CN102614763B - Method for processing Fischer-Tropsch synthesis tail gas - Google Patents
Method for processing Fischer-Tropsch synthesis tail gas Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 133
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 63
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 62
- 239000007789 gas Substances 0.000 claims abstract description 276
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 84
- 239000001257 hydrogen Substances 0.000 claims abstract description 79
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 65
- 238000000926 separation method Methods 0.000 claims abstract description 52
- 238000005261 decarburization Methods 0.000 claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 claims abstract description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 15
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 15
- 239000002737 fuel gas Substances 0.000 claims abstract description 14
- 239000012528 membrane Substances 0.000 claims abstract description 10
- 238000001179 sorption measurement Methods 0.000 claims abstract 2
- 230000008569 process Effects 0.000 claims description 90
- 239000003921 oil Substances 0.000 claims description 72
- 239000010408 film Substances 0.000 claims description 67
- 238000001764 infiltration Methods 0.000 claims description 25
- 230000008595 infiltration Effects 0.000 claims description 25
- 238000010521 absorption reaction Methods 0.000 claims description 23
- 230000002745 absorbent Effects 0.000 claims description 22
- 239000002250 absorbent Substances 0.000 claims description 22
- 238000003672 processing method Methods 0.000 claims description 22
- 239000003245 coal Substances 0.000 claims description 18
- 239000003381 stabilizer Substances 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 229940072033 potash Drugs 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 5
- 235000015320 potassium carbonate Nutrition 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 4
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229920000151 polyglycol Polymers 0.000 claims description 4
- 239000010695 polyglycol Substances 0.000 claims description 4
- 238000005194 fractionation Methods 0.000 claims description 3
- 238000003754 machining Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 238000002453 autothermal reforming Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 238000000629 steam reforming Methods 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- 230000001131 transforming effect Effects 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 abstract description 13
- 238000005406 washing Methods 0.000 abstract description 4
- 230000035515 penetration Effects 0.000 abstract 3
- 239000000047 product Substances 0.000 description 19
- 239000004215 Carbon black (E152) Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IUQJDHJVPLLKFL-UHFFFAOYSA-N 2-(2,4-dichlorophenoxy)acetate;dimethylazanium Chemical compound CNC.OC(=O)COC1=CC=C(Cl)C=C1Cl IUQJDHJVPLLKFL-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Landscapes
- Hydrogen, Water And Hydrids (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a method for processing Fischer-Tropsch synthesis tail gas, which comprises the steps of decarburization, membrane separation, low temperature oil washing, tail gas conversion and pressure swing adsorption(PSA). The method is characterized in that tail gas from a Fischer-Tropsch synthesis apparatus is passed through a decarburization unit for removing CO2 component; decarburization tail gas is sent to a membrane separation unit for recovering hydrogen, membrane separation penetration gas with rich hydrogen is boosted and then sent to a PSA unit for hydrogen production, also can be returned to the Fischer-Tropsch synthesis apparatus after boosting, the membrane separation unit can be returned to the Fischer-Tropsch synthesis apparatus according to the required gas with any H2/CO proportion, membrane separation non-penetration gas can be passed through a low temperature oil washing unit for recovering liquefied gas component and then sending to a tail gas conversion unit, and also can be sent to the tail gas conversion unit directly for hydrogen production; in the tail gas conversion unit, oil washing dry gas or membrane separation non-penetration gas are conversed, methane and hydrocarbons components are conversed to crude synthetic gas; the conversed crude synthetic gas converses CO and H2O to CO2 and H2, the conversed gas after decarburization removes CO2 to obtain hydrogen rich gas, the hydrogen rich gas is passed through the PSA unit for recovering hydrogen, hydrogen in the PSA unit can be used for whole plant, the analytic gas can be used as fuel gas.
Description
Technical field
The present invention relates to a kind of processing method of Fischer-Tropsch process exhaust, be that coal is in gasification and then the indirect liquefaction process through the synthetic production of Fischer-Tropsch liquid fuel, the method that the Fischer-Tropsch process exhaust of its generation is processed, it is through comprising that five processing steps in decarburization unit, film separation unit, low temperature oil wash unit, tail gas conversion unit and PSA unit optimize the process after integrated.
