CN111215084A - Copper-based catalyst for preparing methanol by carbon dioxide hydrogenation, preparation and application thereof - Google Patents
Copper-based catalyst for preparing methanol by carbon dioxide hydrogenation, preparation and application thereof Download PDFInfo
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- CN111215084A CN111215084A CN201811411702.3A CN201811411702A CN111215084A CN 111215084 A CN111215084 A CN 111215084A CN 201811411702 A CN201811411702 A CN 201811411702A CN 111215084 A CN111215084 A CN 111215084A
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 59
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 33
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 30
- 239000010949 copper Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims abstract description 20
- 238000001556 precipitation Methods 0.000 claims abstract description 15
- 239000011701 zinc Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 20
- 239000002244 precipitate Substances 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000004062 sedimentation Methods 0.000 claims description 12
- 239000012716 precipitator Substances 0.000 claims description 11
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 150000001768 cations Chemical class 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 230000005012 migration Effects 0.000 claims description 5
- 238000013508 migration Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910001415 sodium ion Inorganic materials 0.000 claims description 5
- 238000007664 blowing Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 150000002739 metals Chemical group 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229910000027 potassium carbonate Inorganic materials 0.000 claims 1
- 229910001414 potassium ion Inorganic materials 0.000 claims 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 13
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 abstract description 10
- 229960001545 hydrotalcite Drugs 0.000 abstract description 9
- 229910001701 hydrotalcite Inorganic materials 0.000 abstract description 9
- -1 copper-zinc-aluminum Chemical compound 0.000 abstract description 6
- 239000002243 precursor Substances 0.000 abstract description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000008021 deposition Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000004317 sodium nitrate Substances 0.000 description 3
- 235000010344 sodium nitrate Nutrition 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910017518 Cu Zn Inorganic materials 0.000 description 2
- 229910017752 Cu-Zn Inorganic materials 0.000 description 2
- 229910017943 Cu—Zn Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910017773 Cu-Zn-Al Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 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
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a preparation method of a copper-based catalyst for preparing methanol by carbon dioxide hydrogenation, which mainly solves the problem that the traditional copper-zinc-aluminum catalyst is poor in carbon dioxide hydrogenation activity, especially poor in stability. One of the reasons for influencing the stability of the catalyst in the carbon dioxide hydrogenation reaction is that the component zinc is in CO2And the active copper component is easy to migrate in a water vapor atmosphere, so that the active copper component is wrapped. The catalyst of the invention takes copper-zinc-aluminum as an active component, and the preparation method of the catalyst is changed, firstly, the zinc-aluminum component is precipitated, aged and roasted at low temperature, the reaction conditions are controlled, so as to obtain a zinc-aluminum hydrotalcite precursor which has higher stability and is more beneficial to copper dispersion, then, the active component copper and the precursor are subjected to deposition and precipitation reaction, and finally, the novel catalyst suitable for preparing methanol by carbon dioxide hydrogenation is obtainedCopper-zinc-aluminum catalyst. The catalyst prepared by the method has higher selectivity and stability.
Description
Technical Field
The invention relates to a preparation method of a copper-based catalyst for preparing methanol by carbon dioxide hydrogenation.
Background
The resource utilization of the carbon dioxide is one of the best ways for realizing emission reduction, environmental benefits and economic benefits can be better balanced, the core competitiveness of an enterprise can be effectively improved, and the enterprise can walk on a sustainable development road. In recent years, CO2Hydrogenation to methanol has received a great deal of attention (content Chem Ind, 2015(11): 2622-2624). Nobel prize earners Euler, in particular, have raised the above process to the height of the "methanol economy" (Catalysis Letters, 2004, 93: 1-2). This is because of the presence of CO2In numerous processes of resource utilization, CO2The process for preparing the methanol by hydrogenation is relatively simple, and can greatly reduce the industrial amplification risk of the process by referring to the mature industrial process for preparing the methanol by the synthesis gas. Simultaneously, methanol is taken as a product, and CO is reserved2The oxygen in (2) can reduce the consumption of hydrogen resources, so that the process is more economical. Besides being a clean energy source, the product methanol can also be used for producing downstream products such as olefin, aromatic hydrocarbon, gasoline and the like by a catalytic means, and is an ideal high-value-added chemical product for replacing traditional resources such as petroleum and natural gas. Thus, use of CO2The process of preparing methanol by hydrogenation solves the problem of CO2Effective means for emission and exhaustion of fossil energy.
