CN111790391A - Synthesis of Ni/Zn bimetallic oxide catalyst and application thereof in oxidative dehydrogenation reaction of n-butane - Google Patents
Synthesis of Ni/Zn bimetallic oxide catalyst and application thereof in oxidative dehydrogenation reaction of n-butane Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 title claims abstract description 21
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000011701 zinc Substances 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000003751 zinc Chemical class 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 150000002815 nickel Chemical class 0.000 claims abstract description 8
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- -1 butylene butadiene Chemical compound 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 229910001868 water Inorganic materials 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 17
- 239000003570 air Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 13
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000012216 screening Methods 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical group [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 3
- 238000001354 calcination Methods 0.000 claims 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 abstract description 9
- 150000001336 alkenes Chemical class 0.000 abstract description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 4
- 239000001273 butane Substances 0.000 abstract description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 abstract description 4
- 239000008139 complexing agent Substances 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 230000032683 aging Effects 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 238000000935 solvent evaporation Methods 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 15
- 229910052760 oxygen Inorganic materials 0.000 description 15
- 239000001301 oxygen Substances 0.000 description 15
- 239000012153 distilled water Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 5
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 229960004106 citric acid Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910003962 NiZn Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910007541 Zn O Inorganic materials 0.000 description 1
- 229910007746 Zr—O Inorganic materials 0.000 description 1
- MGFAJHVKMKDQIT-UHFFFAOYSA-N [C].[C].[C].[C].[C] Chemical compound [C].[C].[C].[C].[C] MGFAJHVKMKDQIT-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000001483 mobilizing effect Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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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
- B01J23/70—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
- B01J23/80—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 zinc, cadmium or mercury
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
- C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
-
- 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
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with zinc, cadmium or mercury
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses synthesis of a Ni/Zn bimetallic oxide catalyst and application thereof in oxidative dehydrogenation reaction of n-butane, belonging to the technical field of catalysts for oxidative dehydrogenation reaction of n-butane. The Ni/Zn bimetal oxide material is prepared by adopting a sol-gel method. The catalyst catalyzes the oxidative dehydrogenation of n-butane to generate dehydrogenation products such as butylene butadiene and the like under the conditions of no water vapor protection and low alkane feed ratio. More specifically, nickel salt, zinc salt and deionized water are prepared according to a certain molar ratio, citric acid is used as a complexing agent, spongy green powder is obtained after full stirring, solvent evaporation, aging and drying, and then the Ni/Zn bimetallic oxide catalyst is obtained through roasting. Unlike single composition NiO catalysts, the Ni/Zn bimetallic oxide catalyst of the present invention can effectively catalyze the conversion of butane to olefins. And the catalyst has good stability, is not easy to burn and inactivate in the reaction process, and is not easy to deposit carbon.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to synthesis of a Ni/Zn bimetallic oxide catalyst and application of the Ni/Zn bimetallic oxide catalyst in oxidative dehydrogenation of n-butane.
Background
C4Hydrocarbon components are of general interest for use in both fuels and chemical industries, where butane is widely found in petrochemical and coal chemical by-products and is no longer suitable as a fuel, and the corresponding dehydrogenated olefin products such as butene, butadiene, etc. are chemical intermediates in great demand. The development of the technology for preparing butadiene by using n-butane dehydrogenation has important significance for the efficient utilization of the carbon-tetracarbon resource. Compared with a butane catalytic dehydrogenation process, the n-butane oxidative dehydrogenation reaction has the remarkable advantages that: there is no thermodynamic limitation; relatively low temperature; oxygen is present in the reaction medium and coke deposition is less. Therefore, the technology for preparing butadiene by oxidative dehydrogenation of n-butane can effectively adjust the balance of supply and demand of butadiene, relieve the olefin resources which are scarce in the market and realize the high value-added utilization of n-butane.
The catalysts applied to the oxidative dehydrogenation reaction of n-butane are mostly concentrated on supported catalysts such as V-MgO, Ni-Bi and Mo, which show high olefin selectivity for the oxidative dehydrogenation reaction of butane, but are insufficient in reaction activity due to difficulty in mobilizing active oxygen species of a bulk phase, and require harsh reaction conditions. In recent years, Ni-based catalysts have been used in the field of lower hydrocarbons (C)2，C3) The method is widely applied to oxidative dehydrogenation reaction, and particularly, Ni is modified by other elements to form composite metal oxides, such as Ni-Zr-O, Ni-Ce-O and the like. The development of the Ni/Zn bimetallic oxide catalyst with excellent activity is of great significance.
Disclosure of Invention
The invention aims to provide a synthesis method of a Ni/Zn bimetallic oxide catalyst and an application thereof in an n-butane oxidative dehydrogenation reaction, wherein the catalyst has better stability and can be used forCatalyzing n-butane oxidation dehydrogenation to generate C under the condition of lower temperature and no steam protection4An olefin.
The purpose of the invention is realized by the following technical scheme:
and placing the prepared bimetallic oxide catalyst in a reactor, introducing mixed gas into the reactor, and keeping a certain airspeed and the temperature of a catalyst bed layer for reaction to obtain dehydrogenation products such as butylene butadiene and the like.
The mixed gas comprises n-butane, air and nitrogen, and the mixing volume ratio is 1 (5-10) to 1-6. The mixing volume ratio is preferably 1:5: 6.
The certain airspeed is 14400-16200 mL/(g.h), and the temperature of the catalyst bed is set to be 400-500 ℃.
The bi-component oxide catalyst comprises Ni and Zn, wherein the molar ratio of the Ni to the Zn is 1: 0.01-5.
In the catalyst, the molar ratio of nickel to zinc is preferably 1: 0.1-0.5.
In the catalyst, zinc is derived from zinc salt, and the zinc salt is zinc nitrate; the nickel is derived from a nickel salt, which is nickel nitrate.
The preparation process of the bimetallic oxide catalyst comprises the following steps:
step (1), arranging a certain mass of nickel salt, zinc salt and deionized water in a container, arranging citric acid monohydrate and deionized water in another container, slowly dropwise adding a citric acid solution into a mixed solution containing nickel and zinc salt, and fully stirring to ensure that the molar ratio of nickel to zinc is 1: 0.01-5, and the molar ratio of citric acid monohydrate to metal ions in the solution is 1.5: 1;
the molar ratio of the zinc salt to the deionized water is 0.01-5: 1000;
the molar ratio of the nickel salt to the deionized water is 1: 1000;
the mass fraction of the citric acid monohydrate solution is 3.0-16.0%.
Step (2), placing the solution in a water bath at 70 ℃;
step (3), stirring the solution obtained in the step (2) to be viscous, and transferring the solution to an oven for drying;
the oven temperature during drying was 120 ℃.
And (4) roasting and cooling the obtained spongy green powder, and grinding and screening to obtain the 40-60-mesh two-component catalyst.
The roasting temperature is 550-900 ℃, and the roasting time is 2-5 h.
The invention has the beneficial effects that:
the invention adopts a sol-gel method, and the catalyst is prepared and used (Ni (NO)3)2·6H2O and (Zn (NO)3)2·6H2O) is a precursor, and citric acid is a complexing agent. The introduction of Zn element helps the catalyst to form a crystal phase Ni-Zn-O solid solution which is beneficial to alkane activation, thereby having great influence on the oxygen mobility and the oxygen capacity (the oxygen amount in the catalyst participating in the reaction) of the catalyst, so that the catalyst has better activity and stability, and can catalyze the oxidative dehydrogenation of n-butane to C under the conditions of lower than 500 ℃ and low alkane feeding ratio4An olefin.
Drawings
Figure 1 is an XRD pattern of the catalysts of examples 3-6 and NiO catalyst without Zn addition.
FIG. 2 is a Temperature Programmed Reduction Oxidation (TPRO) plot of the catalyst of example 3 and a NiO catalyst without Zn addition in accordance with the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention thereto.
Example 1
Process for preparing catalyst
1.4540g of Ni (NO)3)2·6H2O and 0.0149g Zn (NO)3)2·6H2O was dissolved in 90mL of distilled water and the solution was designated solution A, which was then transferred to a 70 deg.C water bath and 1.5917g of citric acid monohydrate (C)6H8O7·H2O) was dissolved in 50mL of distilled water, and the solution was designated as solution B. Slowly dripping the solution B into the solution A, and continuing to perform water bath at 70 DEG CThe mixed solution was stirred to be viscous and the viscous mass was transferred to a 120 ℃ oven to be dried overnight. A spongy green powder was obtained. Roasting the dried sample in a tubular furnace in an oxygen atmosphere at 800 ℃ for 3 hours, cooling, grinding and screening to obtain a 40-60-mesh nickel oxide catalyst, wherein the catalyst is recorded as NiZn0.01And sealing and storing.
Oxidative dehydrogenation process
0.2g of the above catalyst was packed in a stainless steel reactor having an inner diameter of 8mm, and n-butane was used as a raw material gas in an amount of 99.9% by weight. Simultaneously introducing air and nitrogen, setting the molar ratio of n-butane to air to nitrogen as 1:10:1, introducing the mixed gas into a reactor, wherein the space velocity is 14400 mL/(g.h), the temperature of a catalyst bed layer is 400 ℃, carrying out reaction, and analyzing the reaction results of the products after 1h and 4h by gas chromatography as follows:
example 2
Process for preparing catalyst
1.4540g of Ni (NO)3)2·6H2O and 0.1487g Zn (NO)3)2·6H2O was dissolved in 90mL of distilled water and the solution was designated solution A, which was then transferred to a 70 deg.C water bath and 1.7336g of citric acid monohydrate (C)6H8O7·H2O) was dissolved in 50mL of distilled water, and the solution was designated as solution B. The solution B was slowly added dropwise to the solution A, the mixed solution was stirred continuously in a 70 ℃ water bath until viscous, and the viscous mass was transferred to a 120 ℃ oven to be dried overnight. A spongy green powder was obtained. Roasting the dried sample for 5 hours at 550 ℃ in a tubular furnace in an oxygen atmosphere, cooling, grinding and screening to obtain the nickel-zinc composite oxide catalyst with the granularity of 40-60 meshes, wherein the catalyst is recorded as NiZn0.1And sealing and storing.
Oxidative dehydrogenation process
0.2g of the above catalyst was packed in a stainless steel reactor having an inner diameter of 8mm, and n-butane was used as a raw material gas in an amount of 99.9% by weight. Simultaneously introducing air and nitrogen, setting the molar ratio of n-butane to air to nitrogen as 1:5:6, introducing the mixed gas into a reactor, wherein the space velocity is 16200 mL/(g.h), the temperature of a catalyst bed layer is 500 ℃, carrying out reaction, and analyzing the reaction results of the products after 1h and 4h by gas chromatography as follows:
example 3
Process for preparing catalyst
1.4540g of Ni (NO)3)2·6H2O and 0.7437g Zn (NO)3)2·6H2O was dissolved in 90mL of distilled water and the solution was designated solution A, which was then transferred to a 70 deg.C water bath and 2.3640g of citric acid monohydrate (C)6H8O7·H2O) was dissolved in 50mL of distilled water, and the solution was designated as solution B. The solution B was slowly added dropwise to the solution A, the mixed solution was stirred continuously in a 70 ℃ water bath until viscous, and the viscous mass was transferred to a 120 ℃ oven to be dried overnight. A spongy green powder was obtained. Roasting the dried sample in a tubular furnace in an oxygen atmosphere at 800 ℃ for 3 hours, cooling, grinding and screening to obtain a 40-60-mesh nickel-zinc composite oxide catalyst, wherein the catalyst is recorded as NiZn0.5And sealing and storing.
Oxidative dehydrogenation process
0.2g of the above catalyst was packed in a stainless steel reactor having an inner diameter of 8mm, and n-butane was used as a raw material gas in an amount of 99.9% by weight. Simultaneously introducing air and nitrogen, setting the molar ratio of n-butane to air to nitrogen as 1:5:6, introducing the mixed gas into a reactor, wherein the space velocity is 14400 mL/(g.h), the temperature of a catalyst bed layer is 440 ℃, carrying out reaction, and analyzing the reaction results of the products after 1h and 4h by gas chromatography as follows:
example 4
Process for preparing catalyst
1.4540g of Ni (NO)3)2·6H2O and 1.4874g Zn (NO)3)2·6H2O was dissolved in 90mL of distilled water and the solution was designated solution A, which was then transferred to a 70 deg.C water bath and 3.1520g of citric acid monohydrate (C)6H8O7·H2O) was dissolved in 50mL of distilled water, and the solution was designated as solution B. The solution B was slowly added dropwise to the solution A, the mixed solution was stirred continuously in a 70 ℃ water bath until viscous, and the viscous mass was transferred to a 120 ℃ oven to be dried overnight. A spongy green powder was obtained. Roasting the dried sample in a tubular furnace in an oxygen atmosphere at 900 ℃ for 2 hours, cooling, grinding and screening to obtain the nickel-zinc composite oxide catalyst with the granularity of 40-60 meshes, wherein the catalyst is recorded as NiZn1And sealing and storing.
Oxidative dehydrogenation process
0.2g of the above catalyst was packed in a stainless steel reactor having an inner diameter of 8mm, and n-butane was used as a raw material gas in an amount of 99.9% by weight. Simultaneously introducing air and nitrogen, setting the molar ratio of n-butane to air to nitrogen as 1:5:6, introducing the mixed gas into a reactor, wherein the space velocity is 14400 mL/(g.h), the temperature of a catalyst bed layer is 440 ℃, carrying out reaction, and analyzing the reaction results of the products after 1h and 4h by gas chromatography as follows:
example 5
Process for preparing catalyst
1.4540g of Ni (NO)3)2·6H2O and 4.4622g Zn (NO)3)2·6H2O was dissolved in 90mL of distilled water and the solution was designated solution A, which was then transferred to a 70 deg.C water bath and 6.3039g of citric acid monohydrate (C)6H8O7·H2O) dissolved in 50mL of distilled waterThis solution is denoted as solution B. The solution B was slowly added dropwise to the solution A, the mixed solution was stirred continuously in a 70 ℃ water bath until viscous, and the viscous mass was transferred to a 120 ℃ oven to be dried overnight. A spongy green powder was obtained. Roasting the dried sample in a tubular furnace in an oxygen atmosphere at 800 ℃ for 3 hours, cooling, grinding and screening to obtain a 40-60-mesh nickel-zinc composite oxide catalyst, wherein the catalyst is recorded as NiZn3And sealing and storing.
Oxidative dehydrogenation process
0.2g of the above catalyst was packed in a stainless steel reactor having an inner diameter of 8mm, and n-butane was used as a raw material gas in an amount of 99.9% by weight. Simultaneously introducing air and nitrogen, setting the molar ratio of n-butane to air to nitrogen as 1:5:6, introducing the mixed gas into a reactor, wherein the space velocity is 14400 mL/(g.h), the temperature of a catalyst bed layer is 440 ℃, carrying out reaction, and analyzing the reaction results of the products after 1h and 4h by gas chromatography as follows:
example 6
Process for preparing catalyst
1.4540g of Ni (NO)3)2·6H2O and 7.4370g Zn (NO)3)2·6H2O was dissolved in 90mL of distilled water and the solution was designated solution A, which was then transferred to a 70 deg.C water bath and 9.4558g of citric acid monohydrate (C)6H8O7·H2O) was dissolved in 50mL of distilled water, and the solution was designated as solution B. The solution B was slowly added dropwise to the solution A, the mixed solution was stirred continuously in a 70 ℃ water bath until viscous, and the viscous mass was transferred to a 120 ℃ oven to be dried overnight. A spongy green powder was obtained. Roasting the dried sample in a tubular furnace in an oxygen atmosphere at 800 ℃ for 4 hours, cooling, grinding and screening to obtain a 40-60-mesh nickel-zinc composite oxide catalyst, wherein the catalyst is recorded as NiZn5And sealing and storing.
Oxidative dehydrogenation process
0.2g of the above catalyst was packed in a stainless steel reactor having an inner diameter of 8mm, and n-butane was used as a raw material gas in an amount of 99.9% by weight. Simultaneously introducing air and nitrogen, setting the molar ratio of n-butane to air to nitrogen as 1:5:6, introducing the mixed gas into a reactor, wherein the space velocity is 14400 mL/(g.h), the temperature of a catalyst bed layer is 500 ℃ for reaction, and the reaction results of the products after 1h and 4h of gas chromatographic analysis are as follows:
as a result of XRD characterization as shown in FIG. 1, it was found that the introduction of Zn element formed Ni0.9Zn0.1O solid solution of NiZn0.5The catalyst has a relatively large content of this type of phase. Making NiZn as shown in FIG. 20.5A comparison of the temperature-programmed reduction oxidation (TPRO) of the catalyst with the NiO catalyst without Zn addition shows that the introduction of Zn element has a large influence on the oxygen mobility and oxygen capacity (oxygen amount in the catalyst participating in the reaction) of the catalyst. From fig. 1 and 2, it can be known that the introduction of Zn element forms a solid solution beneficial to alkane activation, which is beneficial to promote oxygen mobility, so that the catalyst has better activity and stability.
While the invention has been described in further detail with reference to specific preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. The Ni/Zn bimetallic oxide catalyst is characterized in that the Ni/Zn bimetallic oxide catalyst comprises Ni and Zn, wherein the molar ratio of the nickel to the zinc is 1 (0.01-5).
2. The Ni/Zn bimetallic oxide catalyst of claim 1, wherein the molar ratio of nickel to zinc in the catalyst is 1 (0.1-0.5); and the zinc is derived from zinc salt, and the zinc salt is zinc nitrate; the nickel is derived from a nickel salt, which is nickel nitrate.
3. A method of synthesizing a Ni/Zn bimetallic oxide catalyst as in claim 1 or 2, characterized by comprising the steps of:
the method comprises the following steps of (1) arranging nickel salt, zinc salt and deionized water with certain mass in a container, arranging citric acid monohydrate and deionized water in another container, slowly dropwise adding citric acid monohydrate solution into a mixed solution containing the nickel salt and the zinc salt, and fully stirring to ensure that the molar ratio of nickel to zinc is 1 (0.01-5); the molar ratio of citric acid monohydrate to metal ions in the solution is 1.5: 1;
step (2), placing the solution in a water bath at 70 ℃;
step (3) stirring the solution obtained in the step (2) to be viscous, and transferring the solution to an oven for drying;
roasting and cooling the spongy green powder obtained in the step (4), and grinding and screening to obtain the 40-60-mesh two-component catalyst.
4. The method for synthesizing Ni/Zn bimetal oxide catalyst as claimed in claim 3, wherein the molar ratio of the zinc salt, the nickel salt and the deionized water is (0.01-5) 1: 1000; the mass fraction of the citric acid monohydrate solution is 3.0-16.0%.
5. The method for synthesizing a Ni/Zn bimetallic oxide catalyst as in claim 3 or 4, characterized in that the oven temperature for drying in step (3) is 120 ℃.
6. The synthesis of Ni/Zn bimetal oxide catalyst and the application thereof in the oxidative dehydrogenation of n-butane as claimed in claim 5, wherein the calcination temperature in the step (4) is 550-900 ℃ and the calcination time is 2-5 h.
7. Use of a Ni/Zn bimetallic oxide catalyst in an n-butane oxidative dehydrogenation reaction according to claim 1 or 6, characterized in that:
placing the prepared Ni/Zn bimetallic oxide catalyst in a reactor, introducing mixed gas into the reactor, and keeping a certain airspeed and the temperature of a catalyst bed layer for reaction to obtain a dehydrogenation product of butylene butadiene;
the mixed gas comprises n-butane, air and nitrogen, and the mixing volume ratio is 1 (5-10) to 1-6;
the certain airspeed is 14400-16200 mL/(g.h), and the temperature of the catalyst bed is set to be 400-500 ℃.
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