CN109096024A - CO adds the reaction method of hydrogen producing light olefins - Google Patents
CO adds the reaction method of hydrogen producing light olefins Download PDFInfo
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- CN109096024A CN109096024A CN201710478217.7A CN201710478217A CN109096024A CN 109096024 A CN109096024 A CN 109096024A CN 201710478217 A CN201710478217 A CN 201710478217A CN 109096024 A CN109096024 A CN 109096024A
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- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 33
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 239000001257 hydrogen Substances 0.000 title claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 81
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 37
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 32
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 31
- 239000007789 gas Substances 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 43
- 150000001875 compounds Chemical class 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 3
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
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- 239000003795 chemical substances by application Substances 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- -1 solve the problems Chemical class 0.000 abstract description 3
- 239000000284 extract Substances 0.000 description 30
- 238000002803 maceration Methods 0.000 description 30
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 19
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- 238000011156 evaluation Methods 0.000 description 16
- 239000011572 manganese Substances 0.000 description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- 239000011701 zinc Substances 0.000 description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
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- 238000005516 engineering process Methods 0.000 description 12
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- 239000000047 product Substances 0.000 description 8
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- 230000000694 effects Effects 0.000 description 6
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- 229910052742 iron Inorganic materials 0.000 description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
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- 230000000052 comparative effect Effects 0.000 description 4
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- BYOBIQOEWYNTMM-UHFFFAOYSA-N manganese;nitric acid Chemical compound [Mn].O[N+]([O-])=O BYOBIQOEWYNTMM-UHFFFAOYSA-N 0.000 description 3
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- 229910017061 Fe Co Inorganic materials 0.000 description 2
- 241000772415 Neovison vison Species 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
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- 230000003197 catalytic effect Effects 0.000 description 2
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- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 2
- 238000001725 laser pyrolysis Methods 0.000 description 2
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- 239000011882 ultra-fine particle Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910020598 Co Fe Inorganic materials 0.000 description 1
- 229910020630 Co Ni Inorganic materials 0.000 description 1
- 229910020637 Co-Cu Inorganic materials 0.000 description 1
- 229910002519 Co-Fe Inorganic materials 0.000 description 1
- 229910002440 Co–Ni Inorganic materials 0.000 description 1
- 229910020514 Co—Y Inorganic materials 0.000 description 1
- 229910002551 Fe-Mn Inorganic materials 0.000 description 1
- 229910017112 Fe—C Inorganic materials 0.000 description 1
- 229910018666 Mn—K Inorganic materials 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
- WXOMTJVVIMOXJL-BOBFKVMVSA-A O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O[Al](O)O.O[Al](O)O.O[Al](O)O.O[Al](O)O.O[Al](O)O.O[Al](O)O.O[Al](O)O.O[Al](O)O.O[Al](O)OS(=O)(=O)OC[C@H]1O[C@@H](O[C@]2(COS(=O)(=O)O[Al](O)O)O[C@H](OS(=O)(=O)O[Al](O)O)[C@@H](OS(=O)(=O)O[Al](O)O)[C@@H]2OS(=O)(=O)O[Al](O)O)[C@H](OS(=O)(=O)O[Al](O)O)[C@@H](OS(=O)(=O)O[Al](O)O)[C@@H]1OS(=O)(=O)O[Al](O)O Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O[Al](O)O.O[Al](O)O.O[Al](O)O.O[Al](O)O.O[Al](O)O.O[Al](O)O.O[Al](O)O.O[Al](O)O.O[Al](O)OS(=O)(=O)OC[C@H]1O[C@@H](O[C@]2(COS(=O)(=O)O[Al](O)O)O[C@H](OS(=O)(=O)O[Al](O)O)[C@@H](OS(=O)(=O)O[Al](O)O)[C@@H]2OS(=O)(=O)O[Al](O)O)[C@H](OS(=O)(=O)O[Al](O)O)[C@@H](OS(=O)(=O)O[Al](O)O)[C@@H]1OS(=O)(=O)O[Al](O)O WXOMTJVVIMOXJL-BOBFKVMVSA-A 0.000 description 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- PGDDJXSLIWMIRI-UHFFFAOYSA-N acetic acid;molybdenum Chemical compound [Mo].CC(O)=O PGDDJXSLIWMIRI-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
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- 229910045601 alloy Inorganic materials 0.000 description 1
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- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
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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
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/885—Molybdenum and copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8898—Manganese, technetium or rhenium containing also molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
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Abstract
The present invention relates to CO plus the reaction methods of hydrogen producing light olefins, mainly solve the problems, such as that catalyst choice is low in synthesis gas alkene, the present invention by using preparation of low carbon olefines by synthetic gas reaction method, low-carbon alkene is generated including synthesis gas and catalyst haptoreaction, in terms of catalyst weight percent, the catalyst includes following components: (1) 30~70% active component containing Mo；The technical solution of (2) 30~70% carrier, preferably solves the problems, such as this, can be used for the industrial applications of preparation of low carbon olefines by synthetic gas.