At present, about 75 percent of methanol in the world is produced by adopting a copper catalyst of ICI company in British by a medium-pressure and low-pressure method, and the raw material is synthesis gas. After the copper-based catalyst is applied in large-scale industrialization, the optimization is continuously obtained, and the adjustment and improvement of the component proportion and the preparation process are included. And CO2Most of the catalysts for preparing methanol by hydrogenation are developed on the basis of catalysts for preparing methanol by synthesis gas. But the catalyst for preparing methanol by directly hydrogenating CO is used for CO2In the hydrogenation reaction, there are still more problems because of CO2The mechanism of preparing methanol by hydrogenation is different from that of preparing methanol by synthesis gas, and aims at CO2The hydrogenation characteristics of (a) are currently relatively few. CO 22Hydrogenation to methanol process except CO2Difficult to activate, CO2The effect of such acid gases on catalyst stability is also not negligible. By conventional coprecipitationCatalysts (CN 1274618, CN 103721719B), in which the zinc oxide component is difficult to avoid due to long-term exposure to CO2And aggregation, growth, and migration occurring in a water vapor atmosphere. However, it is difficult to obtain a stable zinc-aluminum hydrotalcite precursor by the general fractional precipitation method (CN 103272607 a).
Disclosure of Invention
Application of traditional catalyst for preparing methanol from synthesis gas to CO2Hydrogenation reactions have a number of challenges. Because of CO2Not only has strong inertia and is not easy to activate, but also has CO2As an acid gas, it also has a corrosive migration effect on the catalyst support, causing catalyst deactivation. The invention aims at CO2The characteristic of hydrogenation reaction provides CO with high activity, especially higher stability2A catalyst for preparing methanol by hydrogenation.
The invention converts CO into2Pre-precipitating active component zinc easy to agglomerate in atmosphere and carrier aluminum, adding anions and controlling heat treatment conditions to obtain more stable zinc-aluminum hydrotalcite material or hydrotalcite-like material, and performing deposition and precipitation on the material and main active component copper to obtain the final product in CO2The novel catalyst has high activity and good stability in hydrogenation reaction.
The technical problem to be solved by the invention is to aim at CO2The method has the advantages that the activation is difficult, the stability of the copper-zinc-aluminum catalyst is influenced, the preparation method of the catalyst is improved, the active zinc component in the improved catalyst is more stable, and the stability and the activity of the catalyst in the reaction of preparing methanol by carbon dioxide hydrogenation are further improved.
The invention obtains the zinc-aluminum hydrotalcite material which has stable performance and is easy to combine with active metal copper by controlling the adding amount of anions and the roasting temperature, thereby achieving the purpose of improving the CO content of the catalyst2For stability in the atmosphere. The addition of anions plays an important role in the formation and stabilization of the layered structure of the hydrotalcite, and the addition amount of the anions directly influences the properties of the hydrotalcite. The roasting temperature has great influence on the stability of the zinc-aluminum hydrotalcite structure, the temperature is too low, the heat treatment cannot play a role in stabilizing the hydrotalcite structure, and the temperature is too highHigh, a large amount of oxides will be formed, causing a weakening of the next step of interaction with the active metal copper, affecting the catalyst activity.
