CN106588526B - A method of using coal and oil refinery dry gas as the system of raw material alkene and alkene processed - Google Patents
A method of using coal and oil refinery dry gas as the system of raw material alkene and alkene processed Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 137
- 239000003245 coal Substances 0.000 title claims abstract description 122
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 85
- 239000002994 raw material Substances 0.000 title claims abstract description 22
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 354
- 239000007789 gas Substances 0.000 claims abstract description 314
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 273
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 273
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 142
- 238000002407 reforming Methods 0.000 claims abstract description 84
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 81
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 67
- 238000002309 gasification Methods 0.000 claims abstract description 59
- 238000002360 preparation method Methods 0.000 claims abstract description 47
- 239000003250 coal slurry Substances 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims description 99
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 90
- 239000001257 hydrogen Substances 0.000 claims description 65
- 229910052739 hydrogen Inorganic materials 0.000 claims description 65
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 63
- 239000003795 chemical substances by application Substances 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 238000003795 desorption Methods 0.000 claims description 39
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 38
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 229910001868 water Inorganic materials 0.000 claims description 28
- 239000012752 auxiliary agent Substances 0.000 claims description 25
- 238000002803 maceration Methods 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 10
- 150000002910 rare earth metals Chemical class 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 239000003034 coal gas Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 238000006057 reforming reaction Methods 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 230000009466 transformation Effects 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 239000005431 greenhouse gas Substances 0.000 abstract description 10
- 229960004424 carbon dioxide Drugs 0.000 description 61
- 238000000926 separation method Methods 0.000 description 41
- 239000000047 product Substances 0.000 description 35
- 230000008569 process Effects 0.000 description 25
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 230000008859 change Effects 0.000 description 10
- 238000001802 infusion Methods 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052593 corundum Inorganic materials 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000004615 ingredient Substances 0.000 description 8
- 230000000737 periodic effect Effects 0.000 description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000005265 energy consumption Methods 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000003345 natural gas Substances 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 238000004939 coking Methods 0.000 description 4
- 238000010494 dissociation reaction Methods 0.000 description 4
- 230000005593 dissociations Effects 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000011343 solid material Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000003077 lignite Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 2
- 239000003830 anthracite Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229960002413 ferric citrate Drugs 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 2
- 150000002680 magnesium Chemical class 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 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
- 239000002904 solvent Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical class [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- -1 for example Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 150000003109 potassium Chemical class 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0485—Set-up of reactors or accessories; Multi-step processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- 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
- C01B3/346—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 heat generated by superheated steam
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of using coal and oil refinery dry gas as the system of raw material alkene and using the system using coal and oil refinery dry gas as the method for raw material alkene, wherein, the system includes sequentially connected water-coal-slurry preparation unit, coal gasification unit, purified synthesis gas unit, F- T synthesis unit, the carbon dioxide outlet of F- T synthesis unit and/or the carbon dioxide outlet of purified synthesis gas unit are connected to the carbon dioxide entrance of methane dry reforming unit, the methane outlet of oil refinery dry gas separative unit is connected to the methane entrance of methane dry reforming unit, or the methane outlet of oil refinery dry gas separative unit and the methane outlet of F- T synthesis unit are connected to the methane entrance of methane dry reforming unit.It is provided by the invention using coal and oil refinery dry gas as the system of raw material alkene, carbon dioxide and methane both greenhouse gases are used simultaneously, it is allowed to be changed into the product with high added value, reduces greenhouse gas emission, significantly improve resource, the energy utilization rate of integrated artistic.
Description
Technical field
The present invention relates to a kind of using coal and oil refinery dry gas as the system of raw material alkene, and with coal and oil refinery dry gas is original
Expect the method for alkene processed.
Background technique
Alkene is basic chemical industry raw material important in chemical industry production, and measures a national oil chemical industry hair
Open up horizontal mark.27,500,000 tons of China's ethylene production capacity in 2015 is expected, domestic supportability is 64%；It expects 2015
24,000,000 tons of China's propylene production capacity, domestic supportability are 77%, and China's alkene supply-demand relationship is nervous.Preparing low-carbon olefins at present
Method can be divided into 3 major class: petroleum path, natural gas route and coal route by raw material.Using the method for light oil cracking,
The method that i.e. petroleum path carrys out preparing low-carbon olefins is used by most countries in the world, and account for about olefin yield 65% is left
It is right.Using natural gas as raw material, by oxidative coupling or Benson method preparing low-carbon olefins technology, mainly it is with ethylene in product
Main, the yield of propylene is lower.Research with coal based synthetic gas through methanol-to-olefins also achieves rapid development, builds at home
More set process units.
China's energy is in the resource distribution situation of rich coal, more natural gases, oil starvation, will be between coal or natural gas by F- T synthesis
Switch through that turn to clean, highly effective liquid fuel be the importance for rationally utilizing resource, China's oil imbalance between supply and demand can be alleviated
Major Technology.Coal chemical technology coal in China's emerges rapidly through methanol-to-olefins in recent years, and coal is through synthesis gas alkene directly processed
Hydrocarbon (FTO technique) is another coal-to-olefin technique.The technique first by coal or natural gas be converted into synthesis gas (carbon monoxide and
Hydrogen), the process of low-carbon alkene of the carbon atom number less than or equal to 4 is directly made using F- T synthesis.Currently used FTO
Technique olefin process process is shown in Fig. 1, including sequentially connected water-coal-slurry preparation unit, coal gasification unit, Water gas shift/WGS list
Member, purified synthesis gas unit, F- T synthesis unit and separation of olefins unit, detailed process are to prepare fine coal and water in water-coal-slurry
Water-coal-slurry is made in unit, water-coal-slurry is delivered into coal gasification unit, generates coal gasification crude synthesis gas with oxygen, coal gasification is thick
Synthesis gas complies with the requirement of Fischer-Tropsch synthesis through the molar ratio of WGS unit adjustment hydrogen and carbon monoxide, then
Sour gas and sulfide are removed through synthesis gas clean unit, synthesis gas is purified, obtained decontaminating syngas is conveyed into
F- T synthesis occurs for F- T synthesis unit, generates the logistics of olefin-containing, which isolates alkene, Fischer-Tropsch through separation of olefins unit
The carbon dioxide and methane then outlet that synthesis unit generates.Its main problem is: 1, energy consumption is high, carbon atom utilization rate is low；2,
CO2 emissions are 5~6 times of conventional petroleum route；Since Fischer-Tropsch synthetic is distributed by Anderson-Schulz-
The limitation of Flory rule (chain growth is with the molar distribution of exponential decrease), and it is limited by a large amount of first caused by the strongly exothermic property of reaction
Alkane, carbon dioxide generate, and FTO technique entirety efficiency is relatively low, seriously affects the process of industrialization of FTO technique.Therefore, optimize FTO
Technique, selects that a kind of efficiency is high, the system of GHG emissions mitigation is extremely important.
Summary of the invention
In order to overcome drawbacks described above, the present invention provides a kind of using coal and oil refinery dry gas as the system of raw material alkene and side
Method prepares alkene using system provided by the invention, has the advantages that greenhouse gas emissions are few and system energy efficiency is high.
To achieve the goals above, the present invention provides a kind of using coal and oil refinery dry gas as the system of raw material alkene, special
Sign is, which includes that water-coal-slurry preparation unit, coal gasification unit, purified synthesis gas unit, F- T synthesis unit, refinery are dry
Gas separative unit and methane dry reforming unit, the water-coal-slurry preparation unit, coal gasification unit, purified synthesis gas unit, Fischer-Tropsch
Synthesis unit is sequentially connected, the carbon dioxide outlet of the F- T synthesis unit and/or the carbon dioxide of purified synthesis gas unit
Outlet is connected to the carbon dioxide entrance of methane dry reforming unit, the methane outlet and methane dry reforming of oil refinery dry gas separative unit
The methane entrance of unit be connected to or the methane outlet of oil refinery dry gas separative unit and the methane outlet of F- T synthesis unit with
The methane entrance of methane dry reforming unit is connected to.
The present invention also provides a kind of using coal and oil refinery dry gas as the method for raw material alkene, which is characterized in that this method
The following steps are included:
1) water-coal-slurry is made in fine coal and water；
2) with oxygen high-temperature gasification is occurred into for the water-coal-slurry and reacts obtained coal gasification crude synthesis gas；
3) the coal gasification crude synthesis gas is purified, is purified synthesis gas and carbon dioxide gas；
4) make the decontaminating syngas that Fischer-Tropsch synthesis occur, and gained mixture is separated, obtain olefin-containing
Logistics and carbon dioxide and methane；
5) oil refinery dry gas is separated, isolates methane therein；
6) by step 3) and/or the resulting carbon dioxide of step 4) and with the resulting methane of step 5) or step 4) and
The resulting methane of step 5) carries out the reaction of methane dry reforming.
The present invention is by joint coal-to-olefin technique, oil refinery dry gas separating technology and methane dry reforming technique, to titanium dioxide
Carbon and methane both greenhouse gases are used simultaneously, are allowed to be changed into the product with high added value, reduce greenhouse gases
Discharge, significantly improves resource, the energy utilization rate of integrated artistic；In addition, the present invention is inhaled by strongly exothermic coal gasification unit and by force
The methane dry reforming unit integration of heat, the reaction for being used as heat medium to pass through methane dry reforming unit VII first crude synthesis gas E
Strongly exothermic coal gasification unit crude synthesis gas is introduced highly endothermic methane dry reforming unit by device preheating furnace, discharges the former
Heat be supplied to the latter, compared with prior art, improve efficiency, reduce energy consumption；Meanwhile being with coal and oil refinery dry gas
During raw material alkene, it is used in combination on the basis of system provided by the invention currently preferred for F- T synthesis
The loaded catalyst of reaction, available higher CO conversion and higher selectivity of light olefin, favorably
In industrialization promotion.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is existing coal through synthesis gas olefin process schematic diagram；
Fig. 2 is the signal that a kind of coal of preferred embodiment according to the present invention combines methane dry reforming system through synthesis gas
Figure；
Fig. 3 is that the coal of another preferred embodiment according to the present invention combines showing for methane dry reforming system through synthesis gas
It is intended to；
Fig. 4 is that the coal of yet another preferred form according to the present invention combines showing for methane dry reforming system through synthesis gas
It is intended to；
Fig. 5 is that the coal of another preferred embodiment according to the present invention combines showing for methane dry reforming system through synthesis gas
It is intended to.
