CN117943017A - Hydrogenation catalyst and preparation method thereof - Google Patents
Hydrogenation catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN117943017A CN117943017A CN202311761805.3A CN202311761805A CN117943017A CN 117943017 A CN117943017 A CN 117943017A CN 202311761805 A CN202311761805 A CN 202311761805A CN 117943017 A CN117943017 A CN 117943017A
- Authority
- CN
- China
- Prior art keywords
- hydrogenation catalyst
- solution
- strontium titanate
- zinc
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 73
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 69
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000011787 zinc oxide Substances 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 239000012266 salt solution Substances 0.000 claims abstract description 18
- 239000013067 intermediate product Substances 0.000 claims abstract description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 15
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 150000001879 copper Chemical class 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 150000003751 zinc Chemical class 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 230000002431 foraging effect Effects 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000010949 copper Substances 0.000 claims description 33
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 30
- 239000011701 zinc Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 18
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 15
- 235000017550 sodium carbonate Nutrition 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000005751 Copper oxide Substances 0.000 claims description 4
- 229910000431 copper oxide Inorganic materials 0.000 claims description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical group C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical group O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 22
- 229910002091 carbon monoxide Inorganic materials 0.000 description 22
- 239000008367 deionised water Substances 0.000 description 19
- 229910021641 deionized water Inorganic materials 0.000 description 19
- 229910002367 SrTiO Inorganic materials 0.000 description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- 229910002651 NO3 Inorganic materials 0.000 description 12
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 12
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000004448 titration Methods 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000012702 metal oxide precursor Substances 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 239000012716 precipitator Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005070 sampling Methods 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
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000014171 carbonated beverage Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a hydrogenation catalyst and a preparation method thereof. The hydrogenation catalyst comprises a strontium titanate carrier; and at least one metal oxide distributed on the strontium titanate carrier; wherein the metal oxide comprises zinc oxide, the zinc oxide being 10 to 50% by weight of the total weight of the zinc oxide and the strontium titanate support. The preparation method of the hydrogenation catalyst comprises the following steps: dropping a metal salt solution and an alkali solution into a strontium titanate solution, and keeping the pH value of the reaction solution between 5.0 and 8.0 to form a reaction solution; heating the reaction solution for aging; filtering the aged reaction solution to obtain an intermediate product; and calcining the intermediate product to form the hydrogenation catalyst, wherein the metal salt solution comprises a zinc salt and a copper salt.
Description
Technical Field
The present invention relates to a hydrogenation catalyst and a preparation method thereof, and more particularly, to a hydrogenation catalyst for synthesizing methanol by hydrogenation of carbon dioxide and a preparation method thereof.
Background
Since the second industrial revolution, fossil energy consumed in industrial production has resulted in a large emission of carbon dioxide (CO 2), so that the CO 2 content in the atmosphere has been drastically increased, which aggravates the greenhouse effect and causes a certain degree of impending environmental hazard, and the management of climate change for survival has been a common challenge for human society.
Among the various countermeasures taken against climate change caused by the greenhouse effect, it is mainly to reduce the concentration of CO 2 in the atmosphere. However, this problem cannot be truly solved by means of recovering CO 2 deep underground or storing it in the ocean, and not only does there be a problem of CO 2 leakage, but also CO 2 stored in the ocean can increase the acidity of the sea water and harm marine organisms. At the same time, this approach is costly to store and is not an ideal solution. Only the CO 2 is recycled, so that the problem can be really solved.
At present, the recycling utilization of CO 2 mainly comprises two aspects of physics and chemistry. Physically, when CO 2 is used as a protective gas, the method can be used for producing carbonated beverages; when CO 2 is used as an inert gas, it is generally used in the shielding gas of electric welding. In addition, the CO 2 can be used as a refrigerant in the field of food refrigeration and can be used as a tobacco shred expanding agent to replace freon. Chemically, the conversion of greenhouse gases into valuable chemical products, such as methanol, formic acid, hydrocarbons, esters, etc., can also generate considerable economic benefits while greatly reducing the content of CO 2 in the atmosphere, and currently, the hydrogenation of CO 2 to prepare methanol is attracting more attention due to its good feasibility and economy.