Description
Technical field
The present invention relates to CO plus the reaction methods of hydrogen producing light olefins.
Background technique
It is the base stock of chemical industry, mesh using ethylene, propylene as the low-carbon alkene (alkene of carbon atom≤4) of representative
Before, the primary raw material of low-carbon alkene is petroleum hydrocarbon in the world, and wherein naphtha accounts for major part, and there are also alkane, hydrogenated diesel oil, portions
Divide mink cell focus etc..Both at home and abroad mostly using natural gas or light petroleum fraction as raw material, using steam cracking work in Ethylene Complex unit
Skill produces low-carbon alkene.Steam cracking is the big power consumption device in petrochemical industry, and is completely dependent on non-renewable petroleum money
Source.With the growing lack of petroleum resources, it is badly in need of finding alternate resources.So with the research of substitute gas petroleum producing olefinic hydrocarbons
Work is then taken seriously, and some famous oil companies and scientific research institutions have all carried out the research and development work of this respect in the world
Make, and achieves achievement attracting people's attention.Adjusting the structure of using energy source currently to gradually reduce the national economic development pair
Under the background of the dependence of petroleum-based energy, using the natural gas resource of China's rich reserves, pass through (the oxidation of gas making producing synthesis gas
Carbon and hydrogen mixed gas), it is then converted to the alkene of C2~C4, in the long term, there is very high strategic importance.
The method that synthesis gas is converted to alkene includes indirect method and direct method, methanol decomposition preparing low-carbon olefins MTO technique
With at gas via dimethyl ether preparing low-carbon olefins SDTO technique, first by synthesis gas synthesizing methanol or dimethyl ether, then by methanol or two
Methyl ether is converted to alkene.
Fischer-Tropsch (Fascher-Tropsch) synthesis is that (main component is CO and H using synthesis gas2) in the effect of catalyst
The process of lower synthesis hydrocarbon, is an important channel of coal and natural gas indirect liquefaction.This method is nineteen twenty-three by Germany scientist
Frans Fischer and Hans Tropsch invention, i.e. heterogeneous catalysis hydrogenation occurs on metallic catalyst for CO, raw
At the process of the mixture based on linear paraffin and alkene.Germany has just carried out research and development in the twenties in last century, and
Industrialization was realized in 1936, is closed after World War II because can not economically be competed with petroleum industry；South Africa possesses abundant
Coal resources, but petroleum resources plaque is weary, and is limited for a long time by international community's economy and political sanction, its Development of Coal system is forced
Oily industrial technology, and in 1955 built up First production capacity be 25~400,000 tons product/year coal base F-T synthetic oil factory
(Sasol-1).1973 and 1979 world oil crisis twice cause world's crude oil price to fall and swing fluctuating, rise greatly greatly
It falls, is laid in based on the considerations of Strategic Technology, F-T synthetic technology arouses the interest of industrialized country again.1980 and nineteen eighty-two,
South Africa Sasol company builds up in succession again and Liang Zuomeiji synthetic oil factory of having gone into operation.But plummeting for World oil price in 1986, pushes away
Late heavy industrialization process of the F-T synthetic technology in other countries.Since twentieth century nineties, petroleum resources are increasingly short
Scarce and in poor quality, while coal and natural gas proved reserves are but continuously increased, fischer-tropsch technologies attract extensive attention again, Fischer-Tropsch
Synthetic technology has also obtained significant progress.Currently used fischer-tropsch catalysts, from active component for be divided into two major classes: iron
Base catalyst and cobalt-base catalyst；And common synthesis technology is divided into two major classes if classifying from synthesis condition angle: high temperature
Fischer-tropsch synthesis process and Low Temperature Fischer Tropsch synthesis technology；Synthesis technology is divided into three if classifying from used reactor difference big
Class: fixed bed fischer-tropsch synthesis process, fluidized bed fischer-tropsch synthesis process (have the recirculating fluidized bed of early stage and later ciculation fluidized
Developed on the basis of bed fixed fluidized bed) and syrup state bed Fischer Tropsch synthesis technology.Fixed bed therein and slurry bed system are general
Applied to low temperature fischer-tropsch process, it is chiefly used in the production of mink cell focus and wax, and fluidized bed is then more suitable for production more lightweight
The high temperature fischer-tropsch technique of hydro carbons.