The catalyst preparation scheme adopted by the invention is as follows:
firstly, respectively preparing copper nitrate, zinc nitrate, aluminum nitrate, sodium carbonate, sodium nitrate and sodium hydroxide into solutions with the concentration of 0.1-10 mol/L; adding a certain volume of deionized water into a reaction kettle to serve as a sedimentation tank, mixing a zinc nitrate solution and an aluminum nitrate solution according to the proportion of a catalyst, then dripping the mixed solution into the sedimentation tank together with a sodium carbonate solution, a sodium nitrate solution, a sodium hydroxide solution or a mixed solution of any two of the sodium carbonate solution, the sodium nitrate solution and the sodium hydroxide solution which serve as a regulator and a precipitator at a constant speed, and keeping the temperature of the sedimentation tank at 40-90 ℃ and the pH value at 5-10 in the whole process; after the precipitation is completed, continuously stirring and aging for 12-24 hours at the temperature of 40-90 ℃; then, filtering and washing the obtained precipitate until no sodium ions exist in the filtrate and the filtrate is neutral; and finally, drying the washed precipitate by blowing for 4-10 hours at the temperature of 40-90 ℃, and roasting for 6-10 hours at the temperature of 100-300 ℃.
Fully grinding the roasted zinc-aluminum particles to be below 400 meshes, and ultrasonically dispersing the zinc-aluminum particles in water with a certain volume; then according to the proportion of the catalyst, simultaneously dripping a certain volume of copper nitrate solution and a precipitator sodium carbonate solution or sodium hydroxide solution into the solution, and keeping the temperature of the solution at 40-90 ℃ and the pH value at 5-10; after the precipitate is completely precipitated, aging for 4-12 hours at the temperature of 40-90 ℃, washing the precipitate until the precipitate is neutral and has no sodium ion residue, drying by blowing at the temperature of 40-90 ℃ for 4-10 hours, roasting at the temperature of 300-500 ℃ for 4-12 hours, and finally grinding and tabletting to obtain a catalyst sample.
The catalyst evaluation, conversion and selectivity calculation methods were as follows:
CO2the activity evaluation of the catalyst in the reaction of synthesizing methanol by hydrogenation is carried out on a fixed bed. The specific experimental process is as follows: a quantity of catalyst was loaded into a stainless steel reaction tube. At atmospheric pressurePure hydrogen is introduced into the reaction tube downwards, and the space velocity is about 1000-5000 h-1And the reduction temperature is about 260-350 ℃, the reduction time is 4-24 hours, nitrogen is switched, and the reaction is blown and cooled to the initial reaction temperature. And then, switching gas in the reaction tube into feed gas (the hydrogen-carbon ratio is 3, and a certain amount of nitrogen is contained as an internal standard substance), boosting the pressure to 3.0-6.0 MPa, and performing online sampling analysis by using a chromatograph after the reaction is stable. The composition of raw material gas and product is detected and analyzed on Agilent 7890B chromatogram on line, two detectors of TCD and FID, two chromatographic columns of TDX-01(2.0m multiplied by 2mm) and FFAP (30.0m multiplied by 0.32mm multiplied by 1.0 μm) are configured, wherein the former chromatographic column is used for detecting and analyzing CO and CO2The latter chromatographic column is used for detecting and analyzing CH4And CH3OH。
Calculation of conversion and Selectivity
CO2Conversion according to CO2Is calculated by the formula:
the reaction product is mainly CH3OH, CO and CH4. The calculation formula for each product selectivity is as follows:
wherein x (in) (x represents CO)2、CO、CH3OH、N2、CH4) Representing the concentration of x in the feed gas and x (out) representing the concentration of x in the tail gas.
The invention mainly solves the problem that the traditional Cu-Zn-Al catalyst has poor hydrogenation activity, especially poor stability when used for carbon dioxide. Influencing the catalyst in carbon dioxideOne of the reasons for the stability in hydrogenation reactions is the presence of the component zinc in CO2And the active copper component is easy to migrate in a water vapor atmosphere, so that the active copper component is wrapped. The catalyst provided by the invention takes copper-zinc-aluminum as an active component, a zinc-aluminum hydrotalcite precursor which is higher in stability and more beneficial to copper dispersion is obtained by changing the preparation method of the catalyst, and then the active component copper and the precursor are subjected to deposition and precipitation reaction, so that the novel copper-zinc-aluminum catalyst suitable for preparing methanol by carbon dioxide hydrogenation is finally obtained. The catalyst prepared by the method has higher selectivity and stability.
