CN119368229A - Zinc oxide-zirconium oxide catalyst and preparation method thereof, composite catalyst and application thereof, and method for producing hydrocarbons by hydrogenating carbon dioxide - Google Patents
Zinc oxide-zirconium oxide catalyst and preparation method thereof, composite catalyst and application thereof, and method for producing hydrocarbons by hydrogenating carbon dioxide Download PDFInfo
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- CN119368229A CN119368229A CN202310886774.8A CN202310886774A CN119368229A CN 119368229 A CN119368229 A CN 119368229A CN 202310886774 A CN202310886774 A CN 202310886774A CN 119368229 A CN119368229 A CN 119368229A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 129
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 45
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 45
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 44
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 5
- XXWNWOGCTPGCCR-UHFFFAOYSA-N [O-2].[Zn+2].[O-2].[Zr+4] Chemical compound [O-2].[Zn+2].[O-2].[Zr+4] XXWNWOGCTPGCCR-UHFFFAOYSA-N 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title abstract description 26
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000011701 zinc Substances 0.000 claims abstract description 56
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 23
- 239000012159 carrier gas Substances 0.000 claims abstract description 18
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 9
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 108
- 239000011787 zinc oxide Substances 0.000 claims description 54
- 239000002808 molecular sieve Substances 0.000 claims description 32
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 32
- 239000007789 gas Substances 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 16
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 239000003085 diluting agent Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000000047 product Substances 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000008187 granular material Substances 0.000 description 8
- 239000010453 quartz Substances 0.000 description 8
- 239000012494 Quartz wool Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- -1 preparation method Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Classifications
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7076—MFS-type, e.g. ZSM-57
-
- 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
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of catalyst preparation, and discloses a zinc oxide-zirconia catalyst, a preparation method, a composite catalyst and application thereof, and a method for preparing hydrocarbons by carbon dioxide hydrogenation. A process for preparing the Zn-Zr oxide catalyst includes such steps as loading Zn oxide to upstream of Zr oxide in the direction of carrier gas, and heat treating. The zinc oxide-zirconia catalyst prepared by the method provided by the invention has excellent catalytic performance. The composite catalyst is applied to the reaction of preparing hydrocarbon compounds by hydrogenating carbon dioxide, and the selectivity of target hydrocarbon products is high.
Description
Technical Field
The invention relates to the field of catalyst preparation, in particular to a zinc oxide-zirconia catalyst, a preparation method, a composite catalyst and application thereof, and a method for preparing hydrocarbons by carbon dioxide hydrogenation.
Background
Carbon dioxide is one of the main gases responsible for the greenhouse effect, and industrial processes emit large amounts of carbon dioxide. As global climate warms, control of carbon emissions becomes particularly important. Carbon dioxide is used as a carbon source for the reaction, and the preparation of chemicals from carbon dioxide is an important way of carbon dioxide utilization. Because of the high molecular symmetry of carbon dioxide, high bond energy and difficult activation, carbon dioxide is usually converted into chemicals such as methanol, formic acid, lower olefins and C 5+ hydrocarbons by hydrogenation.
There are two routes for preparing hydrocarbons from carbon dioxide, one is to use catalysts such as iron-based and cobalt-based catalysts for Fischer-Tropsch synthesis, convert carbon dioxide into carbon monoxide by reverse water gas shift, and prepare hydrocarbons by Fischer-Tropsch synthesis, but the product distribution of the route is limited by the Fischer-Tropsch synthesis product distribution law (ASF). The other is that the hydrogenation of carbon dioxide is carried out by a path of oxygen-containing compounds such as methanol, and then the hydrocarbon (MTH) is generated by the reaction of preparing hydrocarbon from methanol on an acidic molecular sieve, and the path can obtain higher hydrocarbon selectivity. However, in the prior art, when the second route is used for hydrocarbon production, the yields of target hydrocarbons such as lower olefins and C 5+ hydrocarbons are low.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a zinc oxide-zirconia catalyst, a preparation method, a composite catalyst and application thereof, and a method for preparing hydrocarbons by hydrogenation of carbon dioxide. The zinc oxide-zirconia catalyst prepared by the method provided by the invention has excellent catalytic performance. The composite catalyst is applied to the reaction of preparing hydrocarbon compounds by hydrogenating carbon dioxide, and the selectivity of target hydrocarbon products is high.