Description of symbols
I water-coal-slurry preparation unit A fine coal
II coal gasification unit B water
III WGS unit C water-coal-slurry
IV purified synthesis gas cells D oxygen
V F- T synthesis unit E coal gasification crude synthesis gas
Crude synthesis gas after the transformation of VI separation of olefins unit F
VII methane dry reforming unit G methane
VIII oil refinery dry gas separative unit H carbon dioxide
J decontaminating syngas K alkene
L oil refinery dry gas M sulfide
The methane of N Fischer-Tropsch synthesis product P oil refinery dry gas separation
The hydrogen U methane dry reforming of Q oil refinery dry gas separation reacts resulting synthesis gas
Y unreacted synthesis gas Z periodic off-gases
Specific embodiment
Below in conjunction with attached drawing, detailed description of the preferred embodiments.It should be understood that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of using coal and oil refinery dry gas as the system of raw material alkene, which is characterized in that such as Fig. 2-5 institute
Show, which includes water-coal-slurry preparation unit I, coal gasification unit II, purified synthesis gas unit IV, F- T synthesis unit V, refinery
Dry gas separative unit VIII and methane dry reforming unit VII, the water-coal-slurry preparation unit I, coal gasification unit II, synthesis gas are net
Change unit IV, F- T synthesis unit V is sequentially connected；The carbon dioxide outlet and/or purified synthesis gas of the F- T synthesis unit V
The carbon dioxide outlet of unit IV is connected to the carbon dioxide entrance of methane dry reforming unit VII, oil refinery dry gas separative unit
The methane outlet of VIII is connected to the methane entrance of methane dry reforming unit VII or the first of oil refinery dry gas separative unit VIII
The methane outlet of alkane outlet and F- T synthesis unit V are connected to the methane entrance of methane dry reforming unit VII.
In the present invention, the alkene is preferably low-carbon alkene, further preferably C2-C4Alkene.
The system provided according to the present invention, the syngas outlet and F- T synthesis unit V of the methane dry reforming unit VII
Synthesis gas entrance connection, there is no particular limitation for mode of the present invention to connection, for example, can by synthesis letter shoot into
Row connection.
The system provided according to the present invention, the carbon dioxide outlet and purified synthesis gas unit of the F- T synthesis unit V
The carbon dioxide outlet of IV connects each by the carbon dioxide entrance of carbon dioxide conveyance conduit and methane dry reforming unit VII
Logical, under preferable case, the carbon dioxide outlet of the carbon dioxide outlet and purified synthesis gas unit IV of F- T synthesis unit V first leads to
Piping connection, then the two is connected to by carbon dioxide conveyance conduit with the carbon dioxide entrance of methane dry reforming unit VII,
So that the carbon dioxide H that purified synthesis gas unit IV is generated enters together with the carbon dioxide H generated in Fischer-Tropsch synthesis
Methane dry reforming unit VII, is used to it.
The system provided according to the present invention, the methane outlet and methane dry reforming list of the oil refinery dry gas separative unit VIII
The methane entrance of first VII is connected to or methane outlet and the F- T synthesis unit V of the oil refinery dry gas separative unit VIII
Methane outlet be connected to the methane entrance of methane dry reforming unit VII, under preferable case, the F- T synthesis unit V's
Methane outlet and the methane outlet of oil refinery dry gas separative unit VIII are each by methane conveyance conduit and methane dry reforming unit
The methane entrance of VII is connected to, it is further preferred that the methane outlet of F- T synthesis unit V and oil refinery dry gas separative unit VIII
Methane outlet first pass through pipeline connection, both then pass through the methane entrance of methane conveyance conduit and methane reforming unit VII
Connection, so that the methane G that Fischer-Tropsch synthesis generates enters methane dry reforming together with the methane P that oil refinery dry gas unit generates
Unit VII.In methane dry reforming unit VII, to above two greenhouse gases, i.e. carbon dioxide and methane, it is used, makes
Be changed into the synthesis gas U (carbon monoxide and hydrogen) that can be recycled, synthesis gas U passes through pipeline and purified synthesis gas unit
The synthesis gas J that IV is generated delivers into F- T synthesis unit V together, on the one hand to improve the efficiency of system, on the other hand reduces
The discharge of greenhouse gases.
A kind of preferred embodiment of the system provided according to the present invention, as shown in Figure 3 and Figure 5, coal gasification unit II and
It is additionally provided with WGS unit III between purified synthesis gas unit IV, the coal gasification crude synthesis gas E from coal gasification unit II
It is thick after obtained transformation after adjusting the hydrogen of crude synthesis gas E and the molar ratio of carbon monoxide into WGS unit III
Synthesis gas F enters clean unit IV and is purified.
The system provided according to the present invention, in the preferred case, the outlet crude synthesis gas E of coal gasification unit II and methane are dry
The heating medium entrance of the reactor preheating furnace of reformer unit VII is connected to, the reactor preheating furnace of methane dry reforming unit VII
Heating medium outlet is then connected to the feed(raw material)inlet of the feed(raw material)inlet of WGS unit III or clean unit IV, thus
Crude synthesis gas E is used as heat medium to pass through the reactor preheating furnace of methane dry reforming unit VII first, enters back into Water gas shift/WGS
Unit III carries out Water gas shift/WGS or directly carries out purified synthesis gas in purified synthesis gas unit IV again, so that by putting by force
The coal gasification unit crude synthesis gas of heat introduces highly endothermic methane dry reforming unit, improves utilization efficiency of heat energy.
The system provided according to the present invention, the oil refinery dry gas separative unit VIII be equipped with hydrogen outlet, hydrogen outlet with
The crude synthesis gas entrance of purified synthesis gas unit IV is connected to or enters WGS unit together with water-gas crude synthesis gas E
III, preferably as shown in Figure 4 and Figure 5, the hydrogen outlet of oil refinery dry gas separative unit VIII are thick with purified synthesis gas unit IV's
The connection of synthesis gas entrance is closed so that being added into crude synthesis gas F using the hydrogen in oil refinery dry gas as hydrogen source as Fischer-Tropsch
It at the raw material of reaction, and can be used for adjusting the hydrogen of raw material and the molar ratio of carbon monoxide, be allowed to be suitable for Fischer-Tropsch synthesis,
It can be omitted Water gas shift/WGS process in this way, improve the efficiency of system.
According to the present invention, above-mentioned conveyance conduit is preferably provided with control valve, for correspondingly control to be corresponding as needed
The input quantity of gas.
The system provided according to the present invention, the system further include separation of olefins unit VI, can be to from F- T synthesis list
The Fischer-Tropsch synthetic N of first V is separated, and alkene K logistics is obtained, and the present invention is not special to the separation of olefins unit VI
It limits, can be device commonly used in the art, as long as being able to achieve the isolated purpose between each alkene.
Under preferable case, system provided by the invention further include by the outlet of the unreacted synthesis gas of separation of olefins unit VI with
The unstripped gas entrance of F- T synthesis unit V is connected to, and unreacted synthesis gas Y is thus returned to F- T synthesis unit V and carries out Fischer-Tropsch
Synthetic reaction.
The present invention also provides a kind of using coal and oil refinery dry gas as the method for raw material alkene, which is characterized in that this method
The following steps are included:
1) water-coal-slurry C is made in fine coal A and water B；
2) with oxygen D high-temperature gasification is occurred into for the water-coal-slurry C and reacts obtained coal gasification crude synthesis gas E；
3) the coal gasification crude synthesis gas E is purified, is purified synthesis gas J and carbon dioxide gas H；
4) make the decontaminating syngas J that Fischer-Tropsch synthesis occur, and gained mixture is separated, obtain olefin-containing
The logistics and carbon dioxide H and methane G of K；
5) oil refinery dry gas L is separated, isolates methane P therein；
6) step 3) and/or the resulting carbon dioxide H of step 4) and the resulting methane of step 4) and step 5) are carried out
The reaction of methane dry reforming.
There is no particular limitation to the equipment that step 1) uses by the present invention, as long as water-coal-slurry can be made in fine coal A and water B
C can be carried out in the water-coal-slurry preparation unit I in above system provided by the invention in the preferred case.The present invention
To the condition of preparation water-coal-slurry C, there is no particular limitation, for example, the fine coal A can be former for solid commonly used in the art
Material coal obtains after crushing and screening.The partial size of fine coal A is preferably 5mm-50mm.The weight ratio of fine coal A and water B is preferably 1:
0.2-0.5.The fine coal A can be the existing various coal dusts suitable for water-coal-slurry liquefaction process, can be anthracite, poor cigarette,
Meager lean coal, coking coal, rich coal, 1/3 coking coal, gas rich coal, bottle coal, glues coal, weakly caking coal, dross coal, jet coal, lignite in 1/2 at lean coal
One of or it is a variety of.Under preferable case, the fine coal be low ash point, low-sulfur point in above-mentioned coal, high volatile, high ash melting point,
The high-quality thermal coal of high heating value, is particularly preferred as calorific value >=6000cal/kg in above-mentioned coal, ash content≤10%, sulphur content≤1%
Coal.
There is no particular limitation to the equipment that step 2) uses by the present invention, as long as it is high that water-coal-slurry C and oxygen D can be made to occur
Coal gasification crude synthesis gas E is made in warm gasification reaction in the preferred case can be in above system provided by the invention
It is carried out in coal gasification unit II, it is preferable that the reacting furnace temperature of the coal gasification unit II can be 1200-1500 DEG C, pressure
It can be 2.8-3.2MPa, the hydrogen of the crude synthesis gas E of generation and the molar ratio of carbon monoxide can be 0.4-1.2:1.