Compared with the prior art, the invention has the following beneficial effects:
1. aiming at the problem of poor stability of zinc oxide in carbon dioxide and water vapor atmosphere, the invention adopts a step-by-step precipitation method to obtain a zinc oxide component with better stability, thereby improving the stability of the copper-zinc-aluminum catalyst in CO2Stability in the reaction of preparing methanol by hydrogenation.
2. Different from the past about CO2The invention discloses a fractional precipitation method in a patent of preparing methanol by hydrogenation, which can better disperse an active component copper while obtaining a more stable zinc-aluminum hydrotalcite precursor by adding a certain amount of anions and controlling conditions such as roasting temperature, thereby obtaining higher catalytic activity and methanol selectivity while obtaining higher catalyst stability.
3. The preparation method has good repeatability and simple method, and is easy for large-scale industrial amplification.
Detailed Description
Example 1
Firstly, respectively preparing copper nitrate, zinc nitrate, aluminum nitrate, sodium carbonate and sodium hydroxide into solutions with metal ion concentration of 1 mol/L; adding 1000ml of deionized water into a reaction kettle to serve as a sedimentation tank, mixing 300ml of zinc nitrate solution with 100ml of aluminum nitrate solution, then mixing 500ml of sodium carbonate solution with 1000ml of sodium hydroxide solution, then dropping the two mixed solutions into the sedimentation tank at a constant speed, keeping the temperature of the sedimentation tank at 60 ℃ in the whole process, keeping the pH at 8, adjusting the concentration of carbonate to be 0.5 times of the charge concentration of metal cations to be precipitated, and adjusting the concentration of hydroxyl to be 1 time of the charge concentration of the metal cations to be precipitated; after the precipitation is completed, continuously stirring and aging for 12 hours at the temperature of 60 ℃; then, filtering and washing the obtained precipitate until no sodium ions exist in the filtrate and the filtrate is neutral; finally drying at 150 deg.C for 8 hr.
Fully grinding the roasted zinc-aluminum particles to be below 400 meshes, and ultrasonically dispersing the zinc-aluminum particles in 1000ml of water; then, dropwise adding 600ml of copper nitrate solution and 1200ml of sodium hydroxide solution serving as a precipitator into the solution at the same time, keeping the temperature of the solution at 60 ℃ and the pH value at 8, wherein the concentration of hydroxide radical of the precipitator is 1 time of that of metal cation to be precipitated; after the precipitation is completed, aging is carried out for 12 hours at the temperature of 60 ℃, then the precipitate is washed until the precipitate is neutral and no sodium ion remains, air blowing drying is carried out for 10 hours at the temperature of 90 ℃, then roasting is carried out for 12 hours at the temperature of 450 ℃, and finally, after grinding and tabletting, a catalyst sample is obtained. The molar ratio of the metals in the sample is as follows: cu Zn Al 6:3: 1.
Examples 2 to 23
The method is the same as the example 1, the preparation process conditions are respectively changed, and the temperature is 260 ℃, the pressure is 5MPa, and the pressure is 9000h-1The details of the production conditions and evaluation results different from those in example 1 when used in the reaction for producing methanol by hydrogenation of carbon dioxide under the conditions are shown in table 1.
TABLE 1 influence of different preparation process conditions on the performance of catalyst for preparing methanol by carbon dioxide hydrogenation
Comparative example 1
Firstly, respectively preparing copper nitrate, zinc nitrate, aluminum nitrate and sodium hydroxide into solutions with metal ion concentration of 1 mol/L; adding 1000ml of deionized water into a reaction kettle to serve as a sedimentation tank, mixing 600ml of copper nitrate solution, 300ml of zinc nitrate solution and 100ml of aluminum nitrate solution, then dropping 2100ml of sodium hydroxide solution and the mixed solution into the sedimentation tank at a constant speed, and keeping the temperature of the sedimentation tank at 60 ℃ and the pH value at 8 in the whole process; after the precipitation is completed, continuously stirring and aging for 12 hours at the temperature of 60 ℃; then, filtering and washing the obtained precipitate until no sodium ions exist in the filtrate and the filtrate is neutral; finally, the washed precipitate was air-dried at a temperature of 90 ℃ for 6 hours, followed by calcination at a temperature of 450 ℃ for 12 hours. And finally grinding and tabletting to obtain a catalyst sample. The molar ratio of the metals in the sample is as follows: cu Zn Al 6:3: 1.