Present carbon-chemical synthesis hydro carbons purpose is the low-carbon alkene being translated into as basic chemical raw materials,
Middle ethylene and propylene are the materials of current most worthy.Moreover, being single step reaction generation by the direct preparing low-carbon olefins of synthesis gas
Purpose product, process flow is simpler than indirect method, and economic evaluation is also more worthwhile.Last decade is directly synthesized by synthesis gas
Low-carbon alkene starts to cause to pay close attention to.
Synthesis gas is converted into low-carbon alkene by F- T synthesis, in addition to by reaction process condition and thermodynamics and dynamic
The influence of terms of mechanics, catalyst are then one of vital influence factors.Nineteen twenty-three Germany scientist Franz Fisher
The reaction of syngas catalytic conversion hydro carbons is had found with Hans Tropsch, therefore, the side of hydro carbons is prepared by synthesis gas reaction
Method is known as Fiscber-Tropscb synthesis (Fischer-Tropsch synthesis, abbreviation F-T synthesis) method, i.e., with CO and H2React hydro carbons processed, by-product
Water and CO2.Nineteen fifty-five South Africa SASOL (South Africa Coal and Gas Corporation) has been built up with coal as original
The large-scale fixed bed F-T synthesizer of material, has then developed circulating fluidized bed technique, recently again develop it is fixed fluidized bed and
Slurry bed technique.Nowadays, the coal year processing capacity of SASOL has reached 50,000,000, and the annual capacity of oil product and chemicals reaches
7600000 tons.Past F-T synthesis reaction the purpose is to by synthesis gas synthetic fuel liquefied hydrocarbon, although fluidization,
The use of ferrum-based catalyst and the addition of auxiliary agent improve the yield of low-carbon alkene (C2-C4 alkene), but low-carbon to a certain extent
Olefin yields are not still high, only 20-25%.
It is mainly the following at present by preparing low-carbon olefin catalyst system.(1) F-T catalyst Dent etc. is improved
People has found that cobalt-base catalyst can be used for highly selective synthesizing low-carbon alkene, such as: Co-Cu/Al2O3、Co-Fe/SiO2、Fe-Co/
C、Co-Ni/MnO2, the systems such as Fe-Co alloy/C.The improvement FT catalyst result wherein developed with Rule chemical company is preferable,
Fe-ZnO-K2The components such as Mn or Ti are added on O catalyst, and CO conversion ratio 80%, low-carbon alkene are reached using high gas circulation
Selectivity 70%；(2) Ultra-fine Particle Catalysts Venter etc. has obtained the high score of Activated Carbon Supported by carbonyl complex decomposition method
K-Fe-Mn catalyst is dissipated, catalyst has very high activity, C in product2-C4Alkene accounts for 85-90%, and methane is to detect only
One other products.Cupta et al. has the Fe of catalytic activity using laser pyrolysis processes preparationxSiyCzEqual powder CO conversion ratio is
40%, C2 =-C4 =Selectivity reaches 87%, only a small amount of methane.Bright et al. the drop using organic salt complex of Shanxi coalification institute clock
Ultrafine particle Fe/Mn catalyst that is novel, having practical background is successfully developed and developed to solution, and CO conversion ratio is greater than 95%, C2 =-C4 =/C2-C4Greater than 80%.Beijing University of Chemical Technology Zhang Jingchang prepares high degree of dispersion amorphous superfine iron powder using laser pyrolysis processes
And carbon dust, F-T synthesizing activity new species Fe is successfully made through solid phase reaction3C.It prepares with Fe3Fe-C based on C, Fe-
The nanocatalysts such as C-Mn, Fe-C-Mn-K, CO conversion ratio is up to 90%, and olefine selective is up to 80% or more；(3) amorphous state synthesizes
Catalyst Yokoyama et al. uses amorphous state Fe40Ni40P16B4Compound, CO conversion ratio 50%, C2-C5Hydrocarbon-selective is
65%, and crystalline-state catalyst mainly generates methane；(4) zeolite catalyst, which represents system, the catalyst such as Co-A, Co-Y, Fe-Y,
The iron catalyst for the high dispersive that zeolite supports is made in Ballivet-Tketchenko et al., and selectivity of light olefin is quite high,
88-98% is in C2-C4In range, other are also showed that such as the iron catalyst that ZSM-5, mercerising, 13X zeolite support similar to behavior.