Background technology
Coal resources in China is abundant, and oil and natural gas relative inadequacy of resources, coal is converted into liquid fuel on a large scale with the process of high effect cleaning, will effectively alleviate the pressure of oil supply, promotes economic continual and steady development.Coal liquefaction technology can be divided into ICL for Indirect Coal Liquefaction technology and direct coal liquefaction technology.ICL for Indirect Coal Liquefaction technology refers to that coal first contains H through gasification production
2with the coal based synthetic gas of CO, coal based synthetic gas obtains suitable H through processing steps such as conversion and purifications again
2the synthesis gas of/CO ratio, then synthesis gas enters Fischer-Tropsch synthesis device and under certain temperature and pressure, carries out the reaction of Fischer-Tropsch synthesis catalytic, generate the thick product such as gaseous hydrocarbon, liquid hydrocarbon, synthetic wax, liquid hydrocarbon and synthetic wax can be produced the products such as diesel oil, gasoline, naphtha and refining wax again after hydrotreatment.In Ministry of Science and Technology's 863 Program, under the many enterprises such as the government departments such as the Chinese Academy of Sciences and He Luan group of Yi Tai group support, by Zhongke Synthetic Oil Technology Co., Ltd., go through autonomous technological development for many years, obtained and take Fischer-Tropsch synthesizing high temperature slurry state bed process and starch with high temperature the complete indirect coal liquefaction process technology that state bed ferrum-based catalyst is technological core and (see Chinese invention patent ZL200410012189.2, the open CN101396647A of ZL200410012191.X and patent), this technology is through the checking of pilot scale and 160,000 tons/year of ICL for Indirect Coal Liquefaction artificial oil industrialization demonstration plants, possessed the technical conditions of implementing the project construction of megaton large industrialized.
The Fischer-Tropsch process exhaust producing in the Fischer-Tropsch synthesis process of ICL for Indirect Coal Liquefaction is mainly by H
2, CO, lower carbon number hydrocarbons (C
6following hydrocarbon), CO
2, N
2deng composition, Fischer-Tropsch process exhaust is usually used as fuel traditionally, be used for heat supply or generating, but the rise along with International Crude Oil, it is very uneconomical that this way becomes, reduced the use value of resource, if can isolate the products such as hydrogen, liquefied gas, low-carbon alkene from Fischer-Tropsch process exhaust, or being converted into synthesis gas recycles, can greatly improve the economic worth of Fischer-Tropsch process exhaust, improve the complex energy utilization ratio of whole artificial oil factory simultaneously, increase economic benefit and the product category of artificial oil factory.
Dry discloses technological process (the Mark E Dry that a kind of Fischer-Tropsch process exhaust is processed, TheFischer-Tropsch process-commercial aspects, Catalysis Today, 1990,6 (3): 183-206), adopt the method for low-temperature deep separation that Fischer-Tropsch process exhaust is isolated respectively to CO
2, methane, ethene, propylene, C
3-C
5hydrocarbon mixture, then methane is through O
2with water vapour partial oxidation reforming be that synthesis gas loops back in reactor feed gas again, ethene is used for polyethylene processed, propylene is used for polypropylene processed, C
3-C
5hydrocarbon is through products such as oligomerisation reaction gasoline processed, diesel oil and LPG.This technological process is complicated, and energy consumption is large, but the product category forming is more.
The open CN1944358A of Chinese patent has proposed a kind of C reclaiming in Fischer-Tropsch process exhaust
3-C
5the method of hydrocarbon mixture, has adopted the steps such as decarburization, first cold, washing, dehydration, decompression, deep cooling, fractionation, has obtained C
3-C
5hydrocarbon mixture, existing alkene in hydrocarbon mixture, also has alkane.
In the ICL for Indirect Coal Liquefaction artificial oil production process of scale, can produce a large amount of Fischer-Tropsch process exhausts, how to utilize more rationally and effectively and to transform Fischer-Tropsch process exhaust, be related to economy and the feasibility of whole coal oil mill.The present invention sets about from overall technique and products perfection, a kind of technological processes of Fischer-Tropsch process exhaust processing of the optimizations that form through five parts such as decarburization, film separation, low temperature oil wash, tail gas conversion and PSA have been proposed, this technological process fully takes into account the feature that Fischer-Tropsch process exhaust forms, and this technological process can remove the CO in Fischer-Tropsch process exhaust
2, produce highly purified H
2and liquefied gas (LPG), isolate suitable H
2the synthesis gas of/CO ratio circulates used, and this technological process also can be adjusted flexibly kind and the formation of product when operation according to the needs of product.
Summary of the invention
The processing method that the object of this invention is to provide a kind of ICL for Indirect Coal Liquefaction Fischer-Tropsch process exhaust.
The present invention proposes a kind of processing method of ICL for Indirect Coal Liquefaction Fischer-Tropsch process exhaust, comprise decarburization unit, film separation unit, low temperature oil wash unit, tail gas conversion unit and PSA unit five parts, the method is the complete Fischer-Tropsch process exhaust processing method for the feature exploitation of ICL for Indirect Coal Liquefaction artificial oil.