The reaction catalyst used for preparing the methanol by hydrogenating CO 2 in the early stage is researched by referring to a copper (Cu) base catalyst in the hydrogenation reaction of carbon monoxide (CO), but the Cu base catalyst has the defects of poor stability and low high-temperature selectivity, so that the catalyst used for preparing the methanol by hydrogenating CO 2 is further researched and improved. Currently, the main catalytic systems are Cu-based catalysts, noble metal catalysts, indium oxide (In 2O3) based catalysts and other novel catalytic systems. Among them, indium (In) -based catalysts and noble metal catalysts are not suitable for industrial mass production due to their high price. The Cu-based catalyst is one of the most widely studied types of catalysts clear, and has the advantages of large specific surface area, high dispersity, etc. due to its low cost, but still has stability and selectivity problems.
Currently, in the aspect of synthesizing methanol (CH 3 OH) by CO 2 hydrogenation, preparing a hydrogenation catalyst with high activity, high selectivity and good stability under the reaction condition of low temperature and high pressure is an important subject to be solved by current researchers.
Accordingly, there is a need for a hydrogenation catalyst and a method for preparing the same, which can be used for synthesizing methanol from carbon dioxide through hydrogenation reaction, so as to solve the problems in the prior art.
Disclosure of Invention
The main object of the present invention is to provide a hydrogenation catalyst comprising a strontium titanate support and at least one active component, such as a metal oxide. The metal oxide is uniformly distributed on the strontium titanate carrier, so that the activity of the hydrogenation catalyst can be improved. The hydrogenation catalyst can be used for converting carbon dioxide into methanol by hydrogenation, obtains the CO 2 conversion rate of nearly 30 percent and the methanol selectivity of nearly 70 percent, has no obvious deactivation within 36 hours, and has good catalytic activity and stability.
Another object of the present invention is to provide a method for preparing a hydrogenation catalyst, wherein one or more active components are distributed on a strontium titanate carrier in a relatively uniform manner by using a deposition precipitation method, so that the stability and activity of the hydrogenation catalyst can be improved.
To achieve the above object, an embodiment of the present invention provides a hydrogenation catalyst, comprising: a strontium titanate (SrTiO 3) carrier; and at least one metal oxide distributed on the strontium titanate carrier; wherein the metal oxide comprises zinc oxide (ZnO) in an amount of 10 to 50% by weight of the total weight of the zinc oxide and the strontium titanate support.
In one embodiment of the invention, the strontium titanate support has a particle size of 3 to 5 microns.
In an embodiment of the invention, the zinc oxide is 20 to 40% by weight of the total weight of the zinc oxide and the strontium titanate support.
In one embodiment of the present invention, the at least one metal oxide comprises copper oxide.
In one embodiment of the present invention, the hydrogenation catalyst comprises a molar ratio of elemental copper to elemental zinc of from 0.5 to 4.
In one embodiment of the present invention, the hydrogenation catalyst contains a molar ratio of elemental copper to elemental zinc of 1 to 3.
Another embodiment of the present invention provides a method for preparing a hydrogenation catalyst, comprising the steps of:
(1) Dropping a metal salt solution and an alkali solution into a strontium titanate solution, and keeping the pH value of the reaction solution between 5.0 and 8.0 to form a reaction solution;
(2) Heating the reaction solution for aging;
(3) Filtering the aged reaction solution to obtain an intermediate product; and
(4) Calcining the intermediate product to form a hydrogenation catalyst as described above;
Wherein the metal salt solution comprises a zinc salt.
In one embodiment of the present invention, in the step (1), the strontium titanate solution is formed by dissolving a strontium titanate powder in water, wherein the strontium titanate powder has an average particle diameter of 3 to 5 μm.
In one embodiment of the present invention, in the step (1), the metal salt solution has a concentration of 0.5 to 2 mol/liter (mol/L), and the lye has a concentration of 0.5 to 2 mol/liter.
In an embodiment of the present invention, in the step (1), the alkali solution is at least one of sodium hydroxide, sodium bicarbonate, sodium carbonate, potassium hydroxide, potassium carbonate and potassium bicarbonate.