These catalyst are grown up on the basis of original fischer-tropsch catalysts, using Fe, Co or Ni as activity
Component.This kind of catalyst is using preceding necessary reduction activation, that is, just has initial activity under metallic state.Due to synthesis
Low-carbon product in order to obtain in gas preparing low carbon olefin hydrocarbon, usual operation temperature is higher, these metal active constituents can be tied
Structure variation.Metal Fe can be carbonized to form cementite during the reaction, although the formation of cementite does not influence activity or even right
The phenomenon that selectivity is advantageous, but the variation of catalyst structure will lead to catalyst carbon deposition, broken and dusting, therefore catalyst stabilization
Property is poor.Co catalyst is not suitable for using at high temperature, because forming cobalt carbide will lead to catalyst inactivation；And Ni catalyst is in height
Also carbon distribution is easy under temperature, and primary product is methane, selectivity of light olefin is low.
Summary of the invention
Present invention solves the technical problem that being that CO adds hydrogen producing light olefins (C2-C4 alkene) catalyst choice in the prior art
The low problem of property, provides the CO reaction method for adding hydrogen producing light olefins, this method has the characteristics that selectivity of light olefin is high.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows:
CO adds the reaction method of hydrogen producing light olefins, including synthesis gas and catalyst haptoreaction to generate low-carbon alkene, with
Catalyst weight percent meter, the catalyst includes following components:
(1) 30~70% active component containing Mo；
(2) 30~70% carrier.
In above-mentioned technical proposal, reaction temperature is preferably 300-450 DEG C, and unrestricted example can be within this range
350 DEG C, 400 DEG C etc..
In above-mentioned technical proposal, reaction pressure is preferably 0.5~2.5MPa, and unrestricted example can be within this range
It is 1MPa, 1.5MPa, 2MPa etc..Unless specifically stated otherwise, pressure described in description of the invention refers both to gauge pressure.
In above-mentioned technical proposal, CO and the total air volume air speed of hydrogen are preferably 1000-4000h-1, unrestricted within this range
The example of property can be 1500h-1、2000h-1、2500h-1、3000h-1、3500h-1Etc..
In above-mentioned technical proposal, H2Volume ratio with CO is preferably 0.5~3, and unrestricted example can within this range
To be 1,1.5,2,2.5 etc..
In above-mentioned technical proposal, carrier is not particularly limited, it can be using those of commonly used in the art such as but unlimited
In carrier for selected from least one of aluminium oxide, silica, titanium oxide and zirconium oxide.
In above-mentioned technical proposal, the carrier more preferably includes the mixture of aluminium oxide and zirconium oxide, aluminium oxide and oxidation
Zirconium has synergistic effect in terms of improving selectivity of light olefin.
In above-mentioned technical proposal, the dosage of carrier in the catalyst is not particularly limited, and those skilled in the art can close
Reason selection, but the content of carrier is preferably 40-60%.
Catalyst component of the present invention is free of VIII group element, such as, but not limited to without Fe, Co, Ni etc..
In above-mentioned technical proposal, it is preferred that the active component containing Mo can be by following general formula with atomic ratio measuring:
Mo100AaOx。
Wherein A is selected from least one of Mn, Cu, Zn and Ce；
The value range of a are as follows: 0~200；
X is the sum of oxygen atom needed for meeting other element valences.
In above-mentioned technical proposal, preferably a is greater than 0 and 200 hereinafter, the value range of more preferably a is 5~150；Most preferably a
Value range be 20~120.Mo and A has synergistic effect in terms of improving selectivity of light olefin.