The method of the invention describe, in general terms is as follows:
From Fischer-Tropsch synthesis unit tail gas, first through decarburization unit, remove CO wherein
2component, and then deliver to film separation unit.In film separation process, the comparatively faster gas of infiltration rate, as water vapour, H
2isopreference sees through film and by enrichment, permeates gas; And the relatively slow gas of infiltration rate, as methane, N
2, the gas such as CO, hydrocarbon gas in the delay side of film by enrichment, i.e. impermeable gas.The infiltration gas of described film separation unit can return to Fischer-Tropsch synthesizer after boosting, and also can deliver to PSA unit purifying hydrogen of hydrogen, also can a part go a Fischer-Tropsch synthesizer part to go to PSA unit.Through the hydrogen Gong Quan of PSA unit separating-purifying factory consumption hydrogen production device and/or Fischer-Tropsch synthesis unit, use, the resolution gas of PSA unit is made fuel gas and is used.Described impermeable gas is delivered to low temperature oil wash unit and is reclaimed liquefied gas component, and in described low temperature oil wash unit, isolated oil wash dry gas is sent into tail gas conversion unit.Described impermeable gas also can be without low temperature oil wash unit the gas conversion unit that directly truncates.In described tail gas conversion unit, the separated impermeable gas of oil wash dry gas or film obtains crude synthesis gas through transforming, more finally obtains hydrogen-rich gas through operations such as conversion, decarburizations.This hydrogen-rich gas is delivered to PSA unit recover hydrogen, and hydrogen Gong Quan factory consumption hydrogen production device and/or the Fischer-Tropsch synthesis unit of recovery are used, and the resolution gas of PSA unit is made fuel gas and used.
In the present invention, chemical absorption process can be selected in described decarburization unit, physical absorption process or physics-chemical absorption process, typical chemical absorption process has: monoethanolamine process (MEA), hot potash method (as Benfield) etc., typical physical absorption process has: propene carbonate method (Fluor), low-temperature rectisol method (Rectisol), polyglycol dimethyl ether process (Selexol/NHD), 1-METHYLPYRROLIDONE NMP method (Purisol) etc., typical physics-chemical absorption process has: normal temperature methyl alcohol is washed method (Amisol), sulfolane process (sulfolaneprocess) and activation N methyldiethanol amine method (MDEA).
In the present invention, the infiltration gas lift of described film separation unit can return to Fischer-Tropsch synthesis unit after pressing, and also can go to PSA unit, also can go to Fischer-Tropsch synthesis unit and PSA unit simultaneously.The separated infiltration of film gas after described boosting can share PSA system with the hydrogen-rich gas of tail gas conversion unit, independent PSA system also can be set and process film separation unit infiltration gas.Through the hydrogen Gong Quan of PSA separating-purifying factory consumption hydrogen production device and/or Fischer-Tropsch synthesis unit, use, PSA unit resolves gas is made fuel gas and is used.Described film separation unit can be adjusted the amount that decarbonated exhaust gas enters film separation unit as required, and the degree of controlling diaphragm separation, thereby produces arbitrary H after the part impermeable gas that film separation unit obtains and the decarbonated exhaust gas that does not enter film separation unit are mixed
2the gas of/CO ratio returns to Fischer-Tropsch synthesis unit.The diffusion barrier that this film separation unit is selected comprises anisotropic membrane or utilized thin film composite membranes, utilizes the solubility of various gas in film different with diffusion coefficient, and infiltration rate is variant relatively in film to cause gas with various.Under the poor effect of driving force-film pressure at both sides, the comparatively faster gas of infiltration rate, as water vapour, H
2isopreference is through film and by enrichment, and the relatively slow gas of infiltration rate, as methane, N
2, CO, hydrocarbon gas etc. in the delay side of film by enrichment, thereby reach the object of mist separation.
In the present invention, from the impermeable gas of film separation unit, go to low temperature oil wash unit to reclaim liquefied gas component, also can be without the low temperature oil wash unit gas conversion unit that directly truncates.Described low temperature oil wash unit comprises absorption tower, Analytic Tower and stabilizer, if C in absorbent
5constituent content is more, and regenerator (depentanizer) can be set.The Main Function on described absorption tower is the C absorbing in low temperature oil wash unit feed gas
3 +component is (containing C
3component), this absorption tower tower top separates the oil wash dry gas gas shift unit that truncates, and at the bottom of tower, rich absorbent oil removes Analytic Tower.The Main Function of Analytic Tower is the C removing in rich absorbent oil
2 +component is (containing C
2component), the resolution gas obtaining from Analytic Tower tower top returns to absorption tower and again absorbs after cooling, and at the bottom of Analytic Tower tower, deethanization oil is delivered to stabilizer, and stabilizer is also referred to as debutanizing tower.The overhead product of described stabilizer is liquefied gas product, and at the bottom of stabilizer tower, oil can part recycle as absorbent, and part is as the raw material of other device.Described absorbent can be from fischer-tropsch unit, also can be from oil product machining cell or other unit.According to the character of absorbent, regenerator can be set, also referred to as depentanizer, also regenerator can be set.Regenerator raw material is oil at the bottom of stabilizer, and the object of regenerator is the part C removing in circulation absorbent