In the present invention, pressure used is absolute pressure.
There is no particular limitation to the equipment that step 3) uses by the present invention, as long as coal gasification crude synthesis gas E can be carried out
Purification is purified synthesis gas J and carbon dioxide gas H to remove the sour gas and sulfide M in crude synthesis gas E,
The synthesis gas is the gaseous mixture of carbon monoxide and hydrogen.It in the preferred case, can be in above system provided by the invention
Purified synthesis gas unit IV in carry out, the hydrogen of obtained decontaminating syngas J and the molar ratio of carbon monoxide can be 0.8-
2.5:1 preferably 0.9-1.2:1.The mode of purification for example removes CO with low-temp methanol washing method (Rectisol method)2、H2S、
COS, HCN and NH3Deng.The H of high concentration2S gas enters second level Claus conversion technique and carries out sulfur recovery；By CO when Mathanol regenerating2
Desorption, as methane dry reforming raw material.
There is no particular limitation to the equipment that step 4) uses by the present invention, can be used for Fischer-Tropsch for commonly used in the art
The equipment of synthetic reaction, for example, the step can carry out in the F- T synthesis unit V in above system provided by the invention.
The Fischer-Tropsch synthesis is the production process for producing low-carbon alkene, low-carbon alkanes and oil-phase product, while by-product methane, dioxy
Change carbon.
There is no particular limitation for condition of the present invention to the Fischer-Tropsch synthesis, for example, the condition of Fischer-Tropsch synthesis
It can be with are as follows: reaction temperature is 280-370 DEG C, preferably 300-360 DEG C；Reaction pressure is 0.5-2.5MPa, preferably 0.8-
1.8MPa；Gas space velocity can be 2000-100000h-1, preferably 5000-50000h-1。
The method provided according to the present invention, in step (4), catalyst that the present invention uses the Fischer-Tropsch synthesis
There is no particular limitation, can be the selection of this field routine, ferrum-based catalyst such as Fe/Al can be used for example2O3Base catalyst
Or cobalt-base catalyst.In situations where it is preferred, the present invention uses a kind of loaded catalyst, which includes containing
It θ-alumina support of modifying agent and is supported on this and contains the active component and auxiliary agent on θ-alumina support of modifying agent,
In, the modifying agent is one of alkaline components, alkaline earth metal component and group ivb metal component or a variety of, the work
Property group is divided into group VIII metal component, and the auxiliary agent contains alkaline components and/or rare earth component.
In above-mentioned loaded catalyst, the carrier is θ-aluminium oxide containing modifying agent, and without containing modifying agent
θ-aluminium oxide is compared, θ-aluminium oxide CO containing modifying agent2- TPD desorption temperature is higher than θ-oxygen without containing modifying agent
Change the CO of aluminium2- TPD desorption temperature.Therefore, in the present invention, θ-aluminium oxide before modification after performance can be with CO2- TPD table
Sign, CO2- TPD indicates θ-aluminium oxide to CO2Desorption temperature, temperature height indicates that θ-aluminium oxide alkalinity is strong, is conducive to low-carbon alkene
Hydrocarbon desorption.In CO2In-TPD spectrogram, peak temperature appearance position and peak area size show that θ-aluminium oxide alkalinity is strong and weak, CO2It is de-
Attached peak temperature is high, peak area is big illustrates that θ-aluminium oxide alkalinity is strong, is conducive to alkene desorption.A kind of preferred reality according to the present invention
Apply mode, the CO of carrier of the present invention2Figure, which is desorbed, in-TPD has CO at 80-120 DEG C2Desorption peaks.Preferably, the desorption peaks
Peak area be 1-3a.u. (arbitrary unit).In the case where being one of Zr, K and Mg for modifying agent, the carrier
CO2- TPD desorption figure also has another CO at preferred 350-500 DEG C of 300-5502Desorption peaks.Preferably, another described CO2
The peak area of desorption peaks is 0.5-2a.u. (arbitrary unit).And existing carrier does not have above-mentioned desorption peaks.
In the present invention, support C O2- TPD and following catalyst CO-TPD are all made of Mike's chemical adsorption instrument and OMistar
Mass spectrum on-line checking measures.Support C O2- TPD is recorded the signal of nucleocytoplasmic ratio 44 by mass spectrograph, and catalyst CO-TPD is remembered by mass spectrograph
Record the signal of nucleocytoplasmic ratio 28.
In above-mentioned loaded catalyst, the θ-aluminium oxide containing modifying agent can be by being supported on θ-for modifying agent
It is made on aluminium oxide.Wherein, the θ-aluminium oxide can be the existing various aluminium oxide with theta structure, it is preferable that described
θ-aluminium oxide specific surface area is 50-150 meters2/ gram, more preferably 60-100 meters2/ gram；Kong Rongwei 0.2-0.6 ml/g, more
Preferably 0.3-0.5 mls/g.
Further preferably, the average pore size of the θ-aluminium oxide is 18-25 nanometers, more preferably 19-22 nanometers.
Further preferably, the particle diameter distribution of the θ-aluminium oxide is 70-150 microns and accounts for 98-100%.
In above-mentioned loaded catalyst, the θ-aluminium oxide can be obtained by roasting gama-alumina, wherein this hair
Bright to gama-alumina, there is no particular limitation, such as can be commercially available gama-alumina, also, the present invention is to commercially available γ-
The relevant parameter (such as specific surface area, Kong Rong, average pore size and particle diameter distribution) of aluminium oxide is not particularly limited, preferable case
Under, the specific surface area of commercially available gama-alumina is 110-250 meters2/ gram, preferably 120-200 meters2/ gram；Kong Rongwei 0.65-0.9
Ml/g, preferably 0.7-0.8 mls/g；Average pore size is 12-17.5 nanometers, preferably 13-17 nanometers.Preferably, city
The particle diameter distribution for the gama-alumina sold is 70-150 microns and accounts for 85-95%, preferably 90-95%.In the present invention, described
Specific surface area, Kong Rong and average pore size are measured according to nitrogen adsorption methods, specifically, pass through N2It is surveyed under 77K constant temperature
Determine the adsorption isotherm of carrier, then calculates specific surface area and Kong Rong by BET formula, and calculate average pore size by BJH method.
In the present invention, it can be 900- that it includes: maturing temperature that above-mentioned roasting gama-alumina, which obtains θ-aluminium oxide condition,
1150 DEG C, preferably 950-1100 DEG C；Calcining time can be 0.5-5 hours, preferably 1-4 hours.
In above-mentioned loaded catalyst, on the basis of the total amount of the catalyst, with elemental metal, the active group
The content divided is 5-70 weight %, preferably 8-50 weight %, more preferably 10-30 weight %；The content of the auxiliary agent is
0.5-18 weight %, preferably 1-15 weight %；The content of the carrier is 12-94 weight %, preferably 35-91 weight %.
Further, in the present invention, on the basis of θ-alumina support weight by described containing modifying agent, with metal
Element meter, the content of the modifying agent are 1-10 weight %, preferably 2.5-6 weight %.
In above-mentioned loaded catalyst, the modifying agent can be selected from alkaline components, alkaline earth metal component and Section IV B
One of race's metal component is a variety of.The alkaline components are preferably one of Li, Na and K or a variety of.Affiliated alkaline earth
Metal component can be Mg and/or Ca.The group ivb metal component can be Zr and/or Ti.Further, the modification
Agent can be selected from one of Li, Na, K, Mg, Ca, Zr and Ti or a variety of, preferably Zr and/or Mg, more preferably Zr.
There is no particular limitation for carrying method of the present invention to modifying agent, can be method commonly used in the art, example
Infusion process or coprecipitation, preferably infusion process can be such as used, specifically includes and θ-alumina support is immersed in containing above-mentioned
In the maceration extract of modifying agent, then it is dried and roasts.
There is no particular limitation to dipping method by the present invention, can be equi-volume impregnating, or saturation infusion process.
The present invention is not particularly limited the condition of dipping, for example, it can be 10-80 that the condition of dipping, which generally includes dipping temperature,
DEG C, preferably 20-60 DEG C；Dip time can be 0.1-3h, preferably 0.5-1h.
During loaded modified dose of θ-alumina support, there is no particular limitation to dry method by the present invention, can
Method commonly used in the art is thought, for example, actual conditions include: that drying temperature can be using the method for heat drying
80-350 DEG C, preferably 100-300 DEG C, drying time can be 1-24 hours, preferably 2-12 hours.
During loaded modified dose of θ-alumina support, also there is no particular limitation for method of the present invention to roasting,
It can be method commonly used in the art, for example, roasting as long as the modifying agent is separately converted to corresponding oxide
The method of burning is the method for roasting in air atmosphere, and the condition of roasting includes: that maturing temperature is 250 DEG C -900 DEG C, preferably
300 DEG C -850 DEG C, more preferably 350 DEG C -800 DEG C；Calcining time is 0.5-12 hours, preferably 1-8 hours, more preferably 2-
6 hours.
In above-mentioned loaded catalyst, the active component can be group VIII metal component, preferably Fe and/or
Co, more preferably Fe.
In above-mentioned loaded catalyst, the auxiliary agent can contain alkaline components and/or rare earth component,
In, the alkaline components as the auxiliary component can be one of Li, Na and K or a variety of, preferably Li and/or K, more
Preferably K；The rare earth component can be one of Ce, La and Pr or a variety of, preferably Ce and/or La, more preferably
For Ce.
In above-mentioned loaded catalyst, on the basis of the total amount of the catalyst, with elemental metal, helped as described
The content of the alkaline components of agent ingredient can be 0.5-8 weight %, preferably 1-5 weight %, more preferably 1-4 weight %；
The content of rare earth component can be 0.5-4 weight %, and the total amount of auxiliary component is 0.5-18 weight %, preferably 1-15
Weight %.