Comparative example 2
The procedure is as in example 1, except that no sodium carbonate solution is added during the reaction in which the zinc-aluminium precipitate is formed.
Comparative example 3
The procedure of preparation was the same as in example 1, except that the drying temperature of the zinc-aluminum precipitate was changed to 350 ℃.
Comparative example 4
The preparation steps are the same as example 1, except that the zinc-aluminum precipitate is directly subjected to a precipitation reaction with a copper solution without being dried.
Example 29:
catalysts prepared in example 1 and comparative examples 1, 2, 3, 4 at 260 deg.C, 5MPa, 9000h-1The properties of the catalyst used in the reaction of preparing methanol by hydrogenating carbon dioxide under the conditions are shown in Table 2.
TABLE 2 influence of different preparation methods on the catalyst performance for preparing methanol by carbon dioxide hydrogenation
As can be seen from Table 2, the activity of comparative example 2 is poor, which indicates that the structure of the zinc-aluminum hydrotalcite is greatly influenced by the concentration of anions in the precipitation process, and the activity of the catalyst prepared without adding carbonate ions is poor. The worst activity of the comparative example 3 shows that the zinc-aluminum hydrotalcite structure is sensitive to the roasting temperature, and the interaction between the active metal copper and zinc is weakened by the higher heat treatment temperature, thereby affecting the activity of the catalyst.
Example 30:
the catalysts prepared in example 1 and comparative examples 1 and 4 were subjected to a 1000-hour stability test for methanol production by carbon dioxide hydrogenation. The test conditions were the same as in example 4.
TABLE 3 influence of different preparation methods on the conversion of carbon dioxide of the catalyst
As can be seen from table 3, the catalyst obtained by pre-precipitating zinc and aluminum and then performing heat treatment shows the best stability in the reaction of preparing methanol by carbon dioxide hydrogenation, the catalyst prepared by the fractional precipitation method is slightly less stable, while the catalyst prepared by the coprecipitation method is the least stable in the carbon dioxide atmosphere.
Example 31:
the catalysts prepared in example 1 and comparative example 1 were examined for copper dispersion and copper-zinc crystal size at different reaction times. As shown in table 4.
TABLE 4 copper Dispersion and Cu-Zn Crystal size of the catalyst at different reaction times
As can be seen from Table 4, the catalyst of example 1 exhibited little change in performance and good stability as the reaction proceeded. While the specific surface area of the active copper of comparative example 1 was gradually decreased, the degree of dispersion of copper was greatly decreased. However, the change of the grain size of copper is not obvious, and only the crystal size of zinc oxide slightly increases.
Example 32:
the surface element compositions of the catalysts prepared in example 1 and comparative example 1 were examined for different reaction times by XPS characterization. As shown in table 5.
TABLE 5 copper Dispersion and Cu-Zn Crystal size of the catalysts at different reaction times
As can be seen from the experimental data in table 5, the catalyst prepared in comparative example 1 has the zinc component that is unstable in the carbon dioxide atmosphere, and migration and aggregation occur, so that the surface active copper component in the catalyst is wrapped by zinc, and the dispersion degree and the active specific surface area of copper are reduced, thereby causing the catalyst to be deactivated. While example 1 adopts a preparation method of pre-precipitating a zinc-aluminum component, zinc in the catalyst is avoided being in CO2And the migration of zinc in the water vapor atmosphere, thereby improving the stability of the catalyst in the reaction of preparing methanol by hydrogenating carbon dioxide.