5and C
6component, the C obtaining from tower top
5and C
6light naphthar component is gone to other unit, or goes to other unit after dividing oil to mix with tower bottom, and at the bottom of tower, oil can, all as absorbent, also can, partly as absorbent, remove other device after partly mixing with tower top light naphthar.Described technical process can be supplemented absorbent also can not supplement absorbent, and supplementary absorbent can be from fischer-tropsch unit, also can be from oil product machining cell or other unit, and supplementary absorbent can go to absorption tower also can remove other device.Described absorption tower number of theoretical plate is 5～40, and tower top temperature is-40～20 ℃, and column bottom temperature is-40～30 ℃, and operating pressure is 1.0～6.0MPa; Described Analytic Tower number of theoretical plate is 5～40, and tower top temperature is 40～200 ℃, and column bottom temperature is 70～300 ℃, and operating pressure is 1.0～6.0MPa; Described stabilizer number of theoretical plate is 5～40, and tower top temperature is 20～180 ℃, and column bottom temperature is 80～300 ℃, and operating pressure is 0.5～3.0MPa; Described regenerator number of theoretical plate is 3～35, and tower top temperature is 40～200 ℃, and column bottom temperature is 80～300 ℃, and operating pressure is 0.2～1.5MPa.Preferably absorption tower number of theoretical plate is 10-20, and tower top temperature is-10-0 ℃, and column bottom temperature is 0-10 ℃, and operating pressure is 2.5-4.5MPa; Preferably Analytic Tower number of theoretical plate is 10-20, and tower top temperature is 80-120 ℃, and column bottom temperature is 180-220 ℃, and operating pressure is 2.5-4.5MPa; Preferably stabilizer number of theoretical plate is 20-30, and tower top temperature is 60-90 ℃, and column bottom temperature is 180-230 ℃, and operating pressure is 1.0-2.0MPa; Preferably regenerator number of theoretical plate is 10-20, and tower top temperature is 100-140 ℃, and column bottom temperature is 140-180 ℃, and operating pressure is 0.5-1.0MPa.
In the present invention, described tail gas conversion unit comprises transform portion, conversion fraction and decarburization part.In tail gas conversion unit the separated impermeable gas of oil wash dry gas or film first through described transform portion by the hydrocarbons such as feed gas methane and oxygen or steam reaction generation CO and H
2, obtain containing H
2, CO, CO
2, N
2and H
2the crude synthesis gas of O, this crude synthesis gas enters described conversion fraction, and part CO is wherein converted into H
2and CO
2, obtaining conversion gas, this conversion gas partly removes CO wherein through described decarburization
2component obtains hydrogen-rich gas.Described transform portion can be selected Steam Reforming Process, catalytic oxidation process, non-catalytic partial oxidation technique and Auto-thermal reforming process, described conversion fraction, according to the whether resistance to sulphur of catalyst of selecting, is divided into again sulphur-resistant conversion and non-sulfur resistant conversion process, according to the serviceability temperature of catalyst, can be divided into high temperature shift and low-temperature conversion and wide temperature shift, described decarburization part can be selected chemical absorption process, physical absorption process and physics-chemical absorption process, typical chemical absorption process has: monoethanolamine process (MEA), hot potash method (as Benfield) etc., typical physical absorption process has: propene carbonate method (Fluor), low-temperature rectisol method (Rectisol), polyglycol dimethyl ether process (Selexol/NHD), 1-METHYLPYRROLIDONE NMP method (Purisol) etc., typical physical-chemical absorption process has: normal temperature methyl alcohol is washed method (Amisol), sulfolane process (sulfolane process) and activation N methyldiethanol amine method (MDEA).
In the present invention, the described hydrogen-rich gas from tail gas conversion unit goes PSA unit recover hydrogen, and this hydrogen Gong Quan factory consumption hydrogen production device and/or Fischer-Tropsch synthesis unit are used, and PSA unit resolves gas is made fuel gas and used.Feature of the present invention:
(1) Fischer-Tropsch process exhaust passes through the process route of decarburization unit, film separation unit, low temperature oil wash unit, tail gas conversion unit and PSA unit successively, makes overall economic benefit reach optimum;
(2) low temperature oil wash unit has reclaimed the liquefied gas component in tail gas, has improved the added value of synthetic oil;
(3) flow direction and the flow of film separation unit infiltration gas and impermeable gas can be controlled flexibly, to reach different production objects.
Accompanying drawing explanation
Accompanying drawing 1-5 is Fischer-Tropsch process exhaust processing technological flow block diagram, wherein
101-decarburization raw material (Fischer-Tropsch synthesis unit tail gas); 102-decarbonated exhaust gas; 103-impermeable gas; 104-permeates gas; 105-oil wash dry gas; 106-hydrogen-rich gas; 107-PSA-1 unit hydrogen; 108-PSA-1 unit tail gas; 109-returns to a certain H of Fischer-Tropsch synthesis unit
2the gas of/CO ratio; 110-PSA-2 unit hydrogen; 111-PSA-2 unit tail gas; 112-returns to Fischer-Tropsch synthesis unit infiltration gas; 113-liquefied gas
The specific embodiment
Below with reference to accompanying drawing 1-5, method of the present invention is described in further detail.