It should be noted that although alkaline components can be contained in auxiliary agent, but still alkaline components pair can be used
Carrier is modified, and in other no modifying agent, is still necessary to be modified carrier using alkaline components, without
The amount of modifying agent can be replaced by increasing the content of alkaline components in auxiliary agent.
In the present invention, the performance of catalyst can be characterized with CO-TPD, and CO-TPD indicates reduction-state Catalyst Adsorption CO
Afterwards at high temperature to the desorption temperature of CO, desorption temperature is higher to illustrate that catalyst activity is higher, is conducive to alkene generation.In CO-
In TPD spectrogram, peak temperature appearance position and peak area size show the power of catalyst CO dissociation capability, and peak temperature is desorbed in CO
It is high, peak area is big illustrates that catalyst CO dissociation capability is strong, be conducive to olefine selective raising.Supported catalyst provided by the invention
The CO-TPD desorption temperature of agent is higher than the CO-TPD desorption temperature of catalyst in comparative example.
A preferred embodiment of the invention, the CO-TPD desorption figure of the loaded catalyst is in 490-580
DEG C preferably there are CO desorption peaks at 495-575 DEG C.It is further preferred that the peak area of the CO desorption peaks is that 2.5-6a.u. is preferred
3-5.5a.u..In the case where being one of Zr, K and Mg for modifying agent, the CO-TPD desorption figure of the catalyst also exists
510-630 DEG C preferably 520-625 DEG C has another CO desorption peaks.Preferably, the peak area of another CO desorption peaks is
0.9-2a.u. (arbitrary unit).
Above-mentioned loaded catalyst is referred to existing method and is prepared, such as prepares θ-oxidation containing modifying agent
Then aluminium loads to active component and auxiliary agent on θ-alumina support containing modifying agent.The method wherein loaded can be normal
The infusion process of rule, dipping can use single-steeping, can also use step impregnation, step impregnation can be active component and
Auxiliary agent passes sequentially through on dip loading to θ-alumina support containing modifying agent, is also possible to active component and auxiliary agent together
Dissolution forms maceration extract, and maceration extract is impregnated into two times or repeatedly on θ-alumina support containing modifying agent.
A preferred embodiment of the invention, the preparation method packet of above-mentioned loaded catalyst provided by the invention
It includes and loads to active component and auxiliary agent on θ-alumina support containing modifying agent, the active component is group VIII metal
Component, the auxiliary agent contain alkaline components and/or rare earth component, and the method for the load includes that will contain active component
Point be adsorbed at least twice on the θ-alumina support containing modifying agent with the maceration extract of auxiliary agent, and every time after absorption according to
It is secondary to be dried and roast.
In the preferred case, the maceration extract containing active component and auxiliary agent is adsorbed onto two times described containing modifying agent
It is successively dried and roasts on θ-alumina support, and every time after absorption, wherein adsorb the volume of maceration extract used twice
Than for 1:0.5-1.5, preferably 1:1；The concentration ratio of maceration extract is 1:0.5-2, preferably 1:1, and solute in the maceration extract
Total concentration can be 30-70 weight %.
It was found by the inventors of the present invention that by " maceration extract containing active component and auxiliary agent point being adsorbed at least twice
On the θ-alumina support containing modifying agent, and every time absorption after be successively dried and roast " mode load work
Property component and auxiliary agent, can greatly improve the activity and catalytic stability of catalyst.
There is no particular limitation for carrying method of the present invention to active component and auxiliary agent, can be commonly used in the art
Method, such as infusion process or coprecipitation, preferably infusion process can be used, infusion process can be equi-volume impregnating, can also
Think saturation infusion process, preferably saturation infusion process.
The present invention is equal to the drying and method of roasting, and there is no particular limitation, can use side commonly used in the art
Method, as previously mentioned, this is no longer going to repeat them.
θ-the aluminium oxide containing modifying agent and θ-aluminium oxide preparation method have been described above,
This is no longer repeated one by one.
In the present invention, the preparation of maceration extract can be realized by the way that the soluble-salt of respective components to be dissolved in solvent.Institute
Stating soluble-salt for example can be nitrate, can be chloride etc..
Above-mentioned loaded catalyst is applied to by needing in presence of hydrogen before Fischer-Tropsch synthesis, by active component
Reduction activation is carried out, there is no particular limitation for condition of the present invention to the reduction activation, such as can be with are as follows: reduction temperature is
100-800 DEG C, preferably 200-600 DEG C, more preferably 300-500 DEG C；Recovery time is 0.5-72 hours, and preferably 1-36 is small
When, more preferably 2-24 hours；The reduction activation can carry out in pure hydrogen atmosphere, can also be in hydrogen and inert gas
Mixed atmosphere in carry out, such as can be carried out in hydrogen with the mixed atmosphere of nitrogen and/or argon gas, Hydrogen Vapor Pressure 0.1-
4MPa, preferably 0.1-2MPa.
There is no particular limitation to the equipment that step 5) uses by the present invention, can be used for refinery for commonly used in the art
The equipment of dry gas separation, for example, the step can be in the oil refinery dry gas separative unit VIII in above system provided by the invention
Middle progress.There is no particular limitation to the condition that oil refinery dry gas separates by the present invention, as long as the separation of hydrogen and methane may be implemented
, for example, the separate mode condensation at low temperature of oil refinery dry gas.The condition of oil refinery dry gas separation may include: the temperature of separation
It can be -150 DEG C~-200 DEG C.
It is further preferred that the hydrogen Q in the oil refinery dry gas isolated is sent into step 3), with coal gasification crude synthesis gas
E is purified together.
Oil refinery dry gas L mainly contains catalytic cracked dry gas, coking dry gas, reforms dry gas, is hydrocracked dry gas and often subtracts
The fixed gas etc. of pressure device, main component include hydrogen (30-50%), methane (20-40%), carbon monoxide (0.5-5%), nitrogen
Gas (7-15%), carbon dioxide (1-7%), hydro carbons (15-30%) etc..
The flow-rate ratio of a kind of embodiment according to the present invention, the feed coal and oil refinery dry gas L are 1:2-6, preferably
1:3-5.Using aforementioned proportion, it can make the coal gasification crude synthesis gas E generated that there is the hydrogen for being suitble to that Fischer-Tropsch synthesis occurs
With the molar ratio of carbon monoxide and/or the carbon dioxide and methane ratio that are reacted with suitable methane dry reforming.
There is no particular limitation to the equipment that step 6) uses by the present invention, can be carry out methane commonly used in the art
The equipment of dry reforming reaction, for example, the step can be in the methane dry reforming unit VII in above system provided by the invention
It carries out.There is no particular limitation to the condition that the methane dry reforming is reacted by the present invention, for example, the condition of methane dry reforming reaction
May include: reaction temperature be 600-800 DEG C, reaction pressure 0.1-1.0MPa.Catalyst can be anti-with various methane dry reformings
Answer catalyst, for example, Ni/Al2O3Loaded catalyst.The molar ratio of methane and carbon dioxide can be 1:0.6-1.5, preferably
For 1:0.8-1.3, the air speed of mixed gas can be 40000-160000h-1, preferably 60000-140000h-1。
In the preferred case, it carries out the carbon dioxide of methane dry reforming reaction and methane can come from step 3) and/or step
Rapid 4) resulting carbon dioxide H and step 4) and the resulting methane of step 5), this allows to net to coal gasification crude synthesis gas
The greenhouse gases for two kinds of serious pollution environment that change process, Fischer-Tropsch synthesis process and oil refinery dry gas separation process generate
(carbon dioxide and methane) is used, and reduces environmental pollution, and improves the energy utilization rate of integrated artistic.
The method provided according to the present invention further includes in the preferred case that methane dry reforming is reacted to gained synthesis gas U to return
Step 4) is returned, the Fischer-Tropsch synthesis is carried out.
The method provided according to the present invention, in the preferred case, this method further include by the resulting crude synthesis gas E of step 2)
Water gas shift/WGS is carried out, to improve the molar ratio of hydrogen and carbon monoxide, crude synthesis gas E carries out step after then converting gained
3) purification.Preferably, the molar ratio of the crude synthesis gas E hydrogen and carbon monoxide is 0.4-0.8:1, is become through water-gas
It changes, the molar ratio of the hydrogen of synthesis gas J and carbon monoxide is 0.9-1.2:1 after purified synthesis gas.
The method provided according to the present invention, in the preferred case, this method further include by crude synthesis gas E first as heating
Medium passes through the reactor preheating furnace of methane dry reforming unit VII, enters back into WGS unit III and carries out Water gas shift/WGS
Or purified synthesis gas directly is carried out in purified synthesis gas unit IV again, so that by strongly exothermic coal gasification unit crude synthesis gas
Highly endothermic methane dry reforming unit is introduced, utilization efficiency of heat energy is improved.
The method provided according to the present invention, in the preferred case, this method further include by the object of olefin-containing obtained by step 4)
Stream is separated, and alkene K logistics is obtained.
Under preferable case, method provided by the invention further include by unreacted synthesis gas Y return F- T synthesis unit V into
Row Fischer-Tropsch synthesis.The periodic off-gases Z that separation of olefins obtains then outlet.
The method provided according to the present invention, in the preferred case, this method further include the hydrogen Q for obtaining step 5) and step
The rapid crude synthesis gas F 2) obtained is purified together, the synthesis gas J being purified.
