CN109651035A - The method of one-step method from syngas producing light olefins - Google Patents
The method of one-step method from syngas producing light olefins Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 37
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 105
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 29
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 23
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 8
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 38
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 5
- -1 solve the problems Chemical class 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000012530 fluid Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 239000002002 slurry Substances 0.000 description 23
- 239000011572 manganese Substances 0.000 description 21
- 239000011701 zinc Substances 0.000 description 21
- 238000011068 loading method Methods 0.000 description 19
- 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 18
- 229910002651 NO3 Inorganic materials 0.000 description 17
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 17
- 239000010949 copper Substances 0.000 description 17
- 239000007921 spray Substances 0.000 description 16
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 16
- 239000002994 raw material Substances 0.000 description 13
- 230000009467 reduction Effects 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 238000011084 recovery Methods 0.000 description 10
- 229910052681 coesite Inorganic materials 0.000 description 9
- 229910052906 cristobalite Inorganic materials 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 229910052682 stishovite Inorganic materials 0.000 description 9
- 229910052905 tridymite Inorganic materials 0.000 description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 8
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 8
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 8
- 239000000908 ammonium hydroxide Substances 0.000 description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- XQBXQQNSKADUDV-UHFFFAOYSA-N lanthanum;nitric acid Chemical compound [La].O[N+]([O-])=O XQBXQQNSKADUDV-UHFFFAOYSA-N 0.000 description 8
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 8
- 239000011268 mixed slurry Substances 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 238000005507 spraying Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000001694 spray drying Methods 0.000 description 7
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 229910052792 caesium Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 229910001845 yogo sapphire 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
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
- C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
-
- 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
- B01J23/8892—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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to the methods of one-step method from syngas producing light olefins, mainly solve the problems, such as that selectivity of light olefin is lower in the prior art, the present invention by using one-step method from syngas producing light olefins method, it is included in the presence of ferrum-based catalyst, synthesis gas reaction generates low-carbon alkene, the catalyst includes carrier and active component, and the active component contains with atomic ratio measuring, the following composition of chemical formula: Fe100MnaZnbCucQfOx, Q includes that the technical solution selected from least one of lanthanide series preferably solves the problems, such as this, be can be used in the industrial production of fluid bed syngas synthesizing low-carbon alkene.
Description
Technical field
The present invention relates to the methods of one-step method from syngas producing light olefins.
Background technique
It is nineteen twenty-three by Germany scientist Frans that synthesis gas, which is passed through the method that catalyst action is converted into hydro carbons,
Fischer and Hans Tropsch invention, heterogeneous catalysis hydrogenation occurs on metallic catalyst for abbreviation F-T synthesis, i.e. CO
Reaction generates the process of the mixture based on linear paraffin and alkene.Germany the twenties in last century just carried out research and
Exploitation, and industrialization was realized in 1936, it is closed after World War II because can not economically be competed with petroleum industry；South Africa possesses
Coal resources abundant, but petroleum resources plaque is weary, and is limited for a long time by international community's economy and political sanction, its hair is forced
Coal-to-oil industry technology is opened up, and having built up First production capacity in 1955 is ten thousand tons of product/year coal base F-T synthesis of 25-40
Oily factory (Sasol-1).
1973 and 1979 world oil crisis twice cause world's crude oil price to fall and swing fluctuating, big rise and big fall,
It 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
Non- Sasol company builds up in succession again and Liang Zuomeiji synthetic oil factory of having gone into operation.But World oil price in 1986 plummets, and postpones
Heavy industrialization process of the F-T synthetic technology in other countries.
Since twentieth century nineties, petroleum resources shortage and in poor quality, while coal and natural gas proved reserves increasingly
But it is continuously increased, F-T synthetic technology attracts extensive attention again.Currently, the primary raw material of low-carbon alkene is petroleum hydrocarbon in the world
Class, wherein naphtha accounts for major part, and there are also alkane, hydrogenated diesel oil, part mink cell focuses etc..Both at home and abroad mostly with natural gas or lightweight stone
Oil distillate is raw material, produces low-carbon alkene using steam cracking process in Ethylene Complex unit, steam cracking is in petrochemical industry
Big power consumption device, and be completely dependent on non-renewable petroleum resources, with the growing lack of petroleum resources, be badly in need of finding and replace
For resource.So the research work with other substitution of resources petroleum producing olefinic hydrocarbons is gradually paid attention to, it is some famous in the world
Oil company and scientific research institutions all carried out the research of this respect, and achieve good achievement.