Fischer-Tropsch process exhaust handling process mainly comprises decarburization unit, film separation unit, low temperature oil wash unit, tail gas conversion unit and PSA unit five parts, and in actual production, each logistics whereabouts can be controlled flexibly, gives an explaination below from five angles.
Flow process one:
From the tail gas (logistics 101) of Fischer-Tropsch synthesis unit, through decarburization unit, remove CO wherein
2component; Decarbonated exhaust gas (logistics 102) can all or part of striping separative element recover hydrogen, the infiltration gas (logistics 104) that is rich in hydrogen goes the hydrogen manufacturing of PSA unit, impermeable gas (logistics 103) can go to low temperature oil wash unit to reclaim liquefied gas component wherein, the gas conversion unit that can directly truncate, does not enter a certain H obtaining after the decarbonated exhaust gas of film separation unit and the part impermeable gas of film separation unit mix in addition yet
2the gas of/CO ratio (logistics 109) returns to Fischer-Tropsch synthesis unit; Liquefied gas component in the separated impermeable gas of low temperature oil wash unit reclamation film, obtain liquefied gas (logistics 113) product, oil wash dry gas (logistics 105) the gas conversion unit that truncates, in tail gas conversion unit the separated impermeable gas of oil wash dry gas or film first through transform portion by the hydrocarbons such as feed gas methane and oxygen or steam reaction generation CO and H
2, obtain containing H
2, CO, CO
2, N
2and H
2the crude synthesis gas of O, crude synthesis gas enters conversion fraction, and part CO is wherein converted into H
2and CO
2, obtaining conversion gas, conversion gas partly removes CO wherein through decarburization
2component obtains hydrogen-rich gas (logistics 106); Together with the infiltration gas of the hydrogen-rich gas of tail gas conversion unit and film separation unit, go to PSA unit, hydrogen (logistics 107) the Gong Quan factory consumption hydrogen production device and/or the Fischer-Tropsch synthesis unit that through PSA unit, reclaim are used, and PSA unit tail gas (logistics 108) is made fuel gas and used.
Flow process two:
From the tail gas (logistics 101) of Fischer-Tropsch synthesis unit, through decarburization unit, remove CO wherein
2component; Decarbonated exhaust gas can all or part of (logistics 102) striping separative element recover hydrogen, the infiltration gas (logistics 104) that is rich in hydrogen goes independently PSA unit hydrogen manufacturing, the hydrogen (logistics 110) reclaiming returns to Fischer-Tropsch synthesis unit, tail gas (logistics 111) is made fuel gas and is used, film separation unit impermeable gas (logistics 103) can go to low temperature oil wash unit to reclaim liquefied gas component wherein, the gas conversion unit that can directly truncate, does not enter a certain H obtaining after the decarbonated exhaust gas of film separation unit and the part impermeable gas of film separation unit mix in addition yet
2the gas of/CO ratio (logistics 109) returns to Fischer-Tropsch synthesis unit; Liquefied gas component in the separated impermeable gas of low temperature oil wash unit reclamation film, obtain liquefied gas (logistics 113) product, oil wash dry gas (logistics 105) the gas conversion unit that truncates, through tail gas conversion unit, obtain hydrogen-rich gas (logistics 106) and go to PSA unit, hydrogen (logistics 107) the Gong Quan factory consumption hydrogen production device and/or the Fischer-Tropsch synthesis unit that through PSA unit, reclaim are used, and PSA unit tail gas (logistics 108) is made fuel gas and used.
Flow process three:
From the tail gas (logistics 101) of Fischer-Tropsch synthesis unit, through decarburization unit, remove CO wherein
2component; Decarbonated exhaust gas can all or part of (logistics 102) striping separative element recover hydrogen, the infiltration gas (logistics 104) that is rich in hydrogen returns to Fischer-Tropsch synthesis unit, impermeable gas (logistics 103) can go to low temperature oil wash unit to reclaim liquefied gas component wherein, the gas conversion unit that can directly truncate, does not enter a certain H obtaining after the decarbonated exhaust gas of film separation unit and the part impermeable gas of film separation unit mix in addition yet
2the gas of/CO ratio (logistics 109) returns to Fischer-Tropsch synthesis unit; Liquefied gas component in the separated impermeable gas of low temperature oil wash unit reclamation film, obtain liquefied gas (logistics 113) product, oil wash dry gas (logistics 105) the gas conversion unit that truncates, through tail gas conversion unit, obtain hydrogen-rich gas (logistics 106) and go to PSA unit, hydrogen (logistics 107) the Gong Quan factory consumption hydrogen production device and/or the Fischer-Tropsch synthesis unit that through PSA unit, reclaim are used, and PSA unit tail gas (logistics 108) is made fuel gas and used.
