CN117324012A - Catalyst for preparing olefin from synthesis gas, and preparation method and application thereof - Google Patents
Catalyst for preparing olefin from synthesis gas, and preparation method and application thereof Download PDFInfo
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- CN117324012A CN117324012A CN202210739249.9A CN202210739249A CN117324012A CN 117324012 A CN117324012 A CN 117324012A CN 202210739249 A CN202210739249 A CN 202210739249A CN 117324012 A CN117324012 A CN 117324012A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 37
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 35
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 25
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
- 239000007789 gas Substances 0.000 claims description 41
- 239000002002 slurry Substances 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- 238000001694 spray drying Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- 238000009718 spray deposition Methods 0.000 claims description 12
- 238000004537 pulping Methods 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 6
- 229910001882 dioxygen Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- -1 carrier Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 125000002947 alkylene group Chemical group 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 46
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 31
- 238000005507 spraying Methods 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 229910052742 iron Inorganic materials 0.000 description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 9
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 description 7
- 229910000159 nickel phosphate Inorganic materials 0.000 description 7
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910017116 Fe—Mo Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003034 coal gas Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009904 heterogeneous catalytic hydrogenation reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
-
- 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
- C07C1/0445—Preparation; Activation
-
- 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
Abstract
The invention discloses a catalyst for preparing olefin from synthesis gas, a preparation method and application thereof. The catalyst comprises 20-50 parts of carrier and 50-80 parts of active component by weight; the active component comprises a composition of the formula: fe (Fe) 100 Mo a B b Ni 1.5c P c O x . The catalyst is suitable for the reaction of synthesis gas to prepare olefin, especially lower CO/H 2 The reaction of the synthesis gas to olefins in molar ratio has the advantage of high efficiency conversion of the synthesis gas with higher alkylene ratio in the product.
Description
Technical Field
The invention belongs to the field of olefin preparation from synthesis gas, and particularly relates to a catalyst for olefin preparation from synthesis gas, a preparation method and application thereof.
Background
Fischer-Tropsch (Fascher-Tropsch) synthesis is a heterogeneous catalytic hydrogenation of CO over metal catalysts, which was discovered in 1923 by German scientists Frans Fischer and Hans Tropsch, and is an important route for the indirect liquefaction of coal and natural gas. The Chinese energy is characterized by rich coal, less gas and oil, and environmental pollution caused by direct combustion of coal is also becoming important. The development of the process of converting the coal/natural gas into petroleum products through the synthesis gas can reduce the dependence on foreign energy sources, and has important significance for solving the environmental pollution problem caused by fire coal.
Depending on the type of metal catalyst employed, the primary product of the Fischer-Tropsch CO hydrogenation will vary. Generally, ni catalysts have extremely strong hydrogenation properties and are used in the production of methane from synthesis gas. CN110339855a reports a Ni catalyst for methane production from synthesis gas and a method for preparing the same. Cu/Zn/Mo is mainly used for preparing low-carbon alcohol by synthesis gas, especially for producing raw material methanol indirectly converted by synthesis gas, and Fe and Co are used as C in large scale 2+ Is a process for the production of an alkene hydrocarbon.
Fischer-Tropsch synthesis is a strong exothermic chemical process, especially a synthesis process of products mainly comprising organic hydrocarbons with lighter carbon chain lengths less than 20, the adiabatic temperature of the products rises to 1500 ℃, when a fixed bed is used, the heat in the reactor is difficult to remove, the temperature is easy to fly, the catalyst is easy to deactivate, and the fluidized bed can well overcome the problems of the fixed bed. Fluidized beds typically use iron-based catalysts, but fluidized bed iron-based Fischer Tropsch is typically used for CO/H conversion 2 Higher coal-based syngas for CO/H 2 When the conversion of the natural gas-based synthesis gas is low, the problems of high alkane selectivity and low alkene selectivity in the product exist.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a catalyst for preparing olefin from synthesis gas, and a preparation method and application thereof. The catalyst is suitable for the reaction of synthesis gas to prepare olefin, especially lower CO/H 2 The reaction of the synthesis gas to olefins in molar ratio has the advantage of high efficiency conversion of the synthesis gas with higher alkylene ratio in the product.
The invention provides a catalyst for preparing olefin from synthesis gas, which comprises 20-50 parts of carrier and 50-80 parts of active component in parts by weight;
the active component comprises a composition with the following chemical formula in terms of atomic ratio: fe (Fe) 100 Mo a B b Ni 1.5c P c O x ，
Wherein B comprises at least one member selected from the group consisting of alkali metals,
a has a value ranging from 3 to 30;
b has a value ranging from 0.1 to 10;
c has a value range of 0.05-2;
x is the total number of oxygen atoms required to satisfy the valence of each element in the catalyst.