In one embodiment of the present invention, in the step (2), the reaction solution is heated to 70 ℃ for aging for 1 to 3 hours.
In one embodiment of the present invention, the metal salt solution further comprises a copper salt, wherein a molar ratio of elemental copper to elemental zinc in the metal salt solution is 0.5 to 4.
In one embodiment of the invention, the copper salt is copper nitrate trihydrate and the zinc salt is zinc nitrate hexahydrate.
In an embodiment of the present invention, the step (3) further includes: the intermediate product is dried at 100 to 120 ℃ for 10 to 14 hours.
In one embodiment of the invention, in said step (4), said intermediate product is calcined at 300 to 500 ℃ for 2 to 5 hours.
In one embodiment of the present invention, in step (1), the reaction solution is further stirred at a rotation speed of 10 to 20 rpm for 2 to 4 hours at 60 to 90 ℃.
The beneficial effects of the invention are as follows:
The strontium titanate is used as a catalyst carrier, and based on the special energy band structure, heterojunction can be formed between the strontium titanate and copper oxide and zinc oxide, interaction between the active component and the strontium titanate carrier is enhanced, and the surface of the catalyst is rich in electrons, so that the activity of the catalyst is improved. Cu and Zn serving as catalytic active components can be uniformly distributed and deposited on a strontium titanate carrier, and the combination degree between the Cu and the carrier is high, so that the stability is good. In addition, the hydrogenation catalyst prepared by the method has short reduction and activation time before use, and reduces the use cost of hydrogen in the reaction.
Detailed Description
The foregoing and other objects, features and advantages of the invention will be apparent from the following more particular description of preferred embodiments of the invention, as illustrated in the accompanying drawings. Furthermore, reference to the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. The numerical range (e.g., 10% -11% of A) includes upper and lower values (i.e., 10% +.A+.11%) unless specified; if the lower limit (e.g., less than 0.2% B, or less than 0.2% B) is not defined, the lower limit may be 0 (i.e., 0% B. Ltoreq.0.2%). The above words are used to illustrate and understand the invention, but not to limit it.
An embodiment of the present invention provides a hydrogenation catalyst, which mainly comprises: a strontium titanate (SrTiO 3) carrier; and at least one metal oxide distributed on the strontium titanate support, wherein the metal oxide comprises zinc oxide (ZnO) in an amount of 10 to 50% by weight of the total weight of the zinc oxide and the strontium titanate support. Preferably, the zinc oxide is 20 to 40% by weight of the total weight of the zinc oxide and the strontium titanate support.
In one embodiment, the strontium titanate support has a particle size of 3 to 5 microns.
In one embodiment, the at least one metal oxide may further include copper oxide (CuO), and the hydrogenation catalyst may include a molar ratio of elemental copper to elemental zinc of 0.5 to 4, for example, 0.5, 1, 2,3, or 4, and may include other molar ratios between 0.5 and 4 that are not integers. Preferably, the hydrogenation catalyst contains a molar ratio of elemental copper to elemental zinc of from 1 to 3, and may be, for example, 1, 2,3 or other molar ratios that are not integers.
Another embodiment of the present invention provides a method for preparing a hydrogenation catalyst, which mainly comprises the steps of: (S1) dropwise adding a metal salt solution and an alkali solution into a strontium titanate solution, and keeping the pH value of the reaction solution between 5.0 and 8.0 to form a reaction solution; (S2) heating the reaction solution to age; and (S3) filtering the aged reaction solution to obtain an intermediate product; and (S4) calcining the intermediate product to form the hydrogenation catalyst as described above.
The invention will be described in detail below with respect to details of the implementation of the steps described above and the principles thereof.