Flow process four:
From the tail gas (logistics 101) of Fischer-Tropsch synthesis unit, through decarburization unit, remove CO wherein
2component; Decarbonated exhaust gas can all or part of (logistics 102) striping separative element recover hydrogen, an infiltration gas part (logistics 112) that is rich in hydrogen is returned to Fischer-Tropsch synthesis unit, its cofiltering gas (logistics 104) goes the hydrogen manufacturing of PSA unit, impermeable gas (logistics 103) can go to low temperature oil wash unit to reclaim liquefied gas component wherein, the gas conversion unit that can directly truncate, does not enter a certain H obtaining after the decarbonated exhaust gas of film separation unit and the part impermeable gas of film separation unit mix in addition yet
2the gas of/CO ratio (logistics 109) returns to synthesis unit; Liquefied gas component in the separated impermeable gas of low temperature oil wash unit reclamation film, obtain liquefied gas (logistics 113) product, oil wash dry gas (logistics 105) the gas conversion unit that truncates, through tail gas conversion unit, obtain going to PSA unit together with the infiltration gas of hydrogen-rich gas (logistics 106) and film separation unit, hydrogen (logistics 107) the Gong Quan factory consumption hydrogen production device and/or the Fischer-Tropsch synthesis unit that through PSA unit, reclaim are used, and PSA unit tail gas (logistics 108) is made fuel gas and used.
Flow process five:
From the tail gas (logistics 101) of Fischer-Tropsch synthesis unit, through decarburization unit, remove CO wherein
2component, decarbonated exhaust gas can all or part of (logistics 102) striping separative element recover hydrogen, an infiltration gas part (logistics 112) that is rich in hydrogen is returned to Fischer-Tropsch synthesis unit, its cofiltering gas (logistics 104) goes independently PSA unit hydrogen manufacturing, hydrogen (logistics 110) the Gong Quan factory consumption hydrogen production device and/or the Fischer-Tropsch synthesis unit that reclaim are used, tail gas (logistics 111) is done fuel gas and is used, film separation unit impermeable gas (logistics 103) can go to low temperature oil wash unit to reclaim liquefied gas component wherein, also gas conversion unit can directly truncate, in addition do not enter a certain H obtaining after the decarbonated exhaust gas of film separation unit and the part impermeable gas of film separation unit mix
2the gas of/CO ratio (logistics 109) returns to Fischer-Tropsch synthesis unit, liquefied gas component in the separated impermeable gas of low temperature oil wash unit reclamation film, obtain liquefied gas (logistics 113) product, oil wash dry gas (logistics 105) the gas conversion unit that truncates, through tail gas conversion unit, obtain hydrogen-rich gas (logistics 106) and go to PSA unit, hydrogen (logistics 107) the Gong Quan factory consumption hydrogen production device and/or the Fischer-Tropsch synthesis unit that through PSA unit, reclaim are used, and PSA unit tail gas (logistics 108) is made fuel gas and used.
With specific embodiment, technical scheme of the present invention is done to more detailed invention below, but its protection domain not limiting the present invention in any way.
embodiment 1
According to the flow process one in Fig. 1, be example, provide embodiment 1.From the tail gas (logistics 101) of Fischer-Tropsch synthesis unit, through decarburization unit, select hot potash method to remove CO wherein
2component; A part of striping separative element recover hydrogen in decarbonated exhaust gas (logistics 102), film separation unit selects two-stage film separated, the separated impermeable gas of one-level film and do not enter a certain H that the decarbonated exhaust gas of film separation unit is mixed to get
2the gas of/CO ratio as circulating air (logistics 109) return to Fischer-Tropsch synthesis unit, the separated infiltration of one-level film gas goes secondary film separated, secondary film separated infiltration gas (logistics 104) goes the hydrogen manufacturing of PSA unit, and impermeable gas (logistics 103) goes to low temperature oil wash unit to reclaim liquefied gas component wherein; Liquefied gas component in the separated impermeable gas of low temperature oil wash unit reclamation film, obtain liquefied gas (logistics 113) product, oil wash dry gas (logistics 105) the gas conversion unit that truncates, in tail gas conversion unit oil wash dry gas first through transform portion by the hydrocarbons such as feed gas methane and oxygen or steam reaction generation CO and H
2, obtain containing H
2, CO, CO
2, N
2and H
2the crude synthesis gas of O, crude synthesis gas enters conversion fraction, and part CO is wherein converted into H
2and CO
2, obtaining conversion gas, conversion gas partly removes CO wherein through decarburization
2component obtains hydrogen-rich gas (logistics 106); Together with the infiltration gas of the hydrogen-rich gas of tail gas conversion unit and film separation unit, go to PSA unit, hydrogen (logistics 107) the Gong Quan factory consumption hydrogen production device and/or the Fischer-Tropsch synthesis unit that through PSA unit, reclaim are used, and PSA unit tail gas (logistics 108) is done fuel gas and used.Each logistics data is in Table 1:
Table 1 embodiment 1 logistics data
Below described embodiment of the present invention in detail, can do a lot of improvement and variation obviously for a person skilled in the art and can not deviate from essence spirit of the present invention.All these changes and improvements are all within protection scope of the present invention.