After decades of development, F-T synthetic catalyst has also obtained significant progress, and fischer-tropsch synthetic catalyst usually wraps
Include following component: active metal (the VIIIth group 4 transition metal), oxide carrier or structural promoter (SiO2,Al2O3Deng), chemistry helps
Agent (alkali metal oxide, transition metal) and precious metal additive (Ru, Re etc.).Fe largely generates alkene and oxygenatedchemicals, Ru,
Co mainly generates long-chain saturated hydrocarbons, and Ni mainly generates methane.When due to Ni compressive reaction easily formed carbonyls be lost with
And methanation is serious, Ru, Rh etc. are expensive, currently used catalyst, from active component for be divided into two major classes: it is iron-based
Catalyst and cobalt-base catalyst.Co-catalyst influences very big, the raising of selectivity of light olefin for the selectivity of low-carbon alkene
It is mainly realized by co-catalyst, the selection of co-catalyst and adding technique are the key technologies for developing excellent catalyst
One of.
According to the difference of used catalyst and the difference of target product, it is anti-that F-T synthesis reactor is divided into fixed bed again
Answer device, fluidized-bed reactor and paste state bed reactor.Structure is complicated for fixed bed reactors, expensive, and cooling is difficult, entire to fill
The production capacity set is lower.The characteristics of slurry bed system is that reaction temperature is lower, easily controllable, but conversion ratio is lower, and product is mostly high-carbon hydrocarbon
And in reactor slurries solid-liquor separation it is more difficult.The characteristics of fluidized-bed reactor is that temperature is higher, and conversion ratio is higher, does not deposit
In the difficulty of solid-liquor separation, product is mostly lower carbon number hydrocarbons；It builds and operating cost is lower, and low pressure difference saves a large amount of pressure
Contracting expense, and be more conducive to except the heat released in dereaction, simultaneously because gas linear velocity is low, wear problem is smaller, this makes to grow
Phase operating is possibly realized.
Iron catalyst have the advantages that it is very much, such as obtain low-carbon alkene with high selectivity, prepare high-octane gasoline etc.,
In addition ferrum-based catalyst also has the characteristics that operating condition is wide, product adjustability is big.The preparation method of Fe-series catalyst mainly has
Three kinds: the precipitation method (precipitated catalyst), ingredient is in addition to Fe, and there are also the auxiliary agents such as Mn, Zn, K, it is made into mixing by a certain percentage
Solution after being heated to boiling, is added precipitating reagent stirring, is then filtered, washed.Gained filter cake is added into water pulp again, it is fixed to be added
Then the potassium silicate of amount, grinds, sieves through drying, extrusion forming；Sintering process (sintered catalyst)；Oxide mixing method is (molten
Iron catalyst), raw material is made with the mill scale or magnetite powder of steel rolling mill, adds auxiliary agent A l2O3, MgO, MnO and CuO etc., be sent into 1500
The melting of DEG C electric arc furnaces, the fusant of outflow is through mold, cooling, multiple stage crushing.
The direct F-T synthesizing low-carbon alkene of ferrum-based catalyst carries out mostly in fixed bed at present, in patent CN1040397C
It is just referred to a kind of ferrum-based catalyst for F- T synthesis low-carbon alkene, the selectivity of low-carbon alkene can be up to 69%.But
It is that structure is complicated for fixed bed reactors, expensive, cooling is difficult, and the production capacity of whole device is lower.The spy of fluidized-bed reactor
Point is that temperature is higher, and conversion ratio is higher, and there is no the difficulty of solid-liquor separation, product is mostly lower carbon number hydrocarbons；Build and operating cost compared with
It is low, and low pressure difference saves a large amount of compression expense, and is more conducive to except the heat released in dereaction, simultaneously because gas
Linear velocity is low, and wear problem is smaller, this makes it possible to operate for a long time.The currently reported fluidized bed F-T that is applied to is synthesized
Be mostly molten iron type catalyst, as be referred in patent CN1704161A it is a kind of for F-T synthesize molten iron type catalyst；But mesh
There are products not enough to concentrate for preceding fluidized bed F-T synthesis, the not high enough problem of the selectivity of low-carbon alkene.
Summary of the invention
The technical problem to be solved by the present invention is to the lower problems of selectivity of light olefin in the prior art, provide one kind
The method of one-step method from syngas producing light olefins, this method have the characteristics that selectivity of light olefin is high.
