesis step comprises lower alcohol synthesis of at least a portion of the reformate obtained from the methane and carbon dioxide reforming step and separation of the synthesis product to obtain a crude lower alcohol and separated synthesis gas.
32. The method of claim 31, wherein the conditions for the synthesis of the lower alcohol comprise: the temperature is 250-290 ℃, the pressure is 2-6MPa, and the airspeed is 10000-30000h -1.
33. The method of claim 32, wherein the means of separation comprises atmospheric or vacuum distillation.
34. The method of claim 33, wherein the atmospheric distillation conditions comprise a temperature of 80-150 ℃.
35. The method of claim 33, wherein the conditions of reduced pressure distillation comprise a temperature of 80-150 ℃, a pressure of-0.5 to-0.7 MPa.
36. The method of claim 33, wherein the crude lower alcohol comprises at least one of a C1-C6 lower alcohol, a C1-C6 lower aldehyde, a C1-C3 organic acid, and water.
37. The method of claim 36, wherein the lower alcohol is present in an amount of 65-95 mole percent.
38. The method according to claim 36 or 37, wherein the method further comprises the operation of refining the crude lower alcohol to obtain a refined lower alcohol.
39. The method of claim 38, wherein the refined lower alcohol has a lower alcohol content of 99 mole% or more.
40. The method of any one of claims 31-37, wherein the method further comprises recycling the separated synthesis gas to the step of lower alcohol synthesis.
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| US7485767B2 (en) * | 2005-06-29 | 2009-02-03 | Exxonmobil Chemical Patents Inc. | Production of synthesis gas blends for conversion to methanol or Fischer-Tropsch liquids |
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| CN101979468A (en) * | 2010-11-11 | 2011-02-23 | 中国科学院山西煤炭化学研究所 | A Fischer-Tropsch synthesis reaction process with low carbon emissions |
| WO2014111310A1 (en) * | 2013-01-17 | 2014-07-24 | Shell Internationale Research Maatschappij B.V. | Process for the preparation of synthesis gas |
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