Claims (17)
1. a coal-based indirect liquefaction Fischer-Tropsch process exhaust processing method, is characterized in that the method comprises the following steps:
(1) first through decarburization unit from Fischer-Tropsch synthesis unit tail gas, remove CO wherein
2component;
(2) above-mentionedly in decarburization unit, remove CO
2after tail gas send into film separation unit, the infiltration gas lift that obtains being rich in hydrogen after film separation removes pressure-variable adsorption (PSA) unit preparing high purity hydrogen after pressing,
Or the infiltration gas lift that is rich in hydrogen all returns to Fischer-Tropsch synthesis unit after pressing,
Or the infiltration gas lift that is rich in hydrogen presses rear section to go to PSA unit, part is returned to Fischer-Tropsch synthesis unit;
(3) impermeable gas of film separation unit goes to low temperature oil wash unit to reclaim liquefied gas component wherein, the oil wash dry gas the obtaining gas conversion unit that truncates,
Or described impermeable gas is directly delivered to tail gas conversion unit processing processing without low temperature oil wash unit;
(4) in tail gas conversion unit, oil wash dry gas or impermeable gas are first through transforming the hydrocarbons such as methane and oxygen or steam reaction generation CO and H
2, obtain containing H
2, CO, CO
2, N
2and H
2the crude synthesis gas of O, crude synthesis gas, by conversion, is converted into H by part CO wherein
2and CO
2, obtain conversion gas, then remove the CO in this conversion gas
2component obtains hydrogen-rich gas;
(5) hydrogen-rich gas from tail gas conversion unit goes PSA unit recover hydrogen;
(6) the consumption hydrogen production device of the hydrogen Gong Quan factory after purifying in PSA unit and/or Fischer-Tropsch synthesizer use, and the resolution gas of PSA unit is made fuel gas and used.
2. Fischer-Tropsch process exhaust processing method as claimed in claim 1, it is characterized in that described film separation unit can adjust the amount that decarbonated exhaust gas enters film separation unit as required, and the degree of controlling diaphragm separation, thereby after being mixed, the part impermeable gas that film separation unit obtains and the decarbonated exhaust gas that does not enter film separation unit produce arbitrary H
2the gas of/CO ratio returns to Fischer-Tropsch synthesis unit.
3. Fischer-Tropsch process exhaust processing method as claimed in claim 1, when the separated infiltration of the film gas after boosting described in it is characterized in that goes to PSA unit, can share PSA system with the hydrogen-rich gas of tail gas conversion unit, or independent PSA system is set.
4. Fischer-Tropsch process exhaust processing method as claimed in claim 1, is characterized in that the CO of described decarburization unit
2removal methods can adopt monoethanolamine process, hot potash method, propene carbonate method, low-temperature rectisol method, polyglycol dimethyl ether process, 1-METHYLPYRROLIDONE NMP method, normal temperature methyl alcohol to wash any one method in method, sulfolane process and activation N methyldiethanol amine method.
5. Fischer-Tropsch process exhaust processing method as claimed in claim 1, is characterized in that it is anisotropic membrane or utilized thin film composite membranes that described film separation unit carries out separated film used.
6. Fischer-Tropsch process exhaust processing method as claimed in claim 1, is characterized in that described low temperature oil wash unit is provided with absorption tower, desorber and stabilizer; Absorption tower Main Function is to absorb in low temperature oil wash unit feed containing C
3c
3 +component, overhead gas is oil wash dry gas, is rich absorbent oil at the bottom of tower; Desorber Main Function is to remove in rich absorbent oil containing C
2c
2 -component, is deethanization oil at the bottom of tower, and deethanization oil is delivered to stabilizer, and stabilizer overhead product is liquefied gas product, and at the bottom of stabilizer tower, oil part can be used as absorbent, and part is as other device raw material.
7. Fischer-Tropsch process exhaust processing method as claimed in claim 6, is characterized in that absorbent is from fischer-tropsch unit, from oil product machining cell or other parts.
8. Fischer-Tropsch process exhaust processing method as claimed in claim 6, is characterized in that the character according to absorbent, and it is depentanizer that regenerator is set, or regenerator is not set.
9. Fischer-Tropsch process exhaust processing method as claimed in claim 8, is characterized in that if C in absorbent
5constituent content is more, and it is depentanizer that regenerator can be set.