Claims (9)
1. A preparation method of a copper-based catalyst for preparing methanol by carbon dioxide hydrogenation is characterized by comprising the following steps:
(1) adding deionized water into a reaction kettle to serve as a sedimentation tank, mixing a zinc nitrate solution and an aluminum nitrate solution according to a catalyst ratio or taking a mixed solution of the zinc nitrate and the aluminum nitrate, then uniformly dropping the mixed solution together with a regulator and a precipitator, or uniformly dropping a mixed solution of the regulator and the precipitator into the sedimentation tank, keeping the temperature of the sedimentation tank at 40-90 ℃ in the whole process, and keeping the pH at 7-10, wherein the regulator is one or two of sodium carbonate and potassium carbonate, the precipitator is one or two of sodium hydroxide and potassium hydroxide, and in the whole process, the concentration of the regulator is 0.5-3 times of the charge concentration of metal cations to be precipitated, and the concentration of hydroxide radical of the precipitator is 1.0-1.5 times of the charge concentration of the metal cations to be precipitated;
(2) after the precipitation is completed, continuously stirring and aging for 12-24 hours at the temperature of 40-90 ℃;
(3) filtering and washing the obtained precipitate until no sodium ions and potassium ions exist in the filtrate and the filtrate is neutral;
(4) drying the washed precipitate for 4-10 hours at the temperature of 90-260 ℃;
(5) grinding the roasted particles to be below 400 meshes, and ultrasonically dispersing the particles in water;
(6) according to the proportion of a catalyst, simultaneously dripping a copper nitrate solution and a precipitator sodium carbonate solution and/or a sodium hydroxide solution into the solution, and keeping the temperature of the solution at 40-90 ℃ and the pH value at 7-10;
(7) after the precipitate is completely precipitated, aging for 4-12 hours at the temperature of 40-90 ℃, washing the precipitate until the precipitate is neutral and has no sodium ion residue, drying by blowing at the temperature of 40-90 ℃ for 4-10 hours, roasting at the temperature of 300-500 ℃ for 4-12 hours, and finally grinding and tabletting to obtain a catalyst sample.
2. The preparation method of the copper-based catalyst for preparing methanol by hydrogenating carbon dioxide according to claim 1, wherein in the step (1):
the concentration of metal ions in the copper nitrate solution, the zinc nitrate solution and the aluminum nitrate solution is 0.1-10 mol/L;
the concentration of metal ions in the mixed solution of zinc nitrate and aluminum nitrate is 0.1-10 mol/L;
the concentration of metal ions in the regulator and the precipitator is 0.1-10 mol/L;
the concentration of metal ions in the mixed solution of the regulator and the precipitator is 0.1-10 mol/L.
3. The preparation method of the copper-based catalyst for preparing methanol by hydrogenating carbon dioxide according to claim 1, wherein the precipitating agent in the step (1) is preferably sodium hydroxide solution with the concentration of 0.1-10 mol/L; the preferable concentration of the regulator is 0.1-10 mol/L sodium carbonate solution, and the preferable concentration of the use amount of the regulator is 0.5-3 times of the charge concentration of metal cations to be precipitated, so that the appropriate anion amount is ensured, and the regulator is used for forming a good layered zinc-aluminum hydrotalcite structure.
4. The preparation method of the copper-based catalyst for preparing methanol by hydrogenating carbon dioxide according to claim 1, wherein the precipitation condition in the step (1) is preferably pH 7-9.
5. The method for preparing the copper-based catalyst for preparing methanol by hydrogenating carbon dioxide according to claim 1, wherein the drying temperature in the step (4) is preferably 100-200 ℃.
6. A catalyst prepared by the preparation method of the copper-based catalyst for preparing methanol by hydrogenating carbon dioxide as claimed in any one of claims 1 to 5, wherein the catalyst takes copper and zinc as active components and alumina as a carrier, and the molar composition of the metals in the catalyst is as follows: cu: 30-60%; zn: 10-40%; al: 10 to 30 percent.
7. The catalyst of claim 6 wherein the active component zinc is stabilized in the carrier alumina in CO2And migration does not easily occur in a water vapor atmosphere.
8. Use of the catalyst of claim 6 or 7 in the hydrogenation of carbon dioxide to methanol.
9. The use of the catalyst according to claim 8, wherein the reaction conditions of the catalyst for preparing methanol by hydrogenating carbon dioxide are as follows: the molar ratio of the carbon dioxide to the hydrogen is 2-5, the pressure is 3-6 Mpa, the temperature is 180-380 ℃, and the space velocity is 4500-30000 h-1。
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