In order to solve the above technical problems, technical scheme is as follows:
The method of one-step method from syngas producing light olefins, is included in the presence of ferrum-based catalyst, and synthesis gas reaction generates low
Carbon olefin, the catalyst include carrier and active component, and the active component contains with atomic ratio measuring, the following group of chemical formula
Close object:
Fe100MnaZnbCuc QfOx；
Q includes selected from least one of lanthanide series；
The value range of a is 5.0~60.0；
The value range of b is 5.0~60.0；
The value range of c is 1.0~30.0；
The value range of f is 0.9~40.0；
X is to meet the sum of oxygen atom needed for each element chemical valence in catalyst.
In above-mentioned technical proposal, carrier is not particularly limited, can be using those of commonly used in the art, such as, but not limited to
Including at least one of aluminium oxide, silica and titanium oxide.
In above-mentioned technical proposal, the dosage of carrier is not particularly limited, and those skilled in the art can reasonably select and not
With making the creative labor, such as, but not limited to carrier dosage is the 30~70% of catalyst weight by weight percentage.
In above-mentioned technical proposal, it is also preferable to include at least one of IA elements by Q, and lanthanide series and alkali metal element are simultaneously
There are be conducive to improve the selectivity of low-carbon alkene.At this point, Fe100MnaZnbCucQfOxIt can be further represented as
Fe100MnaZnbCucAdLeOx, wherein A is at least one of IA element, and L is at least one of lanthanide series, the value model of d
Enclosing for the value range of 1.0~30.0, e is 0.1~10.0.
In above-mentioned technical proposal, the value range of a is preferably 10.0~50.0.Such as, but not limited to 15.0,20.0,
25.0,30.0,35.0,40.0,45.0 etc..
In above-mentioned technical proposal, the value range of b is preferably 10.0~50.0.Such as, but not limited to 15.0,20.0,
25.0,30.0,35.0,40.0,45.0 etc..
In above-mentioned technical proposal, the value range of c is preferably 5.0~25.0.Such as, but not limited to 10.0,12.0,13.0,
14.0,15.0,16.0,17.0,18.0,19.0,20.0 etc..
In above-mentioned technical proposal, the value range of d is preferably 2.0~25.0.Such as, but not limited to 3.0,4.0,5.0,
8.0,10.0,15.0,20.0 etc..
In above-mentioned technical proposal, the value range of e is preferably 1.0~8.0.Such as, but not limited to 2.0,3.0,4.0,5.0,
6.0,7.0 etc..
In above-mentioned technical proposal, the IA element is selected from least one of Li, Na, K and Cs；The IA element is more preferable
It simultaneously include at least two in Li, K and Cs, at this time between described two elements, such as Li is being mentioned with K, Li and Cs, K and Cs
There is synergistic effect in terms of high-low carbon olefine selective.The atomic ratio between two kinds of elements is not particularly limited at this time, such as but
Be not limited to 0.1~10, wherein more specific atomic ratio can be 0.2,0.4,0.6,0.8,1.0,1.5,2.0,2.5,3.0,
3.5,4.0,4.5,5.0 etc..
In above-mentioned technical proposal, the lanthanide series includes being selected from La.
Catalyst of the present invention, can also not for that can first pass through reduction before the reaction of one-step method from syngas producing light olefins
By reduction, but preferably by reduction.When reduction, reducing condition is not particularly limited, and those skilled in the art can be reasonable
Selection, the reducing condition of catalyst such as, but not limited to produced by the present invention: pressure be 0.05~5MPa, preferably 0.1~
4MPa；Reducing gas can use hydrogen, carbon monoxide or synthesis gas, when with synthesis gas, H2/ CO molar ratio is 0.1~6.0,
Preferably 0.2~6.0；Also the load of Primordial Qi is 100~8000 hours-1, preferably 500~6000 hours-1；Reduction temperature is
200~600 DEG C, preferably 220~500 DEG C；Recovery time is 1~100 hour, preferably 6~72 hours.
In order to year-on-year, reducing condition used in obtained catalyst is equal in the specific embodiment of the invention are as follows:
400 DEG C of temperature
Pressure 3.0MPa
100 grams of loaded catalyst
Catalyst loading 4000 hours-1
Also Primordial Qi H2/ CO=2/1
Recovery time 24 hours.
Key problem in technology of the invention is the selection of catalyst, can for process conditions those skilled in the art of concrete application
It does not need to make the creative labor to reasonably select.
One skilled in the art will appreciate that low-carbon alkene refers to the alkene of C2~C4, more particularly ethylene, propylene and butylene
Or their mixture.Butylene includes butene-1, butene-2, isobutene, butadiene.