10. Fischer-Tropsch process exhaust processing method as claimed in claim 8 or 9, is characterized in that regenerator raw material is oil at the bottom of stabilizer tower, and the object of regenerator is the part C from removed overhead circulation absorbent
5and C
6component, at the bottom of tower, oil is all as absorbent, or part is made absorbent and is partly removed other device.
11. Fischer-Tropsch process exhaust processing methods as claimed in claim 6, is characterized in that described absorption tower number of theoretical plate is 5～40, and tower top temperature is-40～20 ℃, and tower reactor temperature is-40～30 ℃, and operating pressure is 1.0～6.0MPa; Described desorber number of theoretical plate is 5～40, and tower top temperature is 40～200 ℃, and tower reactor temperature is 70～300 ℃, and operating pressure is 1.0～6.0MPa; Described stabilizer number of theoretical plate is 5～40, and tower top temperature is 20～180 ℃, and tower reactor temperature is 80～300 ℃, and operating pressure is 0.5～3.0MPa.
12. Fischer-Tropsch process exhaust processing methods as claimed in claim 11, is characterized in that absorption tower number of theoretical plate is 10-20, and tower top temperature is-10-0 ℃, and tower reactor temperature is 0-10 ℃, and operating pressure is 2.5-4.5MPa; Desorber number of theoretical plate is 10-20, and tower top temperature is 80-120 ℃, and tower reactor temperature is 180-220 ℃, and operating pressure is 2.5-4.5MPa; Stabilizer number of theoretical plate is 20-30, and tower top temperature is 60-90 ℃, and tower reactor temperature is 180-230 ℃, and operating pressure is 1.0-2.0MPa.
13. Fischer-Tropsch process exhaust processing methods as claimed in claim 8 or 9, is characterized in that described regenerator number of theoretical plate is 3～35, and tower top temperature is 40～200 ℃, and tower reactor temperature is 80～300 ℃, and operating pressure is 0.2～1.5MPa.
14. Fischer-Tropsch process exhaust processing methods as claimed in claim 13, is characterized in that regenerator number of theoretical plate is 10-20, and tower top temperature is 100-140 ℃, and tower reactor temperature is 140-180 ℃, and operating pressure is 0.5-1.0MPa.
15. Fischer-Tropsch process exhaust processing methods as claimed in claim 1, it is characterized in that described tail gas conversion unit comprises transform portion, conversion fraction and decarburization part, in tail gas conversion unit the separated impermeable gas of oil wash dry gas or film first through described transform portion by the hydrocarbons such as feed gas methane and O
2or steam reaction generates CO and H
2, obtain containing H
2, CO, CO
2, N
2and H
2the crude synthesis gas of O, this crude synthesis gas enters described conversion fraction, and part CO is wherein converted into H
2and CO
2, obtaining conversion gas, this conversion gas partly removes CO wherein through described decarburization
2component obtains hydrogen-rich gas.
16. Fischer-Tropsch process exhaust processing methods as claimed in claim 1, is characterized in that described transform portion can adopt Steam Reforming Process, catalytic oxidation process, non-catalytic partial oxidation technique and Auto-thermal reforming process in any interior method.
17. Fischer-Tropsch process exhaust processing methods as claimed in claim 1, is characterized in that removing the CO in conversion gas in described step (4)
2the method of component can adopt monoethanolamine process, hot potash method, propene carbonate method, low-temperature rectisol method, polyglycol dimethyl ether process, 1-METHYLPYRROLIDONE NMP method, normal temperature methyl alcohol to wash any one method in method, sulfolane process and activation N methyldiethanol amine method.
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| CN109045929B (en) * | 2018-08-28 | 2024-08-16 | 上海东化环境工程有限公司 | Refinery dry gas recovery system and method |
| CN111116300A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Shallow cooling separation device and method for preparing olefin from synthesis gas |
| CN111467913A (en) * | 2020-03-27 | 2020-07-31 | 大连海奥膜技术有限公司 | Comprehensive recycling process and equipment for refinery tail gas |
| CN111871159A (en) * | 2020-07-15 | 2020-11-03 | 中石化南京化工研究院有限公司 | Membrane separation coupling alcohol amine solution for capturing flue gas CO2Apparatus and method |
| CN113582134A (en) * | 2021-08-10 | 2021-11-02 | 内蒙古伊泰煤制油有限责任公司 | Method and system for recovering reduction tail gas of oil product synthesis device |
| CN114437841A (en) * | 2022-02-14 | 2022-05-06 | 中科合成油技术股份有限公司 | Method and device for co-producing natural gas, LPG and naphtha by using Fischer-Tropsch synthesis tail gas |
| CN115253612B (en) * | 2022-08-25 | 2024-02-02 | 国家能源集团宁夏煤业有限责任公司 | Fischer-Tropsch synthesis tail gas separation and recovery system and method |
| CN115651705A (en) * | 2022-08-25 | 2023-01-31 | 陕西未来能源化工有限公司 | Membrane separation hydrogen extraction system and method for low-carbon hydrocarbon entering working section |
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