In order to achieve the above object, the present invention provides a method for preparing a zinc oxide-zirconia catalyst, which comprises placing zinc oxide upstream of zirconia in a direction in which a carrier gas is introduced under the action of the carrier gas, and then performing heat treatment.
Preferably, the conditions of the heat treatment include a temperature of 500-1000 ℃, preferably 600-800 ℃, and a time of 2-10 hours, preferably 4-6 hours.
Preferably, the volume space velocity of the carrier gas relative to the zinc oxide is in the range of 2000-8000h -1, preferably 3000-7000h -1.
Preferably, the carrier is a reducing gas, preferably at least one selected from the group consisting of hydrogen, carbon monoxide and ammonia.
In a second aspect the invention provides a zinc oxide-zirconia catalyst obtainable by the process of the first aspect.
The third aspect of the invention provides a composite catalyst comprising the zinc oxide-zirconia catalyst of the second aspect and a molecular sieve catalyst;
wherein, the content of the molecular sieve catalyst is 35-95wt% based on the total weight of the composite catalyst, and the content of the zinc oxide-zirconia catalyst is 5-65wt%.
In a fourth aspect, the present invention provides an application of the composite catalyst according to the third aspect in preparing hydrocarbon compounds by hydrogenating carbon dioxide.
In a fifth aspect, the invention provides a method for preparing hydrocarbon compounds by hydrogenating carbon dioxide, comprising the steps of carrying out contact reaction on carbon dioxide, hydrogen and optionally diluent gas under the action of a catalyst to obtain target hydrocarbon products;
wherein the catalyst is the composite catalyst according to the third aspect.
Through the technical scheme, the beneficial effects of the invention include:
The zinc oxide-zirconia catalyst prepared by the method provided by the invention has excellent catalytic performance. The composite catalyst is applied to the reaction of preparing hydrocarbon compounds by hydrogenating carbon dioxide, and the selectivity of target hydrocarbon products is high. The selectivity of C 2-C4 olefin in hydrocarbon product can be up to 84.9%, and the selectivity of C 5+ hydrocarbon can be up to 68.2%. And the selectivity of the byproduct CH 4 is low and can reach 4.3 percent at the minimum.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In one aspect, the invention provides a method for preparing a zinc oxide-zirconia catalyst, which comprises placing zinc oxide upstream of zirconia along the direction of carrier gas inlet under the action of carrier gas, and then performing heat treatment.
According to a preferred embodiment of the invention, the heat treatment causes zinc oxide to be deposited on the zirconia.
The present inventors have found that performing the heat treatment under specific conditions is more advantageous in obtaining the catalyst of the present invention having excellent catalytic performance.
According to the invention, the conditions of the heat treatment preferably comprise a temperature of 500-1000 ℃, preferably 600-800 ℃, and a time of 2-10 hours, preferably 4-6 hours.
According to the invention, the volume space velocity of the carrier gas relative to the zinc oxide is preferably 2000-8000h -1, preferably 3000-7000h -1. With this preferred embodiment, it is further advantageous to obtain a catalyst according to the invention having excellent catalytic properties. When the volume space velocity of the carrier gas relative to zinc oxide is below this range, incomplete reduction of zinc oxide, uneven reaction and poor deposition effect are caused, and when the volume space velocity of the carrier gas relative to zinc oxide is above this range, the gasified reduction product and zirconium oxide do not react so much that they cannot be deposited onto zirconium oxide effectively.
Preferably, the carrier gas is a reducing gas, and at least one selected from the group consisting of hydrogen, carbon monoxide and ammonia is preferable in order to enhance the deposition effect.
It will be appreciated that during the heat treatment according to the invention, the zinc oxide is first reduced by the carrier gas (reducing gas) to give a reduced product, which is then further vaporised under heat treatment conditions to deposit on the zirconia.