One of in above-mentioned technical proposal, as a preferred technical scheme, at this point, improving low-carbon between following elements two-by-two
There is synergistic effect in terms of olefine selective:
A includes Cu and Mn simultaneously, and ratio mutual between two elements is not particularly limited, such as, but not limited to Mn with
The atomic ratio of Cu is 1~10, and the numerical value as non-limiting specific atomic ratio for example can be 2,3,4,5,6,7,8,9 therebetween；
Or A includes simultaneously Zn and Mn, ratio mutual between two elements is not particularly limited, such as, but not limited to
The atomic ratio of Mn and Zn is 1~10, therebetween the numerical value as non-limiting specific atomic ratio for example can be 2,3,4,5,6,7,
8,9；
Or A includes simultaneously Zn and Ce, ratio mutual between two elements is not particularly limited, such as, but not limited to
The atomic ratio of Zn and Ce is 1~10, therebetween the numerical value as non-limiting specific atomic ratio for example can be 2,3,4,5,6,7,
8、9。
In above-mentioned technical proposal, as most preferred technical solution, A includes Cu, Zn and Mn simultaneously, to three elements it
Between mutually ratio be not particularly limited, such as, but not limited to the atomic ratio of Mn:Cu:Zn be (2~5): (1~4): 1.
Three kinds of elements have apparent synergistic effect in terms of the selectivity for improving low-carbon alkene at this time.
The preparation method of catalyst described in above-mentioned technical proposal, preferably includes following steps:
(1) by the compound wiring solution-forming I of the element containing active component；
(2) solution I is mixed with carrier；
(3) it roasts.
In above-mentioned technical proposal, the compound of the element containing active component is specifically not particularly limited, as long as containing described
Active component element.Such as, but not limited to nitrate, ammonium salt, acetate etc..
In above-mentioned technical proposal, it can be used to provide the compound of active component elements Mo, such as can be but not limited to
Ammonium paramolybdate, ammonium molybdate and acetic acid molybdenum etc..
In above-mentioned technical proposal, it can be used to provide the compound of active component element Cu, such as can be but not limited to
Copper nitrate, copper acetate etc..
In above-mentioned technical proposal, it can be used to provide the compound of active component element M n, such as can be but not limited to
Manganese nitrate, manganese acetate etc..
In above-mentioned technical proposal, it can be used to provide the compound of active component element Zn, such as can be but not limited to
Zinc nitrate, zinc acetate etc..
In above-mentioned technical proposal, it can be used to provide the compound of active component Elements C e, such as can be but not limited to
Cerous nitrate, cerous acetate etc..
In above-mentioned technical proposal, the solvent that the solution uses is not particularly limited, as long as can dissolve containing active component
The compound of element obtains those of solution solvent, can contain active component according to using to this those skilled in the art
The compound dissolution properties of element reasonably select solvent.But consider from economy and security standpoint, preferably water is solvent.
In above-mentioned technical proposal, the concrete mode that step (2) solution I is mixed with carrier is not particularly limited, to solution I with
Volume ratio between carrier is it is not also specifically limited, geometry and size to carrier are not particularly limited, art technology
Personnel can reasonably select, and can reach the comparable technical effect of the present invention.It such as, but not limited to impregnates, rotate and steam
Hair, spraying, collosol and gel etc..
In above-mentioned technical proposal, the calcination steps step of step of the invention (3) be it is required, in addition to this must step it
It outside, can be with one skilled in the art will appreciate that Active components distribution is more evenly in order to obtain and obtained catalyst strength is higher
Dry step is first undergone before firing.
In above-mentioned technical proposal, whether it includes the step evaporated that those skilled in the art can rationally determine before the drying
Suddenly, in the presence of the material but after step (2) operation obtained has visualizing liquid material, preferably dry evaporation in advance before.
In above-mentioned technical proposal, the temperature of evaporation is not particularly limited, and those skilled in the art can reasonably select, such as
But be not limited to 60 DEG C or more~material boiling temperature hereinafter, the further not limiting example of this temperature range be, for example, 70 DEG C,
80 DEG C, 90 DEG C etc..
In above-mentioned technical proposal, dry condition is not particularly limited, and those skilled in the art can rationally determine.It is dry
Temperature be such as, but not limited to 80~150 DEG C, the specific non-limiting example of this temperature range can be 90 DEG C, 100 DEG C,
110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C etc..The dry time is such as, but not limited to 4~12 hours, non-limiting in this section
Example can be 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours etc..