A preferred embodiment of the invention, method provided by the invention use system shown in Fig. 3 and technique,
Fine coal A and water B are conveyed into the preparation that water-coal-slurry preparation unit I carries out water-coal-slurry first, then by water-coal-slurry C obtained and oxygen
Gas D is conveyed into coal gasification unit II together and generates coal gasification crude synthesis gas E, is then situated between coal gasification crude synthesis gas E as heating
Matter passes through the reactor preheating furnace of methane dry reforming unit VII, and WGS unit III adjustment hydrogen is successively conveyed into after heat exchange
The molar ratio and purified synthesis gas unit IV of gas and carbon monoxide remove sour gas and sulfide M, be purified synthesis gas J and
Carbon dioxide H, by decontaminating syngas J be conveyed into F- T synthesis unit V occur Fischer-Tropsch synthesis, generate the logistics of olefin-containing with
And carbon dioxide H and methane G, the logistics delivery for the olefin-containing that Fischer-Tropsch synthesis generates then is entered into separation of olefins unit VI,
Isolated alkene K, unreacted synthesis gas Y and periodic off-gases Z.Alkene K enters subsequent technique, unreacted synthesis gas Y as product
A part returns to F- T synthesis unit V and carries out Fischer-Tropsch synthesis, and another part is as periodic off-gases Z then outlet.Returning part with
The ratio of outlet part is preferably 95-98:2-5.In addition, the system further includes oil refinery dry gas separative unit VIII and methane dry weight
Oil refinery dry gas L is conveyed into oil refinery dry gas separative unit VIII and generates methane P and hydrogen Q, by F- T synthesis list by whole unit VII
The carbon dioxide H that first V and purified synthesis gas unit IV is generated is conveyed into methane dry reforming unit VII, and oil refinery dry gas is separated
The methane G that the methane P and F- T synthesis unit V that unit VIII is generated are generated also is conveyed into methane dry reforming unit VII, so that two
Carbonoxide and methane react in methane dry reforming unit VII generates synthesis gas U, then will react and generate through methane dry reforming
Synthesis gas U be delivered to together with decontaminating syngas J F- T synthesis unit V carry out Fischer-Tropsch synthesis.
According to another preferred method of implementation of the present invention, method provided by the invention uses system shown in Fig. 2 and work
Skill, the difference of the system and system shown in Fig. 3 are to omit WGS unit, and synthesis gas hydrogen and carbon monoxide rub
You by increasing the hydrogen that oil refinery dry gas separative unit VIII is isolated than being adjusted.
Yet another preferred form according to the present invention, method provided by the invention use system shown in fig. 5 and work
Skill, the difference of the system and system shown in Figure 3 are that oil refinery dry gas separative unit VIII is equipped with hydrogen outlet, oil refinery dry gas L warp
The hydrogen Q generated after oil refinery dry gas separative unit VIII can be exported by hydrogen outlet, be allowed to and coal gasification crude synthesis gas E mono-
It rises and enters the molar ratio adjusting that WGS unit III carries out hydrogen and carbon monoxide, be allowed to meet Fischer-Tropsch synthesis
It is required that then be passed through cleaning up unit IV and purified, so as to omit Water gas shift/WGS process.
Another preferred embodiment according to the present invention, method provided by the invention use system shown in Fig. 4 and work
Skill, the difference of the system and system shown in fig. 5 are to omit WGS unit, and synthesis gas hydrogen and carbon monoxide rub
You by increasing the hydrogen that oil refinery dry gas separative unit VIII is isolated than being adjusted.
Using above-mentioned preferred embodiment, and each step condition is controlled in above-mentioned preferred scope, pass through control fine coal and refinery
The weight flow ratio of dry gas can obtain best overall economic efficiency within the scope of 1:1.5-4.Such as 2000 ton/days are measured
The water-coal-slurry liquefaction device of grade, the flow of the feed coal can be 200-500t/h, preferably 250-400t/h, oil refinery dry gas
The flow of L can be 400-800t/h, preferably 450-700t/h.
The present invention will be described in detail by way of examples below.
In the following Examples and Comparative Examples:
Conversion ratio (the X of COCO)、CH4SelectivityCO2SelectivityC2-C4The selectivity of hydro carbonsAnd C5(C above5+) hydro carbons selectivityIt is calculated by the following formula to obtain respectively:
Wherein, V1、V2Respectively indicate at standard conditions, enter in certain period the unstripped gas of reaction system volume and
Flow out the exhaust gas volumes of reaction system；c1,CO、c2,CORespectively indicate the molar content of CO in unstripped gas and tail gas.nconIt is anti-to participate in
The molal quantity of the CO answered,To generate CO2Molal quantity,For the CH of generation4Molal quantity,For generation
CH4、C2Hydrocarbon, C3Hydrocarbon and C4The sum of molal quantity of hydrocarbon.
In the following Examples and Comparative Examples, the specific surface area of carrier, Kong Rong and average pore size are according to nitrogen adsorption
Method is measured, and specifically, passes through N2The adsorption isotherm that carrier is measured under 77K constant temperature, then presses BET formula calculating ratio table
Area and Kong Rong, and average pore size distribution is calculated by BJH method.
The content of active component, modifying agent and auxiliary agent uses X-ray fluorescence spectra analysis method RIPP132-90 (petroleum
Work analysis method (RIPP experimental method), Yang Cuiding, Gu Kanying, Wu Wenhui are compiled, Science Press's nineteen ninety September first edition, the
371-379 pages) it measures.
In the following Examples and Comparative Examples:
Support C O2- TPD and catalyst CO-TPD is measured using Mike's chemical adsorption instrument with OMistar mass spectrum on-line checking.
Support C O2- TPD is recorded the signal of nucleocytoplasmic ratio 44 by mass spectrograph, and catalyst CO-TPD is recorded the signal of nucleocytoplasmic ratio 28 by mass spectrograph.
Support C O2- TPD middle peak of spectrogram temperature appearance position and peak area size show that carrier alkalinity is strong and weak, CO2Peak temperature height, peak is desorbed
Area is big to illustrate that carrier alkalinity is strong, is conducive to alkene desorption；Catalyst performance is characterized with CO-TPD, CO-TPD middle peak of spectrogram temperature
Appearance position and peak area size show the power of catalyst CO dissociation capability, and CO desorption peak temperature is high, the big explanation of peak area is urged
Agent CO dissociation capability is strong, is conducive to olefine selective raising.
Embodiment 1
The present embodiment is for illustrating system and method provided by the invention.
(1) building of system
It is sequentially connected water-coal-slurry preparation unit I, coal gasification unit II, WGS unit III, purified synthesis gas unit
IV, F- T synthesis unit V and separation of olefins unit VI, and pass through conveyance conduit for the carbon dioxide outlet of F- T synthesis unit V
It is connected to the carbon dioxide outlet of purified synthesis gas unit IV with the carbon dioxide entrance of methane dry reforming unit VII, refinery is dry
The methane of the methane outlet of gas separative unit VIII and the methane outlet of F- T synthesis unit V with methane dry reforming unit VII
The synthesis gas entrance of the syngas outlet of methane dry reforming unit VII and F- T synthesis unit V are passed through delivery pipe by entrance connection
Road connection.There are two entrances for the reactor preheating furnace heat supply entrance of methane dry reforming unit VII, respectively with coal gasification unit II's
The outlet of coal gasification crude synthesis gas is connected.Strongly exothermic water gas shift reaction is strong endothermic reaction methane dry reforming unit VII's
Preheating furnace heat supply；The high-temperature crude synthesis gas E of WGS unit III initially enters methane dry reforming reactor preheating furnace, it
After enter back into purified synthesis gas unit IV.It is provided with flow control valve (not shown) in each conveyance conduit, obtains as shown in Figure 3
System.
(2) preparation of Fischer-Tropsch synthesis catalyst
A, the preparation of carrier
Take the γ-Al of commercially available 100-300 mesh2O3Carrier (Sasol product) 200g, roasts 2h at 980 DEG C, and θ-oxygen is made
Change alumina supporter, BET property is as shown in table 1.It weighs five water zirconium nitrate of 14.1g and is dissolved in 60g deionized water that modified zirconium is made is molten
Liquid, modified zirconium solution is added in the carrier after the above-mentioned roasting of 100.0g, and uniform stirring 5min stands 2h, is put into 120 in baking oven
DEG C dry 5h, roasts 3h at 400 DEG C, is made by elemental metal and on the basis of the weight of modified support, Zr content is 3 weights
Measure the modified support Z1, CO of %2Desorption peak temperature and peak area are shown in Table 2.
B, the preparation of catalyst
16.3g ferric citrate, 1.16g potassium carbonate, 0.87g cerium nitrate hexahydrate are dissolved in 12mL deionized water, in 50
Heating stirring is uniformly mixed in DEG C water-bath, obtains maceration extract.Take above-mentioned half maceration extract, the aluminium oxide after being distributed to modification by calcination
In carrier 15g, after stir thoroughly at room temperature, it is placed in 120 DEG C of baking ovens dry 5h, 3h is roasted at 400 DEG C later and obtains a leaching
Rear catalyst；Remaining maceration extract is added in a leaching rear catalyst, drying and roasting under similarity condition obtains catalyst A1, with
The group of elemental metal and on the basis of the weight of the catalyst of preparation, catalyst A1 becomes 18%Fe-3%K-2%Ce/3%
Zr-Al2O3, CO desorption peak temperature and desorption peak area are shown in Table 3.
(3) preparation of alkene
By solid material coal (Inner Mongol produce lignite) after crushing and screening (partial size 10mm) with the flow of 360t/h with
The water B of 360t/h delivers into water-coal-slurry preparation unit I together, and water-coal-slurry C, water-coal-slurry C and oxygen D is made in coal gasification unit
In II, in 1300 DEG C, under the conditions of 3.0MPa, the crude synthesis gas E based on carbon monoxide and hydrogen is generated；Crude synthesis gas E is first
By the reactor preheating furnace of methane dry reforming unit VII, reaches reactor preheating furnace needed for preheating and enter back into water coal for 600 DEG C
Gas converter unit III adjusts the molar ratio of hydrogen and carbon monoxide to 1 or so and purified synthesis gas unit IV removing sour gas
After sulfide M, clean decontaminating syngas J is obtained, the molar ratio of hydrogen and carbon monoxide is 0.99:1；Purification is synthesized
Gas J, which is delivered in the fluidized-bed reactor of F- T synthesis unit V, carries out Fischer-Tropsch synthesis, and reaction temperature is 320 DEG C, and pressure is
1.0MPa, catalyst are the catalyst A1, gas space velocity 40000h being prepared by step (2)-1, obtain F- T synthesis production
Object, product are sent into separation of olefins unit VI, carry out gas-liquid separation first in separation of olefins unit VI product and obtain oil product and product
Gas, product gas obtain C subsequently into cryogenic separation (- 105 DEG C) by acid gas purifying carbon dioxide removal2-C4Alkene K and
Methane product (- 161 DEG C) and unreacted synthesis gas Y.Unreacted synthesis gas Y is entered by the ratio after separation according to 98%
Fischer-Tropsch synthesis device reacts again, and 2% unreacted synthesis gas is as periodic off-gases Z.Using after line gas-chromatography is to reaction 50h
The composition of obtained product is analyzed, and the results are shown in Table 5.