According to the invention, the support comprises at least one of oxides of Ti and Zr.
According to the invention, said B comprises at least one of Na, K, rb, cs.
According to the XPS result, the catalyst has the molar ratio of Ni to P on the surface of the catalyst of 6-13:1.
According to the benzene invention, the catalyst is microsphere.
The second aspect of the present invention provides a process for preparing the catalyst, the process comprising the steps of:
(1) Fe salt, mo salt, carrier, alkali metal source and Ni 3 (PO 4 ) 2 Mixing and pulping to obtain slurry;
(2) And (3) spray drying, forming and roasting the slurry obtained in the step (1) to obtain the catalyst.
According to the invention, the Fe salt in step (1) is a soluble Fe salt; the Mo salt is soluble Mo salt. The alkali metal source comprises at least one of an alkali metal-containing base and a salt.
According to the present invention, preferably, in the step (1), the Fe salt and the Mo salt are dissolved in water to form a solutionWith a carrier, an alkali metal source and Ni 3 (PO 4 ) 2 Mixing.
According to the present invention, preferably, an acid-base modifier is added in the step (1) to adjust the pH to 1 to 5; the acid-base modifier is selected according to the conventional method, and ammonia water is preferred.
According to the present invention, it is preferable that the solid content in the slurry obtained in the step (1) is 15 to 45% by weight.
According to the invention, the temperature of the mixed beating in the step (1) is 80-100 ℃.
According to the invention, the spray forming device in step (2) is a spray dryer.
According to the invention, the hot air temperature of the spray drying in step (2) is 150 to 350 ℃. Further, the spray-dried hot air medium is a mixed gas of air and non-oxygen gas; preferably, the volume ratio of air to non-oxygen gas in the mixed gas is 1:3-7; more preferably, the non-oxygen gas is nitrogen.
According to the invention, the roasting temperature in the step (2) is 450-700 ℃; roasting for 0.3-5 h; the roasting atmosphere is a mixed gas of nitrogen and air, and the volume ratio of the nitrogen to the air is preferably 2-5:1.
In a third aspect, the present invention provides the use of the catalyst described above or a catalyst prepared by the method described above in a synthesis gas to olefin reaction.
According to the invention, the composition of the synthesis gas comprises CO and hydrogen. Preferably, the volume ratio of CO to hydrogen is 1:3.5-5.
According to the invention, the temperature of the reaction is 300-400 ℃; the pressure of the reaction is 0.5-8 MPa; the catalyst loading (volume space velocity) is 2500-11500 h -1 。
Compared with the prior art, the invention has the main beneficial effects that:
(1) The catalyst comprises 20-50 parts of carrier and 50-80 parts of active component by weight; the active component comprises a composition with the following chemical formula in terms of atomic ratio: fe (Fe) 100 Mo a B b Ni 1.5c P c O x . The invention is realized by the method in the Fe-Mo catalyst groupThe catalyst is doped with Ni and P elements in a specific proportion, and the Ni and P on the surface of the catalyst are further distributed according to a certain proportion range, and the catalyst is particularly suitable for low CO/H 2 Is used for preparing olefin by converting synthesis gas. The catalyst is used for the reaction, and has the advantages of high efficiency of converting synthesis gas and higher alkene-alkane ratio in the product.
(2) In the preparation method of the catalyst, ni is added in the preparation process of the Fe-Mo catalyst 3 (PO 4 ) 2 The catalyst is particularly suitable for the reaction of preparing olefin from synthesis gas with low molar ratio, and has the advantages of high-efficiency conversion of synthesis gas and higher olefin-alkane ratio in the product.
(3) The catalyst of the invention is suitable for conversion reaction for preparing olefin, especially for low CO/H 2 Is used for preparing olefin by converting synthesis gas. The catalyst is applied to the reaction, can efficiently convert the synthesis gas, has higher alkene-alkane ratio, and solves the problem of catalyst deactivation caused by poor heat removal capacity of the strong exothermic reaction.
Detailed Description
In the invention, XPS characterization is carried out on the surface element analysis of the catalyst by adopting an EscalLab xi+X-ray photoelectron spectrometer.
In the present invention, the CO conversion (%) is calculated as mass fraction.