In above-mentioned technical proposal, the atmosphere of roasting is not particularly limited, but generallys use oxygenous atmosphere, for it is economical because
Element meter generallys use the atmosphere that air is roasting.
In above-mentioned technical proposal, the temperature of roasting is preferably 450~650 DEG C, the non-limiting specific example in this section
Son can be 500 DEG C, 550 DEG C, 600 DEG C etc..
In above-mentioned technical proposal, the time of roasting is preferably 2~12 hours, and in this section, non-limiting specific example can
To be 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours etc..
It does not need catalyst reduction into metallic state, just there is oxidation state CO to add hydrogen activation capacity, and catalyst makes
With in the process, metal oxide will not be reduced into metal, can keep oxidation state, and mistake of the metal to Carbides Transformation does not occur
Journey, so as to avoid traditional fischer-tropsch catalysts structural instability and inactivation the problems such as.Simultaneously because the stable structure of oxide
Property, catalyst can use at a higher temperature, and available more low-carbon product improves the selectivity of low-carbon alkene.
It is that the present invention reacts evaluation method is as follows:
Reactor: fixed bed reactors, internal diameter 10mm；
Loaded catalyst: 2.0 grams
H2: CO volume ratio 1.5；
The CO and total air volume air speed 2000h of hydrogen-1；
Reaction temperature is 350 DEG C；
Reaction pressure 1.5MPa.
C2-C4Olefine selective calculation formula is as follows:
Using catalyst prepared by the present invention, at 300-450 DEG C, 0.5-2.5MPa, volume space velocity 1000-4000h-1Item
It is reacted under part, CO conversion ratio > 50%, C2-C4Olefine selective > 55% achieves preferable technical effect.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
It weighs and is equivalent to 50 grams of MoO3Ammonium paramolybdate be dissolved in water, obtain 100 grams of maceration extracts, maceration extract and 50 grams aoxidized
Aluminium (20~60 mesh) mixing is stirred lower 80 DEG C and is steamed extremely without visible liquid, 12 hours dry through 120 DEG C, in 550 DEG C of air atmospheres
Roasting obtains catalyst in 5 hours.
Catalyst forms and evaluation results are shown in Table 1.
[embodiment 2]
It weighs and is equivalent to 50 grams of MoO3And MnO2Ammonium paramolybdate and manganese nitrate (wherein the atomic ratio of Mo and Mn be 100:70)
It is dissolved in water, obtains 100 grams of maceration extracts, maceration extract is mixed with 50 grams of aluminium oxide (20~60 mesh), lower 80 DEG C is stirred and steams to can not
See liquid, it is 12 hours dry through 120 DEG C, it is roasted 5 hours in 550 DEG C of air atmospheres and obtains catalyst.
Catalyst forms and evaluation results are shown in Table 1.
[comparative example 1]
It weighs and is equivalent to 50 grams of MnO2Manganese nitrate be dissolved in water, 100 grams of maceration extracts are obtained, by maceration extract and 50 grams of aluminium oxide
(20~60 mesh) mixing is stirred lower 80 DEG C and is steamed extremely without visible liquid, 12 hours dry through 120 DEG C, roasts in 550 DEG C of air atmospheres
It burns 5 hours and obtains catalyst.
Catalyst forms and evaluation results are shown in Table 1.
[embodiment 3]
It weighs and is equivalent to 50 grams of MoO3(wherein the atomic ratio of Mo and Cu is with the ammonium paramolybdate and Copper nitrate hexahydrate of CuO
It 100:70) is dissolved in water, obtains 100 grams of maceration extracts, maceration extract is mixed with 50 grams of aluminium oxide (20~60 mesh), stirs lower 80 DEG C of steamings
To without visible liquid, is dried 12 hours through 120 DEG C, roasted 5 hours in 550 DEG C of air atmospheres and obtain catalyst.
Catalyst forms and evaluation results are shown in Table 1.
[comparative example 2]
It weighs and is equivalent to the Copper nitrate hexahydrate of 50 grams of CuO and is dissolved in water, 100 grams of maceration extracts are obtained, by maceration extract and 50 grams of oxygen
Change aluminium (20~60 mesh) mixing, stirs lower 80 DEG C and steam extremely without visible liquid, it is 12 hours dry through 120 DEG C, in 550 DEG C of air atmospheres
Middle roasting obtains catalyst in 5 hours.