In addition, oil refinery dry gas L (ingredient is as shown in table 4) is removed after oxygen, the impurity such as hydrogen sulfide with the flow of 600t/h
It is conveyed into oil refinery dry gas separative unit VIII, wherein the ingredient of oil refinery dry gas L is as shown in table 4, and oil refinery dry gas L passes through deep cooling point
From carbon dioxide is isolated first at -80 DEG C, residual gas continues to be cooled to -200 DEG C, successively isolates methane P (- 170
DEG C), carbon monoxide (- 190 DEG C), nitrogen (- 196 DEG C) and hydrogen Q.
The carbon dioxide H and expense that methane P, the purified synthesis gas unit IV that oil refinery dry gas separation process is generated are generated
The carbon dioxide H and methane G that support synthesis process generates are delivered to methane dry reforming unit VII, in temperature is 750 DEG C, pressure is
0.1MPa, catalyst Ni/Al2O3The item of loaded catalyst (load capacity of nickel is 8 weight %, the weight based on catalyst)
Synthesis gas U is generated under part, the hydrogen of synthesis gas U and the molar ratio of carbon monoxide are 0.99:1, then will be generated through methane dry reforming
Synthesis gas U be delivered to together with decontaminating syngas J F- T synthesis unit V carry out Fischer-Tropsch synthesis.
It the results are shown in Table 6.
Embodiment 2
The present embodiment is for illustrating system and method provided by the invention.
(1) building of system
System is constructed in the same manner as shown in Example 1.
(2) preparation of Fischer-Tropsch synthesis catalyst
A, the preparation of carrier
Take the γ-Al of commercially available 100-300 mesh2O3Carrier (Sasol product) 200g, roasts 2h at 980 DEG C, and θ-oxygen is made
Change alumina supporter, BET property is as shown in table 1.It weighs 37.0g magnesium nitrate and is dissolved in 60g deionized water and modified magnesium solution is made, it will
Modified magnesium solution is added in the carrier after the above-mentioned roasting of 100.0g, and uniform stirring 5min stands 2h, is put into baking oven and does for 200 DEG C
Dry 3h roasts 1h at 800 DEG C, is made by elemental metal and on the basis of the weight of modified support, and Mg content is 6 weight %
Modified support Z2.Its CO2Desorption peak temperature and peak area are shown in Table 2.
B, the preparation of catalyst
8.18g ferric nitrate, 1.11g lithium carbonate, 0.87g cerium nitrate hexahydrate are dissolved in 12mL deionized water, in 50 DEG C of water
Heating stirring is uniformly mixed in bath, obtains maceration extract.Take above-mentioned half maceration extract, the alumina support after being distributed to modification by calcination
In 15g, after stir thoroughly at room temperature, it is placed in 200 DEG C of baking ovens dry 3h, roasts after 1h obtains a leaching urge at 800 DEG C later
Agent；Remaining maceration extract is added in a leaching rear catalyst, drying and roasting under similarity condition obtains catalyst A2, with metal
The group of element meter and on the basis of the weight of the catalyst of preparation, catalyst A2 becomes 18%Fe-3%Li-2%Ce/6%Mg-
Al2O3.Its CO desorption peak temperature and desorption peak area are shown in Table 3.
(3) preparation of alkene
Alkene is prepared in the same manner as shown in Example 1, wherein except that the catalysis that Fischer-Tropsch synthesis uses
Agent is the catalyst A2 being prepared by step (2).
It the results are shown in Table 5 and table 6.
Embodiment 3
The present embodiment is for illustrating system and method provided by the invention.
(1) building of system
System is constructed in the same manner as shown in Example 1.
(2) preparation of Fischer-Tropsch synthesis catalyst
A, the preparation of carrier
Take the γ-Al of commercially available 100-300 mesh2O3Carrier (Sasol product) 200g, roasts 2h at 980 DEG C, and θ-oxygen is made
Change alumina supporter, XRD, BET property are as shown in figure 1 and table 1.It weighs 6.5g potassium nitrate and is dissolved in 60g deionized water and modification is made
Potassium solution, modified potassium solution is added in the carrier after the above-mentioned roasting of 100.0g, and uniform stirring 5min stands 2h, is put into baking oven
In 300 DEG C of dry 2h, roast 6h at 500 DEG C, be made by elemental metal and on the basis of the weight of modified support, K content
For the modified support Z3 of 2.5 weight %.Its CO2Desorption peak temperature and peak area are shown in Table 2.
B, the preparation of catalyst
16.3g ferric citrate, 1.16g potassium carbonate, 0.87g cerium nitrate hexahydrate are dissolved in 12mL deionized water, in 50
Heating stirring is uniformly mixed in DEG C water-bath, obtains maceration extract.Take above-mentioned half maceration extract, the aluminium oxide after being distributed to modification by calcination
In carrier 15g, after stir thoroughly at room temperature, it is placed in 300 DEG C of baking ovens dry 2h, 6h is roasted at 500 DEG C later and obtains a leaching
Rear catalyst；Remaining maceration extract is added in a leaching rear catalyst, drying and roasting under similarity condition obtains catalyst A3, with
The group of elemental metal and on the basis of the weight of the catalyst of preparation, catalyst A3 becomes 18%Fe-3%K-2%Ce/
2.5%K-Al2O3.Its CO desorption peak temperature and desorption peak area are shown in Table 3.
(3) preparation of alkene
Alkene is prepared in the same manner as shown in Example 1, wherein except that the catalysis that Fischer-Tropsch synthesis uses
Agent is the catalyst A3 being prepared by step (2).
It the results are shown in Table 5 and table 6.
Embodiment 4
The present embodiment is for illustrating system and method provided by the invention.
(1) building of system
System is constructed in the same manner as shown in Example 1.
(2) preparation of Fischer-Tropsch synthesis catalyst
Using infusion process commercially available 100-300 mesh γ-Al2O3Ferro element is loaded on carrier Z4 (Sasol product), is obtained
Ferrum-based catalyst A4.By elemental metal and on the basis of the weight of the catalyst of preparation, the group of catalyst A4 becomes 18%Fe/
Al2O3。
(3) preparation of alkene
Alkene is prepared in the same manner as shown in Example 1, wherein except that the catalysis that Fischer-Tropsch synthesis uses
Agent is the catalyst A4 being prepared by step (2).
It the results are shown in Table 5 and table 6.
Embodiment 5
The present embodiment is for illustrating system and method provided by the invention.
(1) building of system
Be sequentially connected water-coal-slurry preparation unit I, coal gasification unit II, purified synthesis gas unit IV, F- T synthesis unit V and
Separation of olefins unit VI, and pass through conveyance conduit for the carbon dioxide outlet of F- T synthesis unit V and purified synthesis gas unit IV
Carbon dioxide outlet be connected to the carbon dioxide entrance of methane dry reforming unit VII, the first of oil refinery dry gas separative unit VIII
The methane outlet of alkane outlet and F- T synthesis unit V pass through pipeline and are connected to the methane entrance of methane dry reforming unit VII, will
The syngas outlet of methane dry reforming unit VII is connected to the synthesis gas entrance of F- T synthesis unit V by conveyance conduit.Methane
There are two entrances for the reactor preheating furnace heat supply entrance of dry reforming unit VII, slightly close with the coal gasification of coal gasification unit II respectively
It is connected at gas outlet.Strongly exothermic water gas shift reaction is the preheating furnace heat supply of strong endothermic reaction methane dry reforming unit VII；
The high-temperature crude synthesis gas E of WGS unit III initially enters methane dry reforming reactor preheating furnace, enters back into synthesis later
Gas clean unit IV.In addition, oil refinery dry gas separative unit VIII is equipped with hydrogen outlet, which passes through pipeline and synthesis gas
The crude synthesis gas entrance of clean unit IV is connected to.It is provided with flow control valve (not shown) in each conveyance conduit, obtains such as Fig. 4 institute
The system shown.
(2) preparation of Fischer-Tropsch synthesis catalyst
Catalyst A1 is prepared in the same manner as shown in Example 1.
(3) preparation of alkene
By solid material coal (Datong produce anthracite) after crushing and screening (partial size 10mm) with the stream of 280t/h
Amount delivers into water-coal-slurry preparation unit I together with water B, water-coal-slurry C, water-coal-slurry C and oxygen D is made in coal gasification unit II,
In 1200 DEG C, under the conditions of 2.8MPa, the crude synthesis gas E based on carbon monoxide and hydrogen is generated；Crude synthesis gas E first passes around first
The reactor preheating furnace of alkane dry reforming unit VII makes up to needed for preheating and enters back into purified synthesis gas unit IV (only for 600 DEG C
Change condition crude synthesis gas removes CO with low-temp methanol washing method (Rectisol method)2、H2S, COS, HCN and NH3Deng.High concentration
H2S gas enters second level Claus conversion technique and carries out sulfur recovery；By CO when Mathanol regenerating2Parsing, it is former as methane dry reforming
Material.) after removing sour gas and sulfide M, obtaining clean decontaminating syngas J, the molar ratio of hydrogen and carbon monoxide is
0.9:1；Decontaminating syngas J is delivered in the fluidized-bed reactor of F- T synthesis unit V and carries out Fischer-Tropsch synthesis, reaction temperature
Degree is 280 DEG C, pressure 0.8MPa, and catalyst is the catalyst A1, gas space velocity 20000h being prepared by step (2)-1,
The product of olefin-containing, carbon dioxide H and methane G is obtained, the product of obtained olefin-containing is first passed through into methane dry reforming unit VII
Reactor preheating furnace be re-fed into separation of olefins unit VI, carry out gas-liquid separation first in separation of olefins unit VI product and obtain oil
Product and product gas, product gas obtain C subsequently into cryogenic separation (- 105 DEG C) by acid gas purifying carbon dioxide removal2-
C4Alkene K and methane product (- 161 DEG C) and unreacted synthesis gas Y.Unreacted synthesis gas Y by separation after according to 95%
Ratio enter Fischer-Tropsch synthesis device and react again, 5% unreacted synthesis gas is as periodic off-gases Z.Utilize online gas-chromatography
The composition of the product obtained after reaction 50h is analyzed, the results are shown in Table 5.