In the invention, C 2 + Hydrocarbon selectivity (%) is in mass fraction. C (C) 2 + The hydrocarbon comprising C 2 + Olefins, C 2 + Alkanes.
In the invention, C 2 + The olefin is an olefin having 2 to 20 carbon atoms. C (C) 2 + The alkane is an alkane with 2-20 carbon atoms.
In the invention, C 2 + olefins/C 2 + The alkane is the molar ratio of the alkene with 2-20 carbon atoms to the alkane with 2-20 carbon atoms.
In the present invention, the methods for evaluating the catalysts of examples 1 to 5 and comparative examples 2 to 4 were as follows:
the catalyst is reduced by adopting an in-situ reduction method, and after the reduction is finished, the process conditions are directly switched into the synthesis reaction conditions in a reactor used for reduction to start the reaction;
reactor specification:a millimeter fluidized bed reactor;
catalyst loading: 50 g;
the reduction conditions are as follows: the temperature is 450 DEG C
Pressure of 0.1MPa
Catalyst loading (standard volumetric space velocity) for 6000 hours -1
Reducing gas H 2
Reduction time 12 hours
The synthesis reaction conditions are as follows: the reaction temperature is 360 DEG C
The reaction pressure was 1.5MPa
Catalyst loading (standard volumetric space velocity) for 6000 hours -1
Raw material ratio (mol) of CO/H in synthesis gas 2 ＝1:4
The reaction was run for 100 hours.
[ example 1 ]
Taking 1mol of Fe (NO) 3 ) 3 ·9H 2 O is dissolved in water to prepare 0.5mol/L Fe element solution I, and 0.03mol of ammonium heptamolybdate is taken to prepare 0.5mol/L Mo aqueous solution II; taking a mixture containing 115g of ZrO 2 40wt% zirconium sol, 40wt% KOH solution containing 0.04mol K element and 0.002mol Ni 3 (PO 4 ) 2 Mixing the 40wt% nickel phosphate solution with the solution I and the solution II, stirring and pulping at 90 ℃, adjusting the pH value of the mixture to 5 by using 25wt% ammonia water, and adjusting the solid content of the mixture to 35% by using water to obtain slurry III; spray drying and forming the slurry, wherein the inlet temperature of a spraying machine is 350 ℃, the outlet temperature of the spraying machine is 200 ℃, and a hot air medium of the spraying machine is a mixed gas of air and nitrogen in a volume ratio of 1:5, so as to obtain a spray drying material; thenRoasting for 2 hours at 650 ℃ in a low-oxygen atmosphere with the volume ratio of nitrogen to air being 3, and obtaining the catalyst. The composition of the catalyst is as follows: 50wt% Fe 100 Mo 21 K 4 Ni 0.6 P 0.4 O x +50wt％ZrO 2 。
XPS detects that the molar ratio of Ni to P on the surface of the prepared catalyst is 10:1.
The results of the catalyst evaluation test are shown in Table 1.
[ example 2 ]
Taking 1mol of Fe (NO) 3 ) 3 ·9H 2 O is dissolved in water to prepare 0.5mol/L Fe element solution I, and 0.03mol of ammonium heptamolybdate is taken to prepare 0.5mol/L Mo aqueous solution II; taking a mixture containing 115g of ZrO 2 40wt% zirconium sol, 40wt% KOH solution containing 0.04mol K element and 0.006mol Ni 3 (PO 4 ) 2 Mixing the 40wt% nickel phosphate solution with the solution I and the solution II, stirring and pulping at 90 ℃, adjusting the pH value of the mixture to 5 by using 25wt% ammonia water, and adjusting the solid content of the mixture to 35% by using water to obtain slurry III; spray drying and forming the slurry, wherein the inlet temperature of a spraying machine is 350 ℃, the outlet temperature of the spraying machine is 200 ℃, and a hot air medium of the spraying machine is a mixed gas of air and nitrogen in a volume ratio of 1:5, so as to obtain a spray drying material; and then roasting for 2 hours at 650 ℃ in a low-oxygen atmosphere with the volume ratio of nitrogen to air being 3, so as to obtain the catalyst. The composition of the catalyst is as follows: 50wt% Fe 100 Mo 21 K 4 Ni 1.8 P 1.2 O x +50wt％ZrO 2 。
XPS detects that the molar ratio of Ni to P on the surface of the prepared catalyst is 12:1.
The results of the catalyst evaluation test are shown in Table 1.