Catalyst forms and evaluation results are shown in Table 1.
[embodiment 4]
It weighs and is equivalent to 50 grams of MoO3(wherein the atomic ratio of Mo and Zn is with the ammonium paramolybdate and zinc nitrate hexahydrate of ZnO
It 100:70) is dissolved in water, obtains 100 grams of maceration extracts, maceration extract is mixed with 50 grams of aluminium oxide (20~60 mesh), stirs lower 80 DEG C of steamings
To without visible liquid, is dried 12 hours through 120 DEG C, roasted 5 hours in 550 DEG C of air atmospheres and obtain catalyst.
Catalyst forms and evaluation results are shown in Table 1.
[comparative example 3]
It weighs and is equivalent to the zinc nitrate hexahydrate of 50 grams of ZnO and is dissolved in water, 100 grams of maceration extracts are obtained, by maceration extract and 50 grams of oxygen
Change aluminium (20~60 mesh) mixing, stirs lower 80 DEG C and steam extremely without visible liquid, it is 12 hours dry through 120 DEG C, in 550 DEG C of air atmospheres
Middle roasting obtains catalyst in 5 hours.
Catalyst forms and evaluation results are shown in Table 1.
[embodiment 5]
It weighs and is equivalent to 50 grams of MoO3, CuO and MnO2Ammonium paramolybdate, Copper nitrate hexahydrate and manganese nitrate (wherein Mo:Cu:Mn
Atomic ratio be 100:30:40) be dissolved in water, obtain 100 grams of maceration extracts, maceration extract and 50 grams of aluminium oxide (20~60 mesh) mixed
It closes, stirs lower 80 DEG C and steam extremely without visible liquid, it is 12 hours dry through 120 DEG C, it roasts 5 hours and obtains in 550 DEG C of air atmospheres
Catalyst.
Catalyst forms and evaluation results are shown in Table 1.
[embodiment 6]
It weighs and is equivalent to 50 grams of MoO3, ZnO and MnO2Ammonium paramolybdate, zinc nitrate hexahydrate and manganese nitrate (wherein Mo:Zn:Mn
Atomic ratio be 100:20:50) be dissolved in water, obtain 100 grams of maceration extracts, maceration extract and 50 grams of aluminium oxide (20~60 mesh) mixed
It closes, stirs lower 80 DEG C and steam extremely without visible liquid, it is 12 hours dry through 120 DEG C, it roasts 5 hours and obtains in 550 DEG C of air atmospheres
Catalyst.
Catalyst forms and evaluation results are shown in Table 1.
[embodiment 7]
It weighs and is equivalent to 50 grams of MoO3, ZnO and Ce2O3Ammonium paramolybdate, zinc nitrate hexahydrate and cerium nitrate hexahydrate (wherein Mo:
The atomic ratio of Cu:Ce is 100:50:20) it is dissolved in water, 100 grams of maceration extracts are obtained, by maceration extract and 50 grams of aluminium oxide (20~60
Mesh) mixing, it stirs lower 80 DEG C and steams extremely without visible liquid, it is 12 hours dry through 120 DEG C, it is roasted 5 hours in 550 DEG C of air atmospheres
Obtain catalyst.
Catalyst forms and evaluation results are shown in Table 1.
[embodiment 8]
It weighs and is equivalent to 50 grams of MoO3And Ce2O3Ammonium paramolybdate and cerium nitrate hexahydrate (wherein the atomic ratio of Mo and Ce is
It 100:70) is dissolved in water, obtains 100 grams of maceration extracts, maceration extract is mixed with 50 grams of aluminium oxide (20~60 mesh), stirs lower 80 DEG C of steamings
To without visible liquid, is dried 12 hours through 120 DEG C, roasted 5 hours in 550 DEG C of air atmospheres and obtain catalyst.
Catalyst forms and evaluation results are shown in Table 1.
[comparative example 4]
It weighs and is equivalent to the cerium nitrate hexahydrate of 50 grams of CeO and is dissolved in water, 100 grams of maceration extracts are obtained, by maceration extract and 50 grams of oxygen
Change aluminium (20~60 mesh) mixing, stirs lower 80 DEG C and steam extremely without visible liquid, it is 12 hours dry through 120 DEG C, in 550 DEG C of air atmospheres
Middle roasting obtains catalyst in 5 hours.