In addition, oil refinery dry gas L (ingredient is as shown in table 4) is removed after oxygen, the impurity such as hydrogen sulfide with the flow of 800t/h
It is conveyed into oil refinery dry gas separative unit VIII, wherein the ingredient of oil refinery dry gas L is as shown in table 4, and oil refinery dry gas L passes through deep cooling point
From carbon dioxide is isolated first at -80 DEG C, residual gas continues to be cooled to -200 DEG C, successively isolates methane P (- 170
DEG C), carbon monoxide (- 190 DEG C), nitrogen (- 196 DEG C) and hydrogen Q.
The carbon dioxide H and expense that methane P, the purified synthesis gas unit IV that oil refinery dry gas separation process is generated are generated
The carbon dioxide H and methane G that support synthesis process generates are delivered to methane dry reforming unit VII, in temperature is 600 DEG C, pressure is
0.5MPa, catalyst Ni/Al2O3The item of loaded catalyst (load capacity of nickel is 8 weight %, the weight based on catalyst)
Synthesis gas U is generated under part, the hydrogen of synthesis gas U and the molar ratio of carbon monoxide are 1:1, then the conjunction that will be generated through methane dry reforming
F- T synthesis unit V is delivered to together with decontaminating syngas J at gas U and carries out Fischer-Tropsch synthesis.
In addition, the hydrogen Q that oil refinery dry gas separation process generates is delivered to purified synthesis gas unit together with crude synthesis gas E
IV carries out Fischer-Tropsch synthesis after purified.
It the results are shown in Table 6.
Embodiment 6
The present embodiment is for illustrating system and method provided by the invention.
(1) building of system
It is sequentially connected water-coal-slurry preparation unit I, coal gasification unit II, WGS unit III, purified synthesis gas unit
IV, F- T synthesis unit V and separation of olefins unit VI, and pass through conveyance conduit for the carbon dioxide outlet of F- T synthesis unit V
It is connected to the carbon dioxide outlet of purified synthesis gas unit IV with the carbon dioxide entrance of methane dry reforming unit VII, refinery is dry
The methane outlet and F- T synthesis V methane outlet of gas separative unit VIII connects with the methane entrance of methane dry reforming unit VII
It is logical, the synthesis gas entrance of the syngas outlet of methane dry reforming unit VII and F- T synthesis unit V are connected by conveyance conduit
It is logical.In addition, oil refinery dry gas separative unit VIII is equipped with hydrogen outlet, which passes through pipeline and purified synthesis gas unit IV
Crude synthesis gas entrance connection.There are two entrances for the reactor preheating furnace heat supply entrance of methane dry reforming unit, respectively at coal gas
The coal gasification crude synthesis gas outlet for changing unit is connected.Strongly exothermic water gas shift reaction is strong endothermic reaction methane dry reforming list
The preheating furnace heat supply of member；The high-temperature crude synthesis gas of WGS unit III initially enters methane dry reforming reactor preheating furnace,
Purified synthesis gas unit is entered back into later.It is provided with flow control valve (not shown) in each conveyance conduit, obtains as shown in Figure 5
System.
(2) preparation of Fischer-Tropsch synthesis catalyst
Catalyst A1 is prepared in the same manner as shown in Example 1.
(3) preparation of alkene
By solid material coal (Datong produce coking coal) after crushing and screening (partial size 10mm) with the flow of 320t/h
Water-coal-slurry preparation unit I is delivered into together with water B, and water-coal-slurry C, water-coal-slurry C and oxygen D is made in coal gasification unit II,
In 1500 DEG C, under the conditions of 3.2MPa, the crude synthesis gas E based on carbon monoxide and hydrogen is generated；Crude synthesis gas E first passes around first
The reactor preheating furnace of alkane dry reforming unit VII makes up to needed for waste heat and enters back into WGS unit III tune for 600 DEG C
The molar ratio and purified synthesis gas unit IV (purification condition is with embodiment 1) of whole hydrogen and carbon monoxide remove sour gas and sulphur
After compound M, clean decontaminating syngas J is obtained, the molar ratio of hydrogen and carbon monoxide is 1.2:1；Decontaminating syngas J is defeated
It send into the fluidized-bed reactor of F- T synthesis unit V and carries out Fischer-Tropsch synthesis, reaction temperature is 360 DEG C, and pressure is
1.5MPa, catalyst are the catalyst A1, gas space velocity 50000h being prepared by step (2)-1, obtain olefin-containing, dioxy
Change the product of carbon H and methane G, is sent into separation of olefins unit VI.Gas-liquid separation is carried out first in separation of olefins unit VI product to obtain
To oil product and product gas, product gas is obtained by acid gas purifying carbon dioxide removal subsequently into (- 105 DEG C) of cryogenic separation
To C2-C4Alkene K and methane product (- 161 DEG C) and unreacted synthesis gas Y.Unreacted synthesis gas Y by separation after according to
96% ratio enters Fischer-Tropsch synthesis device and reacts again, and 4% unreacted synthesis gas is as periodic off-gases Z.Utilize online gas phase
Chromatography analyzes the composition of the product obtained after reaction 50h, the results are shown in Table 5.
In addition, oil refinery dry gas L (ingredient is as shown in table 4) is removed after oxygen, the impurity such as hydrogen sulfide with the flow of 700t/h
It is conveyed into oil refinery dry gas separative unit VIII, wherein the ingredient of oil refinery dry gas L is as shown in table 4, and oil refinery dry gas L passes through deep cooling point
From carbon dioxide is isolated first at -80 DEG C, residual gas continues to be cooled to -200 DEG C, successively isolates methane P (- 170
DEG C), carbon monoxide (- 190 DEG C), nitrogen (- 196 DEG C) and hydrogen Q.
The carbon dioxide H and expense that methane P, the purified synthesis gas unit IV that oil refinery dry gas separation process is generated are generated
The carbon dioxide H and methane G that support synthesis process generates are delivered to methane dry reforming unit VII, in temperature is 800 DEG C, pressure is
1.0MPa, catalyst Ni/Al2O3The item of loaded catalyst (load capacity of nickel is 8 weight %, the weight based on catalyst)
Generate synthesis gas U under part, the molar ratio of the hydrogen of synthesis gas U and carbon monoxide is 1.2:1, then will be generated through methane dry reforming
Synthesis gas U is delivered to F- T synthesis unit V together with decontaminating syngas J and carries out Fischer-Tropsch synthesis.
In addition, the hydrogen Q that oil refinery dry gas separation process generates is delivered to purified synthesis gas unit together with crude synthesis gas E
IV carries out Fischer-Tropsch synthesis after purified.
It the results are shown in Table 6.
Comparative example 1
The system and method that this comparative example is used to illustrate currently used FTO technique.
System is constructed according to the same manner as in Example 1, the difference is that is, this is using system shown in FIG. 1
System does not include methane dry reforming unit VII and oil refinery dry gas separative unit VIII, and concrete operations are as follows:
(1) building of system
It is sequentially connected water-coal-slurry preparation unit I, coal gasification unit II, WGS unit III, purified synthesis gas unit
IV, F- T synthesis V and separation of olefins unit VI.It is provided with flow control valve (not shown) in each conveyance conduit, obtains such as Fig. 1 institute
The system shown.
(2) preparation of Fischer-Tropsch synthesis catalyst
Catalyst A1 is prepared in the same manner as shown in Example 1.
(3) preparation of alkene
By solid material coal (Inner Mongol produce lignite) after crushing and screening (partial size 10mm) with the flow of 360t/h with
The water B of 360t/h delivers into water-coal-slurry preparation unit I together, and water-coal-slurry C, water-coal-slurry C and oxygen D is made in coal gasification unit
In II, in 1300 DEG C, under the conditions of 3.0MPa, the crude synthesis gas E based on carbon monoxide and hydrogen is generated；Crude synthesis gas E is successively
Molar ratio (the molar ratio of crude synthesis gas hydrogen and carbon monoxide through WGS unit III adjustment hydrogen and carbon monoxide
Lower, about 0.5-0.8 passes through water-gas reacting condition: CO+H2O=CO2+H2It is CO by CO portions turn2And hydrogen, it improves
The molar ratio of hydrogen and carbon monoxide is to 1 or so) and purified synthesis gas unit IV (purification condition is with embodiment 1) remove sour gas
After body and sulfide M, clean decontaminating syngas J is obtained, the molar ratio of hydrogen and carbon monoxide is 0.99:1；Purification is closed
It is delivered in the fluidized-bed reactor of F- T synthesis unit V at gas J and carries out Fischer-Tropsch synthesis, reaction temperature is 320 DEG C, pressure
For 1.0MPa, catalyst is the catalyst A1, gas space velocity 40000h being prepared by step (2)-1, obtain the production of olefin-containing
The product of obtained olefin-containing is sent into separation of olefins unit VI, isolates alkene K, titanium dioxide by object, carbon dioxide H and methane G
Carbon H and methane G outlet, unreacted synthesis gas Y are reacted again by entering Fischer-Tropsch synthesis device according to 98% ratio after separation,
2% unreacted synthesis gas is as periodic off-gases Z.It is carried out using the composition of the product obtained after line gas-chromatography is to reaction 50h
Analysis.