[ example 3 ]
Taking 1mol of Fe (NO) 3 ) 3 ·9H 2 O is dissolved in water to prepare 0.5mol/L Fe element solution I, and 0.03mol of ammonium heptamolybdate is taken to prepare 0.5mol/L Mo aqueous solution II; taking a mixture containing 115g of ZrO 2 40wt% zirconium sol, 40wt% KOH solution containing 0.04mol K element and 0.00025mol Ni 3 (PO 4 ) 2 Mixing the 40wt% nickel phosphate solution with the solution I and the solution II, stirring and pulping at 90 ℃, adjusting the pH value of the mixture to 5 by using 25wt% ammonia water, and adjusting the solid content of the mixture to 35% by using water to obtain slurry III; spray drying and forming the slurry, wherein the inlet temperature of a spraying machine is 350 ℃, the outlet temperature of the spraying machine is 200 ℃, and a hot air medium of the spraying machine is a mixed gas of air and nitrogen in a volume ratio of 1:5, so as to obtain a spray drying material; and then roasting for 2 hours at 650 ℃ in a low-oxygen atmosphere with the volume ratio of nitrogen to air being 3, so as to obtain the catalyst. The composition of the catalyst is as follows: 50wt% Fe 100 Mo 21 K 4 Ni 0.075 P 0.05 O x +50wt％ZrO 2 。
XPS detects that the molar ratio of Ni to P on the surface of the prepared catalyst is 6:1.
The results of the catalyst evaluation test are shown in Table 1.
[ example 4 ]
Taking 1mol of Fe (NO) 3 ) 3 ·9H 2 O is dissolved in water to prepare 0.5mol/L Fe element solution I, and 0.03mol of ammonium heptamolybdate is taken to prepare 0.5mol/L Mo aqueous solution II; taking a mixture containing 115g of ZrO 2 40wt% zirconium sol, 40wt% KOH solution containing 0.04mol K element and 0.002mol Ni 3 (PO 4 ) 2 Mixing the 40wt% nickel phosphate solution with the solution I and the solution II, stirring and pulping at 90 ℃, adjusting the pH value of the mixture to 5 by using 25wt% ammonia water, and adjusting the solid content of the mixture to 35% by using water to obtain slurry III; spray drying and forming the slurry, wherein the inlet temperature of a spraying machine is 350 ℃, the outlet temperature of the spraying machine is 200 ℃, and a hot air medium of the spraying machine is a mixed gas of air and nitrogen in a volume ratio of 1:5, so as to obtain a spray drying material; and then roasting for 2 hours at 650 ℃ in a low-oxygen atmosphere with the volume ratio of nitrogen to air being 3, so as to obtain the catalyst. The composition of the catalyst is as follows: 50wt% Fe 100 Mo 21 K 4 Ni 0.6 P 0.4 O x +50wt％ZrO 2 。
XPS detects that the molar ratio of Ni to P on the surface of the prepared catalyst is 10:1.
The results of the catalyst evaluation test are shown in Table 1.
[ example 5 ]
Taking 1mol of Fe (NO) 3 ) 3 ·9H 2 O is dissolved in water to prepare 0.5mol/L Fe element solution I, and 0.03mol of ammonium heptamolybdate is taken to prepare 0.5mol/L Mo aqueous solution II; taking a mixture containing 115g of ZrO 2 40wt% zirconium sol containing 0.04mol Ru element, 40wt% RbOH solution and 0.002mol Ni 3 (PO 4 ) 2 Mixing the 40wt% nickel phosphate solution with the solution I and the solution II, stirring and pulping at 90 ℃, adjusting the pH value of the mixture to 5 by using 25wt% ammonia water, and adjusting the solid content of the mixture to 35% by using water to obtain slurry III; spray drying and forming the slurry, wherein the inlet temperature of a spraying machine is 350 ℃, the outlet temperature of the spraying machine is 200 ℃, and a hot air medium of the spraying machine is a mixed gas of air and nitrogen in a volume ratio of 1:5, so as to obtain a spray drying material; and then roasting for 2 hours at 650 ℃ in a low-oxygen atmosphere with the volume ratio of nitrogen to air being 3, so as to obtain the catalyst. The composition of the catalyst is as follows: 50wt% Fe 100 Mo 21 Rb 4 Ni 0.6 P 0.4 O x +50wt％ZrO 2 。
XPS detects that the molar ratio of Ni to P on the surface of the prepared catalyst is 10:1.
The results of the catalyst evaluation test are shown in Table 1.
[ comparative example 1 ]
Taking 1mol of Fe (NO) 3 ) 3 ·9H 2 O is dissolved in water to prepare 0.5mol/L Fe element solution I, and 0.03mol of ammonium heptamolybdate is taken to prepare 0.5mol/L Mo aqueous solution II; taking a mixture of 115g ZrO 2 40wt% zirconium sol, 40wt% KOH solution containing 0.04mol K element and 0.002mol Ni 3 (PO 4 ) 2 Mixing the 40wt% nickel phosphate solution with the solution I and the solution II, stirring and pulping at 90 ℃, adjusting the pH value of the mixture to 5 by using 25wt% ammonia water, and adjusting the solid content of the mixture to 35% by using water to obtain slurry III; spray drying and forming the slurry, wherein the inlet temperature of a sprayer is 350 ℃, the outlet temperature of the sprayer is 200 ℃, and the hot air medium of the sprayer is the mixture of air and nitrogen in a volume ratio of 1:5, so as to obtain a spray dried productDrying the material; and then roasting for 2 hours at 650 ℃ in a low-oxygen atmosphere with the volume ratio of nitrogen to air being 3, so as to obtain the catalyst. The composition of the catalyst is as follows: 50wt% Fe 100 Mo 21 K 4 Ni 0.6 P 0.4 O x +50wt％ZrO 2 。
XPS detects that the molar ratio of Ni to P on the surface of the prepared catalyst is 10:1.
The catalyst evaluation conditions were the same as in the examples, except that the raw material ratio (mole) CO/H of the synthesis gas was evaluated 2 =1:1.5. The test reaction results are shown in Table 1.
[ comparative example 2 ]
Taking 1mol of Fe (NO) 3 ) 3 ·9H 2 O is dissolved in water to prepare 0.5mol/L Fe element solution I, and 0.03mol of ammonium heptamolybdate is taken to prepare 0.5mol/L Mo aqueous solution II; taking a mixture of 115g ZrO 2 40wt% zirconium sol, 40wt% KOH solution containing 0.04mol of K element and 0.006mol of Ni (NO 3 ) 2 Mixing the 40wt% nickel nitrate solution with the solution I and the solution II, stirring and pulping at 90 ℃, adjusting the pH value of the mixture to 5 by using 25wt% ammonia water, and adjusting the solid content of the mixture to 35% by using water to obtain slurry III; spray drying and forming the slurry, wherein the inlet temperature of a spraying machine is 350 ℃, the outlet temperature of the spraying machine is 200 ℃, and a hot air medium of the spraying machine is a mixed gas of air and nitrogen in a volume ratio of 1:5, so as to obtain a spray drying material; and then roasting for 2 hours at 650 ℃ in a low-oxygen atmosphere with the volume ratio of nitrogen to air being 3, so as to obtain the catalyst. The composition of the catalyst is as follows: 50wt% Fe 100 Mo 21 K 4 Ni 0.6 O x +50wt％ZrO 2 。
The results of the catalyst evaluation test are shown in Table 1.
[ comparative example 3 ]
Taking 1mol of Fe (NO) 3 ) 3 ·9H 2 O is dissolved in water to prepare 0.5mol/L Fe element solution I, and 0.03mol of ammonium heptamolybdate is taken to prepare 0.5mol/L Mo aqueous solution II; taking a mixture of 115g ZrO 2 40wt% zirconium sol, 40wt% KOH solution containing 0.04mol K element and 0.004mol H 3 PO 4 40wt%Mixing the phosphoric acid solution (II) with the solution (I) and the solution (II), stirring and pulping at 90 ℃, adjusting the pH value of the mixture to 5 by using ammonia water with the concentration of 25wt%, and adjusting the solid content of the mixture to 35% by using water to obtain slurry (III); spray drying and forming the slurry, wherein the inlet temperature of a spraying machine is 350 ℃, the outlet temperature of the spraying machine is 200 ℃, and a hot air medium of the spraying machine is a mixed gas of air and nitrogen in a volume ratio of 1:5, so as to obtain a spray drying material; and then roasting for 2 hours at 650 ℃ in a low-oxygen atmosphere with the volume ratio of nitrogen to air being 3, so as to obtain the catalyst. The composition of the catalyst is as follows: 50wt% Fe 100 Mo 21 K 4 P 0.4 O x +50wt％ZrO 2 。
The results of the catalyst evaluation test are shown in Table 1.
[ comparative example 4 ]
Taking 1mol of Fe (NO) 3 ) 3 ·9H 2 O is dissolved in water to prepare 0.5mol/L Fe element solution I, and 0.03mol of ammonium heptamolybdate is taken to prepare 0.5mol/L Mo aqueous solution II; taking a mixture containing 115g of ZrO 2 40wt% zirconium sol, 40wt% KOH solution containing 0.04mol K element and 0.002mol Ni 3 (PO 4 ) 2 Mixing the 40wt% nickel phosphate solution with the solution I and the solution II, stirring and pulping at 90 ℃, adjusting the pH value of the mixture to 5 by using 25wt% ammonia water, and adjusting the solid content of the mixture to 35% by using water to obtain slurry III; spray drying and forming the slurry, wherein the inlet temperature of a spraying machine is 350 ℃, the outlet temperature of the spraying machine is 200 ℃, and a hot air medium of the spraying machine is air to obtain a spray drying material; and then roasting for 2 hours at 650 ℃ in an air atmosphere to obtain the catalyst. The composition of the catalyst is as follows: 50wt% Fe 100 Mo 21 K 4 Ni 0.6 P 0.4 O x +50wt％ZrO 2 。
XPS detects that the molar ratio of Ni to P on the surface of the prepared catalyst is 20:1.
The results of the catalyst evaluation test are shown in Table 1.
TABLE 1
| Catalyst | CO conversion (%) | C 2 + Hydrocarbon selectivity (%) | C 2 + olefins/C 2 + Alkanes |
| Example 1 | 92 | 91 | 5.6 |
| Example 2 | 90 | 88 | 7.2 |
| Example 3 | 89 | 89 | 6.7 |
| Example 4 | 91 | 93 | 5.8 |
| Example 5 | 93 | 90 | 5.7 |
| Comparative example 1 | 58 | 90 | 5.7 |
| Comparative example 2 | 95 | 63 | 1.3 |
| Comparative example 3 | 73 | 71 | 2.4 |
| Comparative example 4 | 72 | 48 | 0.3 |
The above describes in detail the specific embodiments of the present invention, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. The catalyst for preparing olefin from synthesis gas is characterized by comprising 20-50 parts of carrier and 50-80 parts of active component in parts by weight;
the active component comprises a composition with the following chemical formula in terms of atomic ratio: fe (Fe) 100 Mo a B b Ni 1.5c P c O x ，
Wherein B comprises at least one member selected from the group consisting of alkali metals,
a has a value ranging from 3 to 30;
b has a value ranging from 0.1 to 10;
c has a value range of 0.05-2;
x is the total number of oxygen atoms required to satisfy the valence of each element in the catalyst.
2. The catalyst of claim 1, wherein the molar ratio of Ni to P on the catalyst surface is 6-13:1.
3. The catalyst of claim 1, wherein the support comprises at least one of oxides of Ti and Zr; and/or, the B includes at least one of Na, K, rb, cs.
4. A process for the preparation of a catalyst as claimed in any one of claims 1 to 3, comprising the steps of:
(1) Fe salt, mo salt, carrier, alkali metal source and Ni 3 (PO 4 ) 2 Mixing and pulping to obtain slurry;
(2) And (3) spray drying, forming and roasting the slurry obtained in the step (1) to obtain the catalyst.
5. The preparation method according to claim 1, wherein the pH is adjusted to 1-5 by adding an acid-base regulator in the step (1).
6. The process for preparing a catalyst according to claim 4, wherein the slurry obtained in the step (1) has a solids content of 15 to 45% by weight.
7. The method for preparing a catalyst according to claim 4, wherein the hot air temperature of spray drying in the step (2) is 150 to 350 ℃;
further, the spray-dried hot air medium is a mixed gas of air and non-oxygen gas;
further preferably, the volume ratio of air to non-oxygen gas is 1:3-7; more preferably, the non-oxygen gas is preferably nitrogen.
8. The method for preparing a catalyst according to claim 4, wherein the calcination temperature in step (2) is 450 to 700 ℃; roasting for 0.3-5 h;
further, the roasting atmosphere is a mixed gas of nitrogen and air, and the volume ratio of the nitrogen to the air is preferably 2-5:1.
9. Use of a catalyst according to any one of claims 1 to 3 or a catalyst prepared by a process according to any one of claims 4 to 8 in a synthesis gas to olefin reaction.
10. The use according to claim 9, wherein the composition of the synthesis gas comprises CO and hydrogen; preferably, the volume ratio of CO to hydrogen is 1:3.5-5.
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