Catalyst forms and evaluation results are shown in Table 1.
[embodiment 9]
It weighs and is equivalent to 50 grams of MoO3, CuO, ZnO and MnO2Ammonium paramolybdate, Copper nitrate hexahydrate, zinc nitrate hexahydrate and nitric acid
Manganese (wherein the atomic ratio of Mo:Cu:Zn:Mn is 100:10:25:35) is dissolved in water, 100 grams of maceration extracts is obtained, by maceration extract and 50
The mixing of gram aluminium oxide (20~60 mesh) is stirred lower 80 DEG C and is steamed to without visible liquid, 12 hours dry through 120 DEG C, in 550 DEG C of air
It is roasted 5 hours in atmosphere and obtains catalyst.
Catalyst forms and evaluation results are shown in Table 1.
[embodiment 10]
It weighs and is equivalent to 50 grams of MoO3, CuO, ZnO and MnO2Ammonium paramolybdate, Copper nitrate hexahydrate, zinc nitrate hexahydrate and nitric acid
Manganese (wherein the atomic ratio of Mo:Cu:Zn:Mn is 100:10:25:35) is dissolved in water, 100 grams of maceration extracts is obtained, by maceration extract and 50
The mixing of gram zirconium oxide (20~60 mesh) is stirred lower 80 DEG C and is steamed to without visible liquid, 12 hours dry through 120 DEG C, in 550 DEG C of air
It is roasted 5 hours in atmosphere and obtains catalyst.
Catalyst forms and evaluation results are shown in Table 1.
[embodiment 11]
It weighs and is equivalent to 50 grams of MoO3, CuO, ZnO and MnO2Ammonium paramolybdate, Copper nitrate hexahydrate, zinc nitrate hexahydrate and nitric acid
Manganese (wherein the atomic ratio of Mo:Cu:Zn:Mn is 100:10:25:35) is dissolved in water, 100 grams of maceration extracts is obtained, by maceration extract and 50
Mixture zirconium oxide (20~60 mesh, the wherein Al of gram aluminium oxide sum2O3: ZrO2Weight ratio be 2:3), stir it is lower 80 DEG C steam extremely
It is 12 hours dry through 120 DEG C without visible liquid, it is roasted 5 hours in 550 DEG C of air atmospheres and obtains catalyst.
Catalyst forms and evaluation results are shown in Table 1.
Table 1
Claims (8)
1.CO adds the reaction method of hydrogen producing light olefins, including synthesis gas and catalyst haptoreaction to generate low-carbon alkene, to urge
Agent weight percent meter, the catalyst includes following components:
(1) 30~70% active component containing Mo；
(2) 30~70% carrier.
2. reaction method according to claim 1, it is characterized in that reaction temperature is 300-450 DEG C.
3. reaction method according to claim 1, it is characterized in that reaction pressure is 0.5~2.5MPa.
4. reaction method according to claim 1, it is characterized in that synthesis gas volume space velocity is preferably 1000-4000h-1。
5. reaction method according to claim 1, it is characterized in that H in synthesis gas2Volume ratio with CO is 0.5~3.
6. reaction method according to claim 1, it is characterised in that the carrier is selected from aluminium oxide, silica, oxygen
Change at least one of titanium and zirconium oxide.
7. reaction method according to claim 1, it is characterised in that the weight content of carrier is preferably 40- in catalyst
60%.
8. reaction method according to claim 1, it is characterised in that catalyst described in any one of claim 1~7
Preparation method, include the following steps:
(1) by the compound wiring solution-forming I of the element containing active component；
(2) solution I is mixed with carrier；
(3) it roasts.
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| CN1522178A (en) * | 2001-05-08 | 2004-08-18 | �յ�-��ѧ��˾ | High Surface Area, Small Grain Size Catalysts for Fischer-Tropsch Synthesis |
| CN104549343A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin from synthesis gas as well as preparation method and application of catalyst |
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| CN1522178A (en) * | 2001-05-08 | 2004-08-18 | �յ�-��ѧ��˾ | High Surface Area, Small Grain Size Catalysts for Fischer-Tropsch Synthesis |
| CN104549343A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin from synthesis gas as well as preparation method and application of catalyst |
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