CN111167459A - A kind of catalyst for making methanol from mixed gas and its preparation method and use - Google Patents
A kind of catalyst for making methanol from mixed gas and its preparation method and use Download PDFInfo
- Publication number
- CN111167459A CN111167459A CN202010088734.5A CN202010088734A CN111167459A CN 111167459 A CN111167459 A CN 111167459A CN 202010088734 A CN202010088734 A CN 202010088734A CN 111167459 A CN111167459 A CN 111167459A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- precursor
- mixed gas
- temperature
- preparation
- 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 239000012266 salt solution Substances 0.000 claims abstract description 35
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 230000009467 reduction Effects 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 239000011159 matrix material Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000007873 sieving Methods 0.000 claims abstract description 16
- 230000032683 aging Effects 0.000 claims abstract description 15
- 239000002244 precipitate Substances 0.000 claims abstract description 15
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 238000001704 evaporation Methods 0.000 claims abstract description 8
- 230000008020 evaporation Effects 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 8
- 238000000967 suction filtration Methods 0.000 claims abstract description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000001879 copper Chemical class 0.000 claims abstract description 3
- 150000003751 zinc Chemical class 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 53
- 239000010949 copper Substances 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 18
- 239000011701 zinc Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 239000000706 filtrate Substances 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 12
- 239000010865 sewage Substances 0.000 abstract description 2
- 239000012452 mother liquor Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- 238000011049 filling Methods 0.000 description 16
- 239000006004 Quartz sand Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000012065 filter cake Substances 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 9
- 238000011946 reduction process Methods 0.000 description 9
- 238000007865 diluting Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005406 washing Methods 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
- B01J23/70—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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention provides a catalyst for preparing methanol from mixed gas, a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) dropwise adding a mixed salt solution of copper salt, zinc salt and aluminum salt and ammonia water into water simultaneously to keep a constant pH value, and stirring to obtain a precursor solution; 2) performing ammonia evaporation aging treatment on the precursor solution to obtain a precursor precipitate; 3) carrying out suction filtration and drying on the precursor precipitate to obtain a catalyst precursor; 4) grinding, roasting and cooling the catalyst precursor, tabletting, forming and sieving to obtain a catalyst matrix; 5) and reducing the catalyst matrix in a reducing atmosphere to obtain the catalyst. The catalyst is prepared by the preparation method and can be used for CO/CO with different proportions2Preparing methanol from the mixed gas. The preparation process is simple, the reaction condition variable is easy to control, and the preparation of the catalyst does not need to be carried outWashing treatment, sewage discharge reduction, water consumption saving, and in addition, mother liquor ammonia can be recycled in the preparation process, and raw material loss is reduced.
Description
Technical Field
The invention belongs to the field of inorganic chemistry, and particularly relates to a catalyst for preparing methanol from mixed gas, and a preparation method and application thereof.
Background
Methanol is an important basic raw material in industrial production and is widely applied to industries such as chemical industry, textile industry, medicine industry, coating industry and the like. The downstream products of methanol are hundreds of types, wherein formaldehyde, dimethyl ether, acetic acid and methyl tert-butyl ether (MTBE) are taken as main products. With the continuous deterioration of natural environment and the gradual exhaustion of fossil fuel, the energy structure will be shifted to clean and renewable energy in the future. The methanol is convenient for storage and transportation, is a good liquid hydrogen storage carrier, has higher oxygen content and high combustion heat