The preparation method of the hydrogenation catalyst in the embodiment of the invention comprises the following steps: (S1) dropwise adding a metal salt solution and an alkali solution into a strontium titanate solution, and keeping the pH value of the reaction solution between 5.0 and 8.0 to form a reaction solution. In this step, the strontium titanate solution is formed by dissolving a strontium titanate powder having an average particle diameter of 3 to 5 μm in water. The metal salt solution contains zinc salt, such as zinc nitrate hexahydrate. In one embodiment of the present invention, the metal salt solution may further include a copper salt, such as copper nitrate trihydrate. Preferably, the metal salt solution has a concentration of 0.5 to 2 moles/liter (mol/L), and the lye has a concentration of 0.5 to 2 moles/liter. In an embodiment, the molar ratio of the copper salt to the zinc salt in the metal salt solution, that is, the molar ratio of elemental copper to elemental zinc, is 0.5 to 4, may be 0.5, 1, 2, 3 or 4, or may be other than an integer between 0.5 and 4. Preferably, the molar ratio of the elemental copper to the elemental zinc is from 1 to 3, which may be, for example, 1, 2, 3 or other molar ratio not an integer. In one embodiment, the lye is formulated from at least one of sodium hydroxide, sodium bicarbonate, sodium carbonate, potassium hydroxide, potassium carbonate, and potassium bicarbonate, and the lye has a concentration of 0.5 to 2 moles/liter, for example, but is not limited thereto.
In one embodiment of the present invention, in this step, stirring the reaction solution at a temperature of 60 to 90 ℃ for 2 to 4 hours at a rotation speed of 10 to 20 rpm is further included.
The preparation method of the hydrogenation catalyst in the embodiment of the invention comprises the following steps: (S2) heating the reaction solution to age. In this step, the reaction solution is heated to 70 ℃ to perform aging, and the aging time may be 1 to 3 hours, for example, 1, 1.5, 2, 2.5, or 3 hours, but is not limited thereto. In addition, the stirring in step (S2) may be continued when the aging is performed.
The preparation method of the hydrogenation catalyst in the embodiment of the invention comprises the following steps: (S3) filtering the aged reaction solution to obtain an intermediate product. In this step, the intermediate product may be obtained by suction filtration and rinsed with deionized water to neutral or near neutral pH.
In one embodiment of the present invention, the step (S3) further comprises a step of drying the intermediate product for 10 to 14 hours at a temperature of 100 to 120 ℃.
The preparation method of the hydrogenation catalyst according to the embodiment of the invention comprises the following steps: (S4) calcining the intermediate product to form the hydrogenation catalyst as described above. In this step, the intermediate product is calcined at 300 to 500 ℃ for 2 to 5 hours. In addition, the hydrogenation catalyst comprises: a strontium titanate (SrTiO 3) carrier; and at least one metal oxide distributed on the strontium titanate support, wherein the metal oxide comprises zinc oxide (ZnO) in an amount of 10 to 50% by weight of the total weight of the zinc oxide and the strontium titanate support. Preferably, the zinc oxide is 20 to 40% by weight of the total weight of the zinc oxide and the strontium titanate support. Preferably, copper oxide is further included in the hydrogenation catalyst, and a molar ratio of elemental copper to elemental zinc included in the hydrogenation catalyst is 0.5 to 4, which may be, for example, 0.5, 1,2,3 or 4, or may be another molar ratio between 0.5 and 4, which is not an integer, preferably, the molar ratio of elemental copper to elemental zinc is 1 to 3, which may be, for example, 1,2,3 or another molar ratio which is not an integer.
In order to make the hydrogenation catalyst of the present invention and the preparation method thereof clearer while verifying the effect of the hydrogenation catalyst, the following experiment was performed.
Experiment 1: preparation of Cu/ZnO/SrTiO 3 (zno=40 wt%, cu: zn=2:1)
7.299G of Zn (NO 3)2·6H2O,11.8751g Cu(NO3)2·3H2 O) is mixed and dissolved in 73.73g of deionized water and is slowly added into a burette, 7.8145g of Na 2CO3 is weighed and dissolved in 73.73g of deionized water to prepare 1M sodium carbonate solution which is used as a precipitant and is slowly added into another burette, 200g of distilled water is added into the beaker and preheated to 70 ℃, 3g of SrTiO 3 powder with the average particle size of 3 to 5 microns is added into the water, the rotating speed is kept at 20 revolutions per minute (r/min), nitrate solution and sodium carbonate solution are respectively dripped into the beaker at the speed of 1 drop per second (1 d/1 s), the pH value is kept at 6.0 to 6.1 in the titration process, the nitrate dripping is finished, then, the solution is aged for 1 hour at 70 ℃, ultrasonic treatment is carried out for 1 hour, air extraction filtration is carried out, a certain amount of deionized water is used for washing to be about neutral, the obtained filter cake is dried at 110 ℃ for 12 hours and then calcined at 350 ℃ for 4 hours, and the hydrogenation catalyst is obtained as Cu/SrTiO 3 (Cu=40: cu=2) with the average particle size of 1 to 5 microns (Cu=2).