The temperature of reaction, which can be reaction temperature, to be 200~600 DEG C, preferably 220~500 DEG C；
The pressure of reaction can be 0.5~10MPa, preferably 1~8MPa；；
H in synthesis gas2/ CO molar ratio can be 0.1~5.0, preferably 0.5~3.0；
The volume space velocity of synthesis gas can be 100~8000 hours-1, preferably 500~6000 hours-1, more preferably 2000
~6000 hours-1。
In order to count on year-on-year basis, the evaluation condition of the catalyst used in the specific embodiment of the invention is equal are as follows:
38 millimeters of fluidized-bed reactors of φ
330 DEG C of reaction temperature
Reaction pressure 2.0MPa
100 grams of loaded catalyst
Catalyst loading 3000 hours-1
Raw material proportioning (mole) H2/ CO=2/1.
Catalyst described in above-mentioned technology can be prepared using method comprising the following steps:
The slurry including catalyst carrier and active component element is obtained, the pH value of slurry is 1~6；
Slurry is sent into spray dryer spray shaping；
Roasting.
When in active component simultaneously containing lanthanide series with alkali metal element, the preparation method of catalyst is preferably comprised
Following processing step:
Obtain the aqueous solution including the metallic element in addition to alkali metal in the composition；
The colloidal sol of aequum carrier is added to above-mentioned aqueous solution, alkali hydroxide soln is added, uses acid-base accommodation
It is 1~6 that agent, which adjusts pH value, obtains slurry；
Slurry is sent into spray dryer spray shaping；
Roasting.
In above-mentioned technical proposal, the temperature of roasting is preferably 400~1000 DEG C, and more preferably 450~800 DEG C.
In above-mentioned technical proposal, the time of roasting is preferably 0.15~10 hour, and more preferably 0.5~8 hour.
The process conditions of spray drying forming are not particularly limited, and those skilled in the art can reasonably select, and can take
Obtain comparable technical effect.Such as, but not limited to spray inlet temperature can be 200~380 DEG C, and outlet temperature can be 100
Spray-dried to be shaped to microspheroidal under conditions of~230 DEG C, finally catalyst is made in roasting.
For convenient for year-on-year, the spray drying condition that the specific embodiment of the invention uses is equal are as follows:
300 DEG C of inlet temperature,
200 DEG C of outlet temperature.
In above-mentioned technical proposal, soluble ferric iron salt can be ferric nitrate or ferric sulfate.
In above-mentioned technical proposal, the soluble compound of Mn, Zn, Cu and lanthanide series can be nitrate, can be analyzed to
The salt of oxide.
In above-mentioned technical proposal, the atmosphere of roasting is not particularly limited, but preferably oxidizing atmosphere or inert atmosphere, is
Economic consideration, more preferably air atmosphere.
In the present invention, unless specifically stated otherwise, the pressure includes that reaction pressure refers both to gauge pressure.
Using the present invention, at 200~600 DEG C of reaction temperature, 0.5~10MPa of reaction pressure, catalyst loading 100~
8000 hours-1, raw material proportioning (mole) H2/ CO=(0.1~5.0): F-T synthetic reaction is carried out under conditions of 1, CO conversion ratio can
Up to 91.7%, the selectivity of low-carbon alkene achieves preferable technical effect up to 71.5% in reaction product.
The present invention will be further described below by way of examples.
Specific embodiment
[embodiment 1]
1, catalyst preparation
Take 343.00 grams of ferric nitrate (Fe (NO3)3·9H2O), add 500g water to dissolve, obtain material I, take 12.20 grams of nitric acid
Lanthanum (La (NO3)3·6H2O) plus 100g water dissolves by heating, and obtains material II, takes 119.10 gram of 50% manganese nitrate (Mn (NO3)2)、
30.46 grams of copper nitrate (Cu (NO3)2·3H2) and 50.51 grams of zinc nitrate (Zn (NO O3)2·6H2O) in Yu Tongyi container, add 200g
Water, stirring and dissolving obtain material III.