It the results are shown in Table 5 and table 6.
1 carrier B ET of table
2 support C O of table2-TPD
3 catalyst CO-TPD of table
Note: into table 3, " -- " indicates to be not present or do not measure table 1.
4 dry gas of table composition
| Dry gas ingredient | H2 | O2 | N2 | CH4 | Hydro carbons | CO | CO2 | H2S |
| Dry gas forms (%) | 31.8 | 0.8 | 10.1 | 29.2 | 22.9 | 0.6 | 4.5 | 0.1 |
Table 5
Note: *: O/P is the alkene (S of C2-C4 in gaseous hydrocarbon productC2 = -C4 =) and alkane (SC2 o -C4 o) ratio.
Table 6
| Water consume (t/tAlkene) | CO2 emission (t/tAlkene) | Energy efficiency (%) | |
| Embodiment 1 | 20 | 3.2 | 45 |
| Embodiment 2 | 20 | 3.5 | 42 |
| Embodiment 3 | 20 | 3.7 | 40 |
| Embodiment 4 | 20 | 2.5 | 40 |
| Embodiment 5 | 20 | 1.9 | 53 |
| Embodiment 6 | 20 | 2.1 | 51 |
| Comparative example 1 | 20 | 6 | 36 |
Note: energy efficiency=final goes out the calorific value of the alkene of device/into originals such as the coal electricity vapor catalyst solvents of device
The sum of calorific value of material, i.e., gained alkene calorific value/produce these alkene needed for comprehensive energy consumption.Wherein, comprehensive energy consumption includes original
Expect calorific value and public work energy consumption.Specifically include that bunker coal and feed coal calorific value, device technique motor pump institute consuming electric power,
The indirect energy consumptions such as recirculated cooling water, boiler feedwater, plant air, instrument air, fresh water.
By above embodiments 1-6 it is found that the present invention passes through joint coal-to-olefin technique, oil refinery dry gas compared with comparative example 1
Separating technology and methane dry reforming technique are used simultaneously to carbon dioxide and methane both greenhouse gases, are allowed to change
For the product with high added value, greenhouse gas emission is reduced, resource, the energy utilization rate of integrated artistic are significantly improved；In addition,
The present invention integrates strongly exothermic coal gasification unit, F- T synthesis unit and highly endothermic methane dry reforming unit, releases the former
The heat put is supplied to the latter, compared with prior art, improves efficiency, reduces energy consumption；Meanwhile with coal and oil refinery dry gas
During for raw material alkene, it is used in combination on the basis of system provided by the invention of the present invention for Fischer-Tropsch conjunction
At the loaded catalyst of reaction, available higher CO conversion and higher selectivity of light olefin,
Be conducive to industrialization promotion.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (27)
1. a kind of using coal and oil refinery dry gas as the method for raw material alkene, which is characterized in that method includes the following steps:
1) water-coal-slurry is made in fine coal and water；
2) with oxygen high-temperature gasification is occurred into for the water-coal-slurry and reacts obtained coal gasification crude synthesis gas；
3) the coal gasification crude synthesis gas is purified, is purified synthesis gas and carbon dioxide gas；
4) make the decontaminating syngas that Fischer-Tropsch synthesis occur, and gained mixture is separated, obtain the object of olefin-containing
Stream and carbon dioxide and methane；
5) oil refinery dry gas is separated, isolates methane therein；
6) by step 3) and/or the resulting carbon dioxide of step 4) and the resulting methane of step 5) or step 4) and step 5)
Resulting methane carries out the reaction of methane dry reforming；
Wherein, the catalyst that the Fischer-Tropsch synthesis uses is a kind of loaded catalyst, which includes containing
There is θ-alumina support of modifying agent and be supported on this and contains the active component and auxiliary agent on θ-alumina support of modifying agent,
It is characterized in that, the modifying agent is one of alkaline components, alkaline earth metal component and group ivb metal component or more
Kind, the active component is group VIII metal component, and the auxiliary agent contains alkaline components and/or rare earth component.
2. according to the method described in claim 1, wherein, this method further includes that methane dry reforming is reacted to gained synthesis gas to return
Step 4) carries out the Fischer-Tropsch synthesis.
3. according to the method described in claim 1, wherein, the condition of the Fischer-Tropsch synthesis includes the decontaminating syngas
The molar ratio of hydrogen and carbon monoxide is 0.8-2.5:1, and reaction temperature is 280-370 DEG C, reaction pressure 0.5-2.5MPa, instead
It should carry out in a fluidized bed reactor.
4. according to the method described in claim 1, wherein, this method further includes the hydrogen isolated in oil refinery dry gas, and should
Hydrogen is sent into step 3), is purified together with coal gasification crude synthesis gas.
5. according to the method described in claim 1, wherein, this method further includes that the resulting crude synthesis gas of step 2) is carried out water coal
Gas transformation, crude synthesis gas carries out the step 3) purification after gained is converted.
6. according to the method described in claim 1, wherein, this method further includes being divided the logistics of olefin-containing obtained by step 4)
From obtaining olefin stream.
7. according to the method described in claim 1, wherein, it is 600- that the condition of the methane dry reforming reaction, which includes reaction temperature,
800 DEG C, reaction pressure 0.1-1.0MPa.
8. according to the method described in claim 1, wherein, the reaction condition of the coal gasification unit closes the coal gasification slightly
It is 0.4-0.8:1 at the hydrogen of gas and the molar ratio of carbon monoxide.
9. according to the method described in claim 1, wherein, the reaction condition of the coal gasification unit includes: that reaction temperature is
1200-1500 DEG C, reaction pressure 2.8-3.2MPa.
10. according to the method described in claim 1, wherein, this method further includes making the crude synthesis gas of the coal gasification unit
For the pre- thermal medium of the preheater of the methane dry reforming unit.
11. method described in any one of -10 according to claim 1, wherein on the basis of the total amount of the catalyst, with
Elemental metal, the content of the active component are 5-70 weight %；The content of the auxiliary agent is 0.5-18 weight %；The load
The content of body is 12-94 weight %.
12. method described in any one of -10 according to claim 1, wherein on the basis of the total amount of the catalyst, with
Elemental metal, the content of the active component are 8-50 weight %；The content of the auxiliary agent is 1-15 weight %；The carrier
Content be 35-91 weight %.
13. method described in any one of -10 according to claim 1, wherein with the θ-carrying alumina containing modifying agent
On the basis of the weight of body, with elemental metal, the content of the modifying agent is 1-10 weight %.
14. method described in any one of -10 according to claim 1, wherein with the θ-carrying alumina containing modifying agent
On the basis of the weight of body, with elemental metal, the content of the modifying agent is 2.5-6 weight %.
15. method described in any one of -10 according to claim 1, wherein the modifying agent is Li, Na, K, Mg, Ca, Zr
With one of Ti or a variety of.
16. method described in any one of -10 according to claim 1, wherein the modifying agent is Zr and/or Mg.
17. method described in any one of -10 according to claim 1, wherein the θ-alumina support containing modifying agent
CO2Figure, which is desorbed, in-TPD has CO at 80-120 DEG C2Desorption peaks.
18. according to the method for claim 17, wherein the peak area of the desorption peaks is 1-3a.u..
19. method described in any one of -10 according to claim 1, wherein the auxiliary agent contains alkaline components and rare earth
Metal component, on the basis of the total amount of the catalyst, with elemental metal, as the auxiliary component alkaline components and
The content of rare earth component is respectively 0.5-8 weight % and 0.5-5 weight %.
20. method described in any one of -10 according to claim 1, wherein the active component is Fe and/or Co；As
The alkaline components of the auxiliary component are one of Li, Na and K or a variety of；The rare earth component is Ce, La and Pr
One of or it is a variety of.
21. according to the method for claim 20, wherein the alkaline components as the auxiliary component are Li and/or K；
The rare earth component is Ce and/or La.
22. method described in any one of -10 according to claim 1, wherein figure is desorbed in the CO-TPD of the loaded catalyst
At 490-580 DEG C.
23. according to the method for claim 22, wherein the CO-TPD desorption figure of the loaded catalyst is at 495-575 DEG C
There are CO desorption peaks.
24. according to the method for claim 23, wherein the peak area of the CO desorption peaks is 2.5-6a.u..
25. according to the method for claim 23, wherein the peak area of the CO desorption peaks is 3-5.5a.u..
26. method described in any one of -10 according to claim 1, wherein the loaded catalyst is by including following steps
Rapid preparation method is made: active component and auxiliary agent loaded on θ-alumina support containing modifying agent, the load
Method includes that the maceration extract containing active component and auxiliary agent point is adsorbed onto the θ-aluminium oxide containing modifying agent at least twice
It is successively dried and roasts on carrier, and every time after absorption.
27. according to the method for claim 26, wherein the maceration extract containing active component and auxiliary agent to be adsorbed onto two times
On the θ-alumina support containing modifying agent, and the volume ratio for adsorbing maceration extract used twice is 1:0.5-1.5, maceration extract
Concentration ratio be 1:0.5-2.
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| US11332417B2 (en) | 2017-06-30 | 2022-05-17 | Huadian Coal Industry Group Co., Ltd. | System and method for preparing aromatics by using syngas |
| CN109704899B (en) * | 2017-10-26 | 2022-07-08 | 中国石油化工股份有限公司 | Method for preparing olefin from synthesis gas |
| CN111116299A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Method and device for product separation and byproduct utilization of olefin prepared from synthesis gas |
| CN111116298A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Separation method and device for preparing olefin from synthesis gas |
| CN111116294A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Device and method for product separation and byproduct utilization of olefin prepared from synthesis gas |
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