Experiment 2: preparation of Cu/ZnO/SrTiO 3 (zno=30 wt%, cu: zn=2:1)
4.6923G of Zn (NO 3)2·6H2O,7.634g Cu(NO3)2·3H2 O) is weighed and mixed and dissolved in 47.4g of deionized water and is slowly added into a burette as a metal oxide precursor solution, 5.0239g of Na 2CO3 is weighed and dissolved in 47.4g of deionized water to prepare a 1M sodium carbonate solution which is used as a precipitant and is slowly added into another burette, 200g of distilled water is added into a beaker and preheated to 70 ℃, 3g of SrTiO 3 powder with an average particle size of 3 to 5 microns is added into the water, the rotating speed is kept at 20r/min, the nitrate solution and the sodium carbonate solution are respectively added into the beaker at a speed of 1d/1s, the pH value is kept at 6.0 to 6.1 during the titration, the nitrate dripping is finished, then the solution is aged for 1 hour at 70 ℃, ultrasonic treatment is carried out for 1 hour, air suction filtration is carried out, a certain amount of deionized water is used for washing to be about neutral, the obtained filter cake is dried at 110 ℃ for 12 hours and then calcined at 350 ℃ for 4 hours, and the obtained hydrogenation catalyst is Cu/ZnO/SrTiO 3 (ZnO=30 wt%, and Cu=2) with an average particle size of 3 to 5 microns is obtained.
Experiment 3:
2.7372g of Zn (NO 3)2·6H2O,4.4527g Cu(NO3)2·3H2 O is mixed and dissolved in 47.4g of deionized water and is slowly added into a burette as a metal oxide precursor solution, 2.93g of Na 2CO3 is weighed and is dissolved in 47.4g of deionized water to prepare a 1M sodium carbonate solution which is used as a precipitator and is slowly added into another burette, 200g of distilled water is added into a beaker and preheated to 70 ℃, 3g of SrTiO 3 powder with the average particle size of 3 to 5 microns is added into the water, the rotating speed is kept at 20r/min, the nitrate solution and the sodium carbonate solution are respectively added into the beaker at the speed of 1d/1s, the pH value is kept at 6.0 to 6.1 during the titration, the nitrate dripping is finished, then the solution is aged at 70 ℃ for 1 hour, the solution is subjected to ultrasonic treatment for 1 hour, air suction filtration and is washed with a certain amount of deionized water until the value is neutral, the obtained filter cake is dried at 110 ℃ for 12 hours and then calcined at 350 ℃ for 4 hours, and the obtained reaction catalyst is named Cu/ZnO/SrTiO 3 (ZnO=20%, cu=2) with the average particle size of 3 to 5 microns is obtained.
Experiment 4:
4.6923g of Zn (NO 3)2·6H2O,11.4518g Cu(NO3)2·3H2 O is mixed and dissolved in 63.2g of deionized water and is slowly added into a burette as a metal oxide precursor solution, 6.6986g of Na 2CO3 is weighed and dissolved in 63.2g of deionized water to prepare a 1M sodium carbonate solution which is used as a precipitator and is slowly added into another burette, 200g of distilled water is added into a beaker and preheated to 70 ℃, 3g of SrTiO 3 powder with an average particle size of 3 to 5 microns is added into the water, the rotating speed is kept at 20r/min, the nitrate solution and the sodium carbonate solution are respectively added into the beaker at a speed of 1d/1s, the pH value is kept at 6.0 to 6.1 in the titration process, the nitrate dripping is finished, then the solution is aged for 1 hour at 70 ℃, ultrasonic treatment is carried out for 1 hour, air suction filtration is carried out, a certain amount of deionized water is used for washing to be about neutral in value, the obtained filter cake is dried at 110 ℃ for 12 hours and then calcined at 350 ℃ for 4 hours, and the hydrogenation reaction catalyst Cu/ZnO/SrTiO 3 (ZnO=30wt%), and Cu=3:3 has an average particle size of 3 to 5 microns is obtained.