By material I, III mixing, the silica solution material of 312.50 gram 40% (weight) is added under stiring, is then added and contains
The aqueous solution 50g of 6.83 grams of KOH makes the pH of mixed slurry with concentration for the pH value that 27% (weight) ammonium hydroxide adjusts above-mentioned slurry
=6.0, manufactured slurry carries out framboid molding in spray dryer after being sufficiently stirred, and specific spray drying condition is spray
300 DEG C of mist machine inlet temperature, 200 DEG C of outlet temperature.It is finally 89 millimeters in internal diameter, length is 1700 millimeters of (φ 89 × 1700
Millimeter) rotary roasting furnace in roasted 2.0 hours in 500 DEG C of air atmospheres, manufactured catalyst composition are as follows:
50 weight %Fe100Mn40Zn20Cu15K12La5Ox+ 50 weight %SiO2
2, the reduction and evaluation of catalyst
Obtained catalyst is carried out in reducing condition:
400 DEG C of temperature
Pressure 3.0MPa
100 grams of loaded catalyst
Catalyst loading 4000 hours-1
Also Primordial Qi H2/ CO=2/1
Recovery time 24 hours
It is restored, then carries out Fischer-Tropsch synthesis under the following conditions:
38 millimeters of fluidized-bed reactors of φ
330 DEG C of reaction temperature
Reaction pressure 2.0MPa
100 grams of loaded catalyst
Catalyst loading 3000 hours-1
Raw material proportioning (mole) H2/ CO=2/1.
The experimental result of synthetic reaction is listed in table 1.
[embodiment 2]
1, catalyst preparation
Take 352.10 grams of ferric nitrate (Fe (NO3)3·9H2O), add 500g water to dissolve, obtain material I, take 12.60 grams of nitric acid
Lanthanum (La (NO3)3·6H2O) plus 100g water dissolves by heating, and obtains material II, takes 122.20 gram of 50% manganese nitrate (Mn (NO3)2)、
31.26 grams of copper nitrate (Cu (NO3)2·3H2) and 51.84 grams of zinc nitrate (Zn (NO O3)2·6H2O) in Yu Tongyi container, add 200g
Water, stirring and dissolving obtain material III.
By material I, III mixing, the silica solution material of 312.50 gram 40% (weight) is added under stiring, is then added and contains
The aqueous solution 50g of 7.09 grams of LiOH makes mixed slurry with the pH value that concentration adjusts above-mentioned slurry for 27% (weight) ammonium hydroxide
PH=6.0, manufactured slurry carries out framboid molding in spray dryer after being sufficiently stirred, and specific spray drying condition is
300 DEG C of spraying machine inlet temperature, 200 DEG C of outlet temperature.Finally internal diameter be 89 millimeters, length be 1700 millimeters (φ 89 ×
1700 millimeters) rotary roasting furnace in roasted 2.0 hours in 500 DEG C of air atmospheres, manufactured catalyst composition are as follows:
50 weight %Fe100Mn40Zn20Cu15Li12La5Ox+ 50 weight %SiO2
2, the reduction and evaluation of catalyst
Obtained catalyst is carried out in reducing condition:
400 DEG C of temperature
Pressure 3.0MPa
100 grams of loaded catalyst
Catalyst loading 4000 hours-1
Also Primordial Qi H2/ CO=2/1
Recovery time 24 hours
It is restored, then carries out Fischer-Tropsch synthesis under the following conditions:
38 millimeters of fluidized-bed reactors of φ
330 DEG C of reaction temperature
Reaction pressure 2.0MPa
100 grams of loaded catalyst
Catalyst loading 3000 hours-1
Raw material proportioning (mole) H2/ CO=2/1.
The experimental result of synthetic reaction is listed in table 1.
[embodiment 3]
1, catalyst preparation
Take 319.10 grams of ferric nitrate (Fe (NO3)3·9H2O), add 500g water to dissolve, obtain material I, take 11.40 grams of nitric acid
Lanthanum (La (NO3)3·6H2O) plus 100g water dissolves by heating, and obtains material II, takes 110.80 gram of 50% manganese nitrate (Mn (NO3)2)、
28.33 grams of copper nitrate (Cu (NO3)2·3H2) and 46.99 grams of zinc nitrate (Zn (NO O3)2·6H2O) in Yu Tongyi container, add 200g
Water, stirring and dissolving obtain material III.
By material I, III mixing, the silica solution material of 312.50 gram 40% (weight) is added under stiring, is then added and contains
The aqueous solution 50g of 1.98 grams of CsOH makes mixed slurry with the pH value that concentration adjusts above-mentioned slurry for 27% (weight) ammonium hydroxide
PH=6.0, manufactured slurry carries out framboid molding in spray dryer after being sufficiently stirred, and specific spray drying condition is
300 DEG C of spraying machine inlet temperature, 200 DEG C of outlet temperature.Finally internal diameter be 89 millimeters, length be 1700 millimeters (φ 89 ×
1700 millimeters) rotary roasting furnace in roasted 2.0 hours in 500 DEG C of air atmospheres, manufactured catalyst composition are as follows:
50 weight %Fe100Mn40Zn20Cu15Cs12La5Ox+ 50 weight %SiO2
2, the reduction and evaluation of catalyst
Obtained catalyst is carried out in reducing condition:
400 DEG C of temperature
Pressure 3.0MPa
100 grams of loaded catalyst
Catalyst loading 4000 hours-1
Also Primordial Qi H2/ CO=2/1
Recovery time 24 hours
It is restored, then carries out Fischer-Tropsch synthesis under the following conditions:
38 millimeters of fluidized-bed reactors of φ
330 DEG C of reaction temperature
Reaction pressure 2.0MPa
100 grams of loaded catalyst
Catalyst loading 3000 hours-1
Raw material proportioning (mole) H2/ CO=2/1.
The experimental result of synthetic reaction is listed in table 1.
[embodiment 4]
1, catalyst preparation
Take 347.50 grams of ferric nitrate (Fe (NO3)3·9H2O), add 500g water to dissolve, obtain material I, take 12.40 grams of nitric acid
Lanthanum (La (NO3)3·6H2O) plus 100g water dissolves by heating, and obtains material II, takes 120.70 gram of 50% manganese nitrate (Mn (NO3)2)、
30.85 grams of copper nitrate (Cu (NO3)2·3H2) and 51.17 grams of zinc nitrate (Zn (NO O3)2·6H2O) in Yu Tongyi container, add 200g
Water, stirring and dissolving obtain material III.
Material I, II, III are mixed, the silica solution material of 312.50 gram 40% (weight) is added under stiring, is then added
Aqueous solution 50g containing 4.10 grams of NaOH makes mixed slurry with the pH value that concentration adjusts above-mentioned slurry for 27% (weight) ammonium hydroxide
PH=6.0, manufactured slurry carries out framboid molding, specific spray drying condition in spray dryer after being sufficiently stirred
It is 300 DEG C of spraying machine inlet temperature, 200 DEG C of outlet temperature.Finally internal diameter be 89 millimeters, length be 1700 millimeters (φ 89 ×
1700 millimeters) rotary roasting furnace in roasted 2.0 hours in 500 DEG C of air atmospheres, manufactured catalyst composition are as follows:
50 weight %Fe100Mn40Zn20Cu15Na12La5Ox+ 50 weight %SiO2
2, the reduction and evaluation of catalyst
Obtained catalyst is carried out in reducing condition:
400 DEG C of temperature
Pressure 3.0MPa
100 grams of loaded catalyst
Catalyst loading 4000 hours-1
Also Primordial Qi H2/ CO=2/1
Recovery time 24 hours
It is restored, then carries out Fischer-Tropsch synthesis under the following conditions:
38 millimeters of fluidized-bed reactors of φ
330 DEG C of reaction temperature
Reaction pressure 2.0MPa
100 grams of loaded catalyst
Catalyst loading 3000 hours-1
Raw material proportioning (mole) H2/ CO=2/1.
The experimental result of synthetic reaction is listed in table 1.
[embodiment 5]
1, catalyst preparation
Take 347.50 grams of ferric nitrate (Fe (NO3)3·9H2O), add 500g water to dissolve, obtain material I, take 12.40 grams of nitric acid
Lanthanum (La (NO3)3·6H2O) plus 100g water dissolves by heating, and obtains material II, takes 120.70 gram of 50% manganese nitrate (Mn (NO3)2)、
30.85 grams of copper nitrate (Cu (NO3)2·3H2) and 51.17 grams of zinc nitrate (Zn (NO O3)2·6H2O) in Yu Tongyi container, add 200g
Water, stirring and dissolving obtain material III.
Material I, II, III are mixed, the silica solution material of 312.50 gram 40% (weight) is added under stiring, is then added
Aqueous solution 50g containing 3.50 grams of LiOH, 3.46 grams of KOH is that 27% (weight) ammonium hydroxide adjusts the pH value of above-mentioned slurry and makes with concentration
The pH=6.0 of mixed slurry is obtained, manufactured slurry carries out framboid molding in spray dryer after being sufficiently stirred, specific to spray
Mist drying condition is 300 DEG C of spraying machine inlet temperature, 200 DEG C of outlet temperature.It is finally 89 millimeters in internal diameter, length is 1700 millis
It is roasted 2.0 hours in the rotary roasting furnace of rice (89 × 1700 millimeters of φ) in 500 DEG C of air atmospheres, manufactured catalyst composition
Are as follows:
50 weight %Fe100Mn40Zn20Cu15Li6K6La5Ox+ 50 weight %SiO2
2, the reduction and evaluation of catalyst
Obtained catalyst is carried out in reducing condition:
400 DEG C of temperature
Pressure 3.0MPa
100 grams of loaded catalyst
Catalyst loading 4000 hours-1
Also Primordial Qi H2/ CO=2/1
Recovery time 24 hours
It is restored, then carries out Fischer-Tropsch synthesis under the following conditions:
38 millimeters of fluidized-bed reactors of φ
330 DEG C of reaction temperature
Reaction pressure 2.0MPa
100 grams of loaded catalyst
Catalyst loading 3000 hours-1
Raw material proportioning (mole) H2/ CO=2/1.
The experimental result of synthetic reaction is listed in table 1.
[embodiment 6]
1, catalyst preparation
Take 334.80 grams of ferric nitrate (Fe (NO3)3·9H2O), add 500g water to dissolve, obtain material I, take 11.90 grams of nitric acid
Lanthanum (La (NO3)3·6H2O) plus 100g water dissolves by heating, and obtains material II, takes 116.20 gram of 50% manganese nitrate (Mn (NO3)2)、
29.73 grams of copper nitrate (Cu (NO3)2·3H2) and 49.30 grams of zinc nitrate (Zn (NO O3)2·6H2O) in Yu Tongyi container, add 200g
Water, stirring and dissolving obtain material III.
By material I, III mixing, the silica solution material of 312.50 gram 40% (weight) is added under stiring, is then added and contains
3.37 grams LiOH, 9.55CsOH grams of aqueous solution 50g is made with the pH value that concentration adjusts above-mentioned slurry for 27% (weight) ammonium hydroxide
The pH=6.0 of mixed slurry, manufactured slurry carries out framboid molding in spray dryer after being sufficiently stirred, specific spraying
Drying condition is 300 DEG C of spraying machine inlet temperature, 200 DEG C of outlet temperature.It is finally 89 millimeters in internal diameter, length is 1700 millimeters
It is roasted 2.0 hours in the rotary roasting furnace of (89 × 1700 millimeters of φ) in 500 DEG C of air atmospheres, manufactured catalyst composition are as follows:
50 weight %Fe100Mn40Zn20Cu15Li6Cs6La5Ox+ 50 weight %SiO2
2, the reduction and evaluation of catalyst
Obtained catalyst is carried out in reducing condition:
400 DEG C of temperature
Pressure 3.0MPa
100 grams of loaded catalyst
Catalyst loading 4000 hours-1
Also Primordial Qi H2/ CO=2/1
Recovery time 24 hours
It is restored, then carries out Fischer-Tropsch synthesis under the following conditions:
38 millimeters of fluidized-bed reactors of φ
330 DEG C of reaction temperature
Reaction pressure 2.0MPa
100 grams of loaded catalyst
Catalyst loading 3000 hours-1
Raw material proportioning (mole) H2/ CO=2/1.
The experimental result of synthetic reaction is listed in table 1.
[embodiment 7]
1, catalyst preparation
Take 330.60 grams of ferric nitrate (Fe (NO3)3·9H2O), add 500g water to dissolve, obtain material I, take 11.80 grams of nitric acid
Lanthanum (La (NO3)3·6H2O) plus 100g water dissolves by heating, and obtains material II, takes 114.80 gram of 50% manganese nitrate (Mn (NO3)2)、
29.36 grams of copper nitrate (Cu (NO3)2·3H2) and 48.69 grams of zinc nitrate (Zn (NO O3)2·6H2O) in Yu Tongyi container, add 200g
Water, stirring and dissolving obtain material III.
Material I, II, III are mixed, the silica solution material of 312.50 gram 40% (weight) is added under stiring, is then added
Aqueous solution 50g containing 3.29 grams of KOH, 9.43 grams of CsOH is that 27% (weight) ammonium hydroxide adjusts the pH value of above-mentioned slurry and makes with concentration
The pH=6.0 of mixed slurry is obtained, manufactured slurry carries out framboid molding in spray dryer after being sufficiently stirred, specific to spray
Mist drying condition is 300 DEG C of spraying machine inlet temperature, 200 DEG C of outlet temperature.It is finally 89 millimeters in internal diameter, length is 1700 millis
It is roasted 2.0 hours in the rotary roasting furnace of rice (89 × 1700 millimeters of φ) in 500 DEG C of air atmospheres, manufactured catalyst composition
Are as follows:
50 weight %Fe100Mn40Zn20Cu15K6Cs6La5Ox+ 50 weight %SiO2
2, the reduction and evaluation of catalyst
Obtained catalyst is carried out in reducing condition:
400 DEG C of temperature
Pressure 3.0MPa
100 grams of loaded catalyst
Catalyst loading 4000 hours-1
Also Primordial Qi H2/ CO=2/1
Recovery time 24 hours
It is restored, then carries out Fischer-Tropsch synthesis under the following conditions:
38 millimeters of fluidized-bed reactors of φ
330 DEG C of reaction temperature
Reaction pressure 2.0MPa
100 grams of loaded catalyst
Catalyst loading 3000 hours-1
Raw material proportioning (mole) H2/ CO=2/1.
The experimental result of synthetic reaction is listed in table 1.
[embodiment 8]
1, catalyst preparation
Take 337.50 grams of ferric nitrate (Fe (NO3)3·9H2O), add 500g water to dissolve, obtain material I, take 12.00 grams of nitric acid
Lanthanum (La (NO3)3·6H2O) plus 100g water dissolves by heating, and obtains material II, takes 117.20 gram of 50% manganese nitrate (Mn (NO3)2)、
29.97 grams of copper nitrate (Cu (NO3)2·3H2) and 49.70 grams of zinc nitrate (Zn (NO O3)2·6H2O) in Yu Tongyi container, add 200g
Water, stirring and dissolving obtain material III.
Material I, II, III are mixed, the silica solution material of 312.50 gram 40% (weight) is added under stiring, is then added
Aqueous solution 50g containing 2.24 grams of KOH, 2.26 grams of LiOH, 6.42 grams of CsOH is that 27% (weight) ammonium hydroxide adjusts above-mentioned slurry with concentration
The pH value of material makes the pH=6.0 of mixed slurry, and manufactured slurry carries out framboid in spray dryer after being sufficiently stirred
Molding, specific spray drying condition are 300 DEG C of spraying machine inlet temperature, 200 DEG C of outlet temperature.It is finally 89 millimeters in internal diameter,
Length is to roast 2.0 hours in the rotary roasting furnace of 1700 millimeters (89 × 1700 millimeters of φ) in 500 DEG C of air atmospheres, manufactured
Catalyst composition are as follows:
50 weight %Fe100Mn40Zn20Cu15Li4K4Cs4La5Ox+ 50 weight %SiO2
2, the reduction and evaluation of catalyst
Obtained catalyst is carried out in reducing condition:
400 DEG C of temperature
Pressure 3.0MPa
100 grams of loaded catalyst
Catalyst loading 4000 hours-1
Also Primordial Qi H2/ CO=2/1
Recovery time 24 hours
It is restored, then carries out Fischer-Tropsch synthesis under the following conditions:
38 millimeters of fluidized-bed reactors of φ
330 DEG C of reaction temperature
Reaction pressure 2.0MPa
100 grams of loaded catalyst
Catalyst loading 3000 hours-1
Raw material proportioning (mole) H2/ CO=2/1.
The experimental result of synthetic reaction is listed in table 1.
Table 1
Claims (8)
1. the method for one-step method from syngas producing light olefins, is included in the presence of ferrum-based catalyst, synthesis gas reaction generates low-carbon
Alkene, the catalyst include carrier and active component, and the active component contains with atomic ratio measuring, the following combination of chemical formula
Object:
Fe100MnaZnbCucQfOx,
Q includes selected from least one of lanthanide series；
The value range of a is 5.0~60.0；
The value range of b is 5.0~60.0；
The value range of c is 1.0~30.0；
The value range of f is 0.9~40.0；
X is to meet the sum of oxygen atom needed for each element chemical valence in catalyst.
2. according to the method described in claim 1, it is characterized in that reaction temperature is 200~600 DEG C.
3. according to the method described in claim 1, it is characterized in that H in synthesis gas2/ CO molar ratio is 0.1~5.0.
4. according to the method described in claim 1, it is characterized in that the volume space velocity of synthesis gas is 100~8000 hours-1。
5. according to the method described in claim 1, it is characterized in that carrier includes in silica, aluminium oxide and titanium oxide
It is at least one.
6. according to the method described in claim 1, it is characterized in that the value range of a is 10.0~50.0.
7. according to the method described in claim 1, it is characterized in that the value range of b is 10.0~50.0.
8. according to the method described in claim 1, it is characterized in that the value range of c is 5.0~25.0.
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