The zinc oxide of the invention can comprise zinc oxide or zinc oxide with other valence states, and the valence states of the zinc oxide do not influence the subsequent reaction effect of preparing hydrocarbon compounds by hydrogenating carbon dioxide, so the zinc oxide is not described in detail.
According to the present invention, zinc oxide and zirconium oxide are preferably used in such amounts that the zinc oxide-zirconium oxide catalyst is produced with a mass ratio of zinc oxide to zirconium oxide of 0.004 to 0.1, preferably 0.01 to 0.08. With the adoption of the preferred embodiment, the composite catalyst obtained later has excellent catalytic performance.
In the present invention, in order to obtain a zinc oxide-zirconia catalyst having the above composition, the zinc oxide excess is generally controlled so that the active sites on the zirconia surface can be sufficiently reacted with the reduction product of zinc oxide. Preferably, the zinc oxide and zirconium oxide are used in an amount of 0.5 to 4 by mass.
The sources of the zinc oxide and the zirconium oxide are not particularly limited, and the zinc oxide and the zirconium oxide can be obtained through commercial purchase or self-preparation by adopting a preparation method conventional in the field.
According to the present invention, preferably, the zinc oxide is spaced apart from the zirconium oxide. With the preferred embodiment, zinc oxide is effectively reduced and reacts with zirconium oxide, and unreacted zinc oxide can be recovered.
The present invention is not particularly limited in the manner of achieving the above-mentioned spaced placement, and may employ technical means conventional in the art. Preferably, an inert filler is placed between the zinc oxide and the zirconium oxide.
The inert filler of the present invention is selected from a wide range of choices and may be conventional in the art. Preferably, the inert filler is selected from at least one of quartz sand, alpha-alumina porcelain balls and quartz wool.
According to a particularly preferred embodiment of the present invention, a method for preparing a zinc oxide-zirconia catalyst comprises placing zinc oxide upstream of zirconia in a direction of carrier gas introduction, and then performing heat treatment;
the heat treatment conditions comprise 600-800 ℃ and 4-6 hours;
the volume space velocity of the carrier gas relative to the zinc oxide is 3000-7000h -1;
The carrier gas is a reducing gas;
The zinc oxide and the zirconium oxide are used in such an amount that the mass ratio of the zinc oxide to the zirconium oxide in the prepared zinc oxide-zirconium oxide catalyst is 0.01 to 0.08.
The zinc oxide-zirconia catalyst prepared by adopting the preferred embodiment further enables the obtained composite catalyst to have excellent catalytic performance.
In a second aspect the invention provides a zinc oxide-zirconia catalyst obtainable by the process of the first aspect.
According to the present invention, preferably, in the zinc oxide-zirconia catalyst, the mass ratio of zinc oxide to zirconia is 0.004 to 0.1, preferably 0.01 to 0.08.
The third aspect of the invention provides a composite catalyst comprising the zinc oxide-zirconia catalyst of the second aspect and a molecular sieve catalyst;
wherein, the content of the molecular sieve catalyst is 35-95wt% based on the total weight of the composite catalyst, and the content of the zinc oxide-zirconia catalyst is 5-65wt%.
According to the present invention, it is preferable that the molecular sieve catalyst is contained in an amount of 45 to 70wt% and the zinc oxide-zirconia catalyst is contained in an amount of 30 to 55wt% based on the total weight of the composite catalyst.
The type of the molecular sieve is not particularly limited in the present invention, and may be a conventional one in the art. Preferably, the molecular sieve is selected from at least one of CHA structure, MFI structure, MFS structure, and MTF structure molecular sieves, preferably at least one selected from SAPO-34, ZSM-5, ZSM-57, and MCM-35 molecular sieves. By adopting the preferred embodiment, the prepared composite catalyst is applied to the reaction of preparing hydrocarbon compounds by hydrogenating carbon dioxide, which is beneficial to improving the selectivity of target hydrocarbon products.
According to the invention, the molecular sieve preferably has a silicon to aluminum atomic ratio of 0.02 to 400, preferably 0.2 to 400.
Preferably, the SAPO-34 molecular sieve has a silicon to aluminum atomic ratio of 0.2 to 0.6.
Preferably, the ZSM-5 molecular sieve has a silicon to aluminum atomic ratio of from 20 to 360.
Preferably, the ZSM-57 molecular sieve has a silicon to aluminum atomic ratio of from 15 to 30.
Preferably, the MCM-35 molecular sieve has a silicon to aluminum atomic ratio of 20-150.
Preferably, the molecular sieve is a hydrogen-type molecular sieve.
The method for obtaining the hydrogen-form molecular sieve according to the present invention is not particularly limited, and may be carried out by referring to a method conventional in the art. The hydrogen form molecular sieve is preferably obtained by adopting an ammonia exchange method.
The ammonia exchange process of the present invention may be carried out with reference to ammonia exchange processes conventional in the art, and the present invention will not be described in detail herein.
The method for preparing the composite catalyst is not particularly limited, and may be carried out by referring to a method conventional in the art. The present invention preferably employs a physical mixing method.
According to one embodiment of the present invention, a zinc oxide-zirconia catalyst is milled with a molecular sieve catalyst to provide a composite catalyst.
The particle size of the composite catalyst is a conventional choice in the art. Preferably, the particle size of the composite catalyst is 20-80 mesh.
The method for obtaining the catalyst having the above particle size is not particularly limited, and the conventional technical means in the art can be referred to.
In a fourth aspect, the present invention provides an application of the composite catalyst according to the third aspect in preparing hydrocarbon compounds by hydrogenating carbon dioxide.
In a fifth aspect, the invention provides a method for preparing hydrocarbon compounds by hydrogenating carbon dioxide, comprising the steps of carrying out contact reaction on carbon dioxide, hydrogen and optionally diluent gas under the action of a catalyst to obtain target hydrocarbon products;
wherein the catalyst is the composite catalyst according to the third aspect.
According to the invention, the molar ratio of hydrogen to carbon dioxide is preferably 3-15:1, preferably 3-10:1.
In the present invention, the term "optionally" means with or without, with or without addition, with or without, unless otherwise specified. Specifically, the method of the invention can add dilution gas or not.
The dilution gas according to the invention may be a conventional choice in the art. Preferably, the diluent gas is selected from at least one of nitrogen, helium, argon and carbon monoxide.
According to the invention, preferably, the molar ratio of dilution gas to carbon dioxide is from 0.1 to 0.2:1.
According to the invention, the reaction conditions are preferably a temperature of 250-450 ℃, preferably 320-450 ℃, a pressure of 0.3-20MPa, preferably 2-15MPa, and a volume space velocity of carbon dioxide of 0.01-10h -1, preferably 0.05-8h -1.
Preferably, the target hydrocarbon product is a C 2-C4 olefin and/or a C 5+ hydrocarbon.
The reactions of the present invention may be carried out in a variety of reactors conventional in the art. For example, the reaction may be carried out in a fixed bed reactor, a fluidized bed reactor, or a moving bed reactor.
Preferably, the composite catalyst is reduced prior to use.
The method of the reduction is not particularly limited, and is carried out by referring to a conventional method in the art.
According to a preferred embodiment of the present invention, the composite catalyst is reduced under the action of a reducing gas at 380-450 ℃ for 2-6 hours.
Preferably, the reducing gas is hydrogen.
The present invention will be described in detail by examples.
In the following examples, the conversion of carbon dioxide was calculated using an internal standard method, and the selectivity of the product was calculated using a normalization method, as follows:
Carbon dioxide conversion = [ (moles of carbon dioxide in feed gas) - (moles of carbon dioxide in product) ]/(moles of carbon dioxide in feed gas) ×100%;
selectivity of hydrocarbon product = moles of hydrocarbon product carbon/sum of moles of hydrocarbon product organics carbon x 100%;
CO selectivity = moles of CO in product/[ moles of carbon dioxide in feed gas-moles of carbon dioxide in product ] ×100%;
the specific sources of molecular sieve catalysts used in the examples below are shown in table 1.
TABLE 1
Example 1
Preparation of zinc oxide-zirconia catalyst
The ZrO 2 carrier is prepared by adding 200mL of water into 18.6g of zirconyl nitrate for dissolution, adding concentrated ammonia water (25-28 wt%) at room temperature until the pH is approximately equal to 8.0, adding sodium hydroxide to adjust the pH to 14 after colloidal precipitation is obtained, aging for 1 hour, filtering, washing, drying, roasting for 3 hours at 500 ℃, naturally cooling to obtain ZrO 2, and sieving into 40-60 mesh particles.
The lower layer of the quartz tube was charged with 1.0gZrO 2 g of zinc oxide, the upper layer was charged with 1.0g of zinc oxide, the middle was separated by quartz wool, and hydrogen gas flowed from the upper layer to the lower layer. The treatment was carried out at 600℃for 6h under a hydrogen atmosphere with a volume space velocity of 6000h -1. And cooling and taking out the lower layer to obtain the zinc oxide-zirconia catalyst, which is marked as Zn@ZrO 2. In the zinc oxide-zirconia catalyst, the mass ratio of the zinc oxide to the zirconia was 0.07:1.
Preparation of composite catalyst
And (3) fully grinding and uniformly mixing the prepared 0.5g Zn@ZrO 2 catalyst and 1.0g HSAPO-34 to obtain a composite catalyst which is marked as C-1. And tabletting and granulating the composite catalyst to prepare 40-60 mesh granules for subsequent reactions.
Example 2
Preparation of zinc oxide-zirconia catalyst
The lower layer of the quartz tube was charged with 1.0gZrO 2 g of zinc oxide prepared in example 1, the upper layer was charged with 1.0g of zinc oxide, the middle was separated by quartz wool, and hydrogen gas flowed from the upper layer to the lower layer. The reaction was carried out under a hydrogen atmosphere at 700℃for 4 hours, with a volume space velocity of the hydrogen of 6000h -1. And cooling and taking out the lower layer to obtain the zinc oxide-zirconia catalyst, which is marked as Zn@ZrO 2. In the zinc oxide-zirconia catalyst, the mass ratio of the zinc oxide to the zirconia was 0.08:1.
Preparation of composite catalyst
The preparation of the HMCM-35 molecular sieve comprises the steps of adding Na-MCM-35 molecular sieve powder into a pre-prepared 1mol/L NH 4 Cl aqueous solution in a hydrothermal synthesis kettle, carrying out exchange reaction for 2h at 80 ℃ in a stirring state, vacuum filtering and washing with water, wherein the solid-liquid mass ratio is 1:10. After 3 times of the above-mentioned operations of exchanging, filtering and washing, the mixture was dried at 120℃for 4 hours. And then roasting at 550 ℃ for 4 hours to obtain the H-MCM-35.
And (3) fully grinding and uniformly mixing 0.5g of Zn@ZrO 2 prepared in the above way and 0.5g of HMCM-35 to obtain a composite catalyst which is marked as C-2. And tabletting and granulating the composite catalyst to prepare 40-60 mesh granules for subsequent reactions.
Example 3
Preparation of zinc oxide-zirconia catalyst
ZrO 2 support preparation was carried out in the manner as in example 1.
The lower layer of the quartz tube was charged with 1.0gZrO 2 g of zinc oxide, the upper layer was charged with 1.0g of zinc oxide, the middle was separated by quartz wool, and hydrogen gas flowed from the upper layer to the lower layer. The treatment was carried out at 800℃for 6h under a hydrogen atmosphere with a volume space velocity of 4000h -1. And cooling and taking out the lower layer to obtain the zinc oxide-zirconia catalyst, which is marked as Zn@ZrO 2. In the zinc oxide-zirconia catalyst, the mass ratio of the zinc oxide to the zirconia was 0.08:1.
Preparation of composite catalyst
The preparation of the H-ZSM-57 molecular sieve comprises the steps of adding Na-ZSM-57 molecular sieve powder into a pre-prepared 1mol/L NH 4 Cl aqueous solution in a hydrothermal synthesis kettle, carrying out exchange reaction for 2H at 80 ℃ in a stirring state, vacuum filtering and washing with water, wherein the solid-liquid mass ratio is 1:10. After 3 times of the above-mentioned operations of exchanging, filtering and washing, the mixture was dried at 120℃for 4 hours. Then after 4 hours of calcination at 550 ℃, H-ZSM-57 is obtained.
And (3) fully grinding and uniformly mixing 0.6g of Zn@ZrO 2 prepared in the above way and 0.8g of HZSM-57 to obtain a composite catalyst which is marked as C-3. And tabletting and granulating the composite catalyst to prepare 40-60 mesh granules for subsequent reactions.
Example 4
Preparation of zinc oxide-zirconia catalyst
ZrO 2 support preparation was carried out in the manner as in example 1.
The lower layer of the quartz tube was charged with 1.0gZrO 2 g of zinc oxide, the upper layer was charged with 1.0g of zinc oxide, the middle was separated by quartz wool, and hydrogen gas flowed from the upper layer to the lower layer. The reaction was carried out at 600℃for 5h under a hydrogen atmosphere with a volume space velocity of 6000h -1. And cooling and taking out the lower layer to obtain the zinc oxide-zirconia catalyst, which is marked as Zn@ZrO 2. In the zinc oxide-zirconia catalyst, the mass ratio of the zinc oxide to the zirconia was 0.05:1.
Preparation of composite catalyst
The 0.5g Zn@Zr 2 prepared above and 1g HZSM-5 (Si/Al=25) were sufficiently ground and mixed uniformly to obtain a composite catalyst, which was designated as C-4. And tabletting and granulating the composite catalyst to prepare 40-60 mesh granules for subsequent reactions.
Example 5
Preparation of zinc oxide-zirconia catalyst
ZrO 2 support preparation was carried out in the manner as in example 1.
The lower layer of the quartz tube was charged with 1.0gZrO 2 g of zinc oxide, the upper layer was charged with 1.0g of zinc oxide, the middle was separated by quartz wool, and hydrogen gas flowed from the upper layer to the lower layer. The treatment was carried out at 600℃for 6h under a carbon monoxide atmosphere with a volume space velocity of 7000h -1. And cooling and taking out the lower layer to obtain the zinc oxide-zirconia catalyst, which is marked as Zn@ZrO 2. In the zinc oxide-zirconia catalyst, the mass ratio of the zinc oxide to the zirconia was 0.07:1.
Preparation of composite catalyst
The 0.5g Zn@Zr 2 prepared above and 1.0g HZSM-5 (Si/Al=130) were sufficiently ground and mixed uniformly to obtain a composite catalyst, which was designated as C-5. And tabletting and granulating the composite catalyst to prepare 40-60 mesh granules for subsequent reactions.
Example 6
The procedure of example 1 was followed except that 550℃treatment was conducted under a hydrogen atmosphere for 6 hours to obtain a composite catalyst, which was designated as C-6. And tabletting and granulating the composite catalyst to prepare 40-60 mesh granules for subsequent reactions. In the zinc oxide-zirconia catalyst, the mass ratio of the zinc oxide to the zirconia was 0.03:1.
Example 7
The procedure of example 1 was followed except that Ar was used as a carrier gas to obtain a composite catalyst. Designated C-7. And tabletting and granulating the composite catalyst to prepare 40-60 mesh granules for subsequent reactions. In the zinc oxide-zirconia catalyst, the mass ratio of the zinc oxide to the zirconia was 0.005:1.
Comparative example 1
A composite catalyst, designated as D-1, was obtained by the same method as in example 1 except that 1.0g of Al 2O3 was charged in the lower layer of the quartz tube. And tabletting and granulating the composite catalyst to prepare 40-60 mesh granules for subsequent reactions. In the zinc oxide-alumina catalyst, the mass ratio of the zinc oxide to the alumina is 0.06:1.
Test example 1
The catalyst prepared in the example and comparative example was charged in an amount of 0.5g into a fixed bed reactor having a quartz tube inner liner (quartz tube inner diameter: 8 mm) with an inner diameter of 13mm, and the temperature was raised to 400℃at 5℃per minute under a hydrogen atmosphere, maintained for 2 hours, cooled to 360℃and fed with a reaction feed gas at a reaction pressure of 3MPa at a molar ratio of 3:1, while containing nitrogen gas (the total volume of the feed gas is the total volume of nitrogen, carbon dioxide and hydrogen) at an 8% total volume of the feed gas, and the volume space velocity of carbon dioxide was 1.63h -1. The reaction temperature was 360 ℃ for 18h, and the reaction results are shown in table 2.
TABLE 2
As can be seen from the results in Table 2, the composite catalyst prepared by the method is applied to the preparation of hydrocarbon compounds by the hydrogenation of carbon dioxide, the selectivity of target products is high, the selectivity of C 2-C4 olefin in hydrocarbon products can be up to 84.9%, and the selectivity of C 5+ hydrocarbon can be up to 68.2%. And the selectivity of the byproduct CH 4 is low and can reach 4.3 percent at the minimum. Therefore, the catalyst provided by the invention has excellent catalytic performance.
The preferred embodiments of the present invention have been described in detail above, 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. A process for preparing the Zn-Zr oxide catalyst includes such steps as loading Zn oxide to upstream of Zr oxide in the direction of carrier gas, and heat treating.
2. The method of claim 1, wherein,
The heat treatment conditions include a temperature of 500-1000 ℃, preferably 600-800 ℃, and a time of 2-10 hours, preferably 4-6 hours;
Preferably, the volume space velocity of the carrier gas relative to the zinc oxide is 2000-8000h -1, preferably 3000-7000h -1;
preferably, the carrier gas is a reducing gas, preferably at least one selected from the group consisting of hydrogen, carbon monoxide and ammonia.
3. The method according to claim 1 or 2, wherein,
The zinc oxide and zirconium oxide are used in such amounts that the mass ratio of zinc oxide to zirconium oxide in the zinc oxide-zirconium oxide catalyst prepared is 0.004 to 0.1, preferably 0.01 to 0.08.
4. A method according to any one of claim 1 to 3, wherein,
The zinc oxide and the zirconium oxide are placed at intervals;
preferably, an inert filler is placed between the zinc oxide and the zirconium oxide.
5. A zinc oxide-zirconia catalyst prepared by the process of any one of claims 1 to 4;
Preferably, in the zinc oxide-zirconia catalyst, the mass ratio of zinc oxide to zirconia is 0.004-0.1, preferably 0.01-0.08.
6. A composite catalyst comprising the zinc oxide-zirconia catalyst of claim 5 and a molecular sieve catalyst;
wherein, the content of the molecular sieve catalyst is 35-95wt% based on the total weight of the composite catalyst, and the content of the zinc oxide-zirconia catalyst is 5-65wt%.
7. The catalyst according to claim 6, wherein,
The content of the molecular sieve catalyst is 45-70wt% based on the total weight of the composite catalyst, and the content of the zinc oxide-zirconia catalyst is 30-55wt%;
Preferably, the molecular sieve is selected from at least one of CHA structure, MFI structure, MFS structure, and MTF structure molecular sieves, preferably at least one selected from SAPO-34, ZSM-5, ZSM-57, and MCM-35 molecular sieves;
Preferably, the molecular sieve has a silicon to aluminum atomic ratio of 0.02 to 400, preferably 0.2 to 400.
8. Use of the composite catalyst according to claim 6 or 7 for preparing hydrocarbon compounds by hydrogenation of carbon dioxide.
9. The hydrogenation process of carbon dioxide to prepare hydrocarbon compound includes the contact reaction of carbon dioxide, hydrogen and optional diluent gas to obtain target hydrocarbon product;
wherein the catalyst is the composite catalyst of claim 6 or 7.
10. The method of claim 9, wherein,
The molar ratio of the hydrogen to the carbon dioxide is 3-15:1, preferably 3-10:1;
Preferably, the diluent gas is selected from at least one of nitrogen, helium, argon and carbon monoxide;
preferably, the molar ratio of the dilution gas to carbon dioxide is 0.1-0.2:1;
Preferably, the conditions of the reaction are a temperature of 250-450 ℃, preferably 320-450 ℃, a pressure of 0.3-20MPa, preferably 2-15MPa, and a volume space velocity of carbon dioxide of 0.01-10h -1, preferably 0.05-8h -1;
Preferably, the target hydrocarbon product is a C 2-C4 olefin and/or a C 5+ hydrocarbon.
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