Experiment 5:
4.6923g of Zn (NO 3)2·6H2O,3.8173g Cu(NO3)2·3H2 O is mixed and dissolved in 31.6g of deionized water and is slowly added into a burette as a metal oxide precursor solution, 3.3493g of Na 2CO3 is weighed and dissolved in 31.6g of deionized water to prepare a 1M sodium carbonate solution which is used as a precipitator and is slowly added into another burette, 200g of distilled water is added into a beaker and preheated to 70 ℃, 3g of SrTiO 3 powder with an average particle size of 3 to 5 microns is added into the water, the rotating speed is kept at 20r/min, the nitrate solution and the sodium carbonate solution are respectively added into the beaker at a speed of 1d/1s, the pH value is kept at 6.0 to 6.1 during the titration, the titration is finished after the nitrate dripping is finished, then the solution is aged for 1 hour at 70 ℃, the solution is subjected to ultrasonic treatment for 1 hour, air extraction filtration and is washed with a certain amount of deionized water until the pH value is about neutral, the obtained filter cake is dried at 110 ℃ for 12 hours and then calcined at 350 ℃ for 4 hours, and the hydrogenation catalyst Cu/ZnO/SrTiO 3 (ZnO=30wt% (Cu=1) with an average particle size of 3: 5 microns) is obtained.
Experiment 6:
4.6923g of Zn (NO 3)2·6H2O,1.9086g Cu(NO3)2·3H2 O) is weighed and mixed and dissolved in 23.7g of deionized water and is slowly added into a burette as a metal oxide precursor solution, 2.5120g of Na 2CO3 is weighed and dissolved in 23.7g of deionized water to prepare a 1M sodium carbonate solution which is taken as a precipitator and is slowly added into another burette, 200g of distilled water is added into a beaker and preheated to 70 ℃, 3g of SrTiO 3 powder with the average particle size of 3 to 5 microns is added into the water, the rotating speed is kept at 20r/min, the nitrate solution and the sodium carbonate solution are respectively added into the beaker at the speed of 1d/1s, the pH value is kept at 6.0 to 6.1 in the titration process, the nitrate dripping is finished, then the solution is aged for 1 hour at 70 ℃, the solution is subjected to ultrasonic treatment for 1 hour, air suction filtration and is washed with a certain amount of deionized water until the pH value is about neutral, the obtained filter cake is dried at 110 ℃ for 12 hours and then calcined at 350 ℃ for 4 hours, and the hydrogenation catalyst is Cu/ZnO/SrTiO 3 (ZnO=30 wt%, and Cu=3: 3 to have the average particle size of 3 to 5 microns is obtained.
Experiment 7: evaluation of catalyst Performance
The hydrogenation catalyst is respectively filled in a fixed bed type reactor and reduced for 1 hour under the atmosphere of 20 percent hydrogen at the temperature of 250 ℃ and the normal pressure; the reaction temperature was 250℃and the feed gas pressure was 3.0MPa, the H 2/CO2 molar ratio was 3, the space velocity was 3000mL/hr, and the reaction time was 36 hours by sampling analysis, and the carbon dioxide conversion and the selectivity to methanol were obtained as shown in Table 1 below.
Table 1:
Filling a hydrogenation catalyst Cu-ZnO-SrTiO 3 (ZnO=30wt%, cu/Zn=2:1) into a fixed bed reactor, and reducing for 1 hour at 220 ℃ under normal pressure in a 20% hydrogen atmosphere; the reaction temperature was 220℃and the feed gas pressure was 5.0MPa, the H 2/CO2 molar ratio was 5, the space velocity was 2000mL/hr, and the reaction time was 36 hours by sampling analysis, and the carbon dioxide conversion and the selectivity to methanol were obtained as shown in Table 2 below.
Table 2:
As can be seen from the reaction data in Table 2, the hydrogenation catalyst Cu-ZnO-SrTiO 3 (ZnO=30wt%, cu/Zn=2:1) prepared by the invention can achieve the conversion rate of CO 2 of nearly 30% and the selectivity of methanol of nearly 70% under the reaction conditions of 220 ℃ of reaction temperature, 5.0MPa of raw gas pressure, 5H 2/CO2 mol ratio and 2000mL/hr of airspeed, and has good catalytic activity and stability without obvious deactivation within 36 hours. The hydrogenation catalyst Cu-ZnO-SrTiO 3 (ZnO=30wt%, cu/Zn=2:1) prepared by the method can achieve 18.42% CO 2 conversion rate and 38.39% methanol selectivity under the reaction conditions of the reaction temperature of 250 ℃, the raw gas pressure of 3.0MPa, the H 2/CO2 mol ratio of 3 and the space velocity of 3000mL/hr, and the CO 2 conversion rate is only 16.93% and the methanol selectivity is only 28.82% under the same reaction conditions.
The invention has been described with respect to the above-described embodiments, however, the above-described embodiments are merely examples of practicing the invention. It must be noted that the disclosed embodiments do not limit the scope of the invention. On the contrary, modifications and equivalent arrangements included within the spirit and scope of the claims are intended to be included within the scope of the invention.
Claims (16)
1. A hydrogenation catalyst characterized by: the hydrogenation catalyst comprises:
A strontium titanate carrier; and
At least one metal oxide distributed on the strontium titanate carrier;
Wherein the metal oxide comprises zinc oxide, the zinc oxide being 10 to 50% by weight of the total weight of the zinc oxide and the strontium titanate support.
2. The hydrogenation catalyst of claim 1, wherein: the strontium titanate support has a particle size of 3 to 5 microns.
3. The hydrogenation catalyst of claim 1, wherein: the zinc oxide is 20 to 40% by weight of the total weight of the zinc oxide and the strontium titanate support.
4. The hydrogenation catalyst of claim 1, wherein: the at least one metal oxide comprises copper oxide.
5. The hydrogenation catalyst of claim 4, wherein: the hydrogenation catalyst contains one mole ratio of elemental copper and elemental zinc of 0.5 to 4.
6. The hydrogenation catalyst of claim 4, wherein: the hydrogenation catalyst contains one mole ratio of elemental copper and elemental zinc of 1 to 3.
7. A preparation method of a hydrogenation catalyst is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) Dropping a metal salt solution and an alkali solution into a strontium titanate solution, and keeping the pH value of the reaction solution between 5.0 and 8.0 to form a reaction solution;
(2) Heating the reaction solution for aging;
(3) Filtering the aged reaction solution to obtain an intermediate product; and
(4) Calcining the intermediate product to form the hydrogenation catalyst of claim 1;
Wherein the metal salt solution comprises a zinc salt.
8. The method for preparing a hydrogenation catalyst according to claim 7, wherein: in the step (1), the strontium titanate solution is formed by dissolving a strontium titanate powder having an average particle diameter of 3 to 5 μm in water.
9. The method for preparing a hydrogenation catalyst according to claim 7, wherein: in the step (1), the metal salt solution has a concentration of 0.5 to 2 mol/liter, and the lye has a concentration of 0.5 to 2 mol/liter.
10. The method for preparing a hydrogenation catalyst according to claim 7, wherein: in the step (1), the alkali liquor is at least one of sodium hydroxide, sodium bicarbonate, sodium carbonate, potassium hydroxide, potassium carbonate and potassium bicarbonate.
11. The method for preparing a hydrogenation catalyst according to claim 7, wherein: in the step (2), the reaction solution is heated to 70 ℃ for aging for 1 to 3 hours.
12. The method for preparing a hydrogenation catalyst according to claim 7, wherein: the metal salt solution further comprises a copper salt, wherein the metal salt solution has a molar ratio of elemental copper to elemental zinc of 0.5 to 4.
13. The method for preparing a hydrogenation catalyst according to claim 12, wherein: the copper salt is copper nitrate trihydrate and the zinc salt is zinc nitrate hexahydrate.
14. The method for preparing a hydrogenation catalyst according to claim 7, wherein: the step (3) further comprises: the intermediate product is dried at 100 to 120 ℃ for 10 to 14 hours.
15. The method for preparing a hydrogenation catalyst according to claim 7, wherein: in the step (4), the intermediate product is calcined at 300 to 500 ℃ for 2 to 5 hours.
16. The method for preparing a hydrogenation catalyst according to claim 7, wherein: in step (1), further comprising stirring the reaction solution at 60 to 90 ℃ at a rotation speed of 10 to 20 rpm for 2 to 4 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311761805.3A CN117943017A (en) | 2023-12-20 | 2023-12-20 | Hydrogenation catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311761805.3A CN117943017A (en) | 2023-12-20 | 2023-12-20 | Hydrogenation catalyst and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117943017A true CN117943017A (en) | 2024-04-30 |
Family
ID=90793449
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311761805.3A Pending CN117943017A (en) | 2023-12-20 | 2023-12-20 | Hydrogenation catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117943017A (en) |
-
2023
- 2023-12-20 CN CN202311761805.3A patent/CN117943017A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113145155B (en) | Nitrogen-doped carbon-coated nickel catalyst applied to assembly of bioethanol to synthesize high-carbon alcohol and preparation method thereof | |
| CN111183115B (en) | Composite oxide, metal carrier, and ammonia synthesis catalyst | |
| CN114570360B (en) | Ru-based catalyst and preparation method and application thereof | |
| CN112619648B (en) | Copper-cobalt-based catalyst for organic sulfur hydrolysis removal and preparation method thereof | |
| CN105195156A (en) | Preparation method and application of high-dispersity copper-based catalyst | |
| CN112495401A (en) | Mo-doped MoO3@ZnIn2S4Z-system photocatalyst and preparation method and application thereof | |
| EP3805159A1 (en) | Composite oxide, metal-supported material, and ammonia synthesis catalyst | |
| CN110586094A (en) | Copper-based nanoflower catalyst for producing methanol and ethylene glycol by ethylene carbonate hydrogenation and preparation method thereof | |
| CN110787789A (en) | Preparation and application of catalyst for preparing methanol by carbon dioxide hydrogenation | |
| CN114405505A (en) | Platinum modified indium-based oxide catalyst and preparation method and application thereof | |
| CN113694929B (en) | Supported single-atom copper-based metal oxide catalyst, and preparation method and application thereof | |
| CN114917912B (en) | Catalyst for preparing methanol and co-producing ethylene glycol through ethylene carbonate hydrogenation, preparation method and use method | |
| CN115155602B (en) | Metal oxide-copper composite catalyst and preparation method and application thereof | |
| CN117943017A (en) | Hydrogenation catalyst and preparation method thereof | |
| CN115318298B (en) | Copper-based three-way catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method and application thereof | |
| CN102294251A (en) | Nano-oxide catalyst for preparing propylene by oxidative dehydrogenation of propane and preparation method thereof | |
| CN115228479A (en) | Alkali metal modified NiSn material and preparation method and application thereof | |
| CN112121805A (en) | Catalyst for synthesizing methanol by carbon dioxide hydrogenation and preparation and application thereof | |
| CN109092312B (en) | Method for preparing copper-based catalyst by hydrothermal method and application | |
| CN115212898A (en) | Catalyst for preparing acetic acid by photocatalytic methane conversion and preparation method thereof | |
| CN115569652B (en) | Platinum cobalt niobium heterogeneous catalyst, preparation method and application thereof, and preparation method of 2, 5-furandicarboxylic acid | |
| CN115259229B (en) | Three-dimensional flower-ball-shaped Mn 3 O 4 Mn of silver-supported 3 O 4 And preparation method and application thereof in ozone degradation | |
| CN113368864B (en) | W-containing photocatalytic hydrogen production catalyst and preparation method thereof | |
| CN116273180B (en) | Catalyst of organic zinc complex and molybdenum sulfide heterostructure, preparation method and application | |
| CN116899574A (en) | Preparation method and application of CuZnZr catalyst for preparing methanol by carbon dioxide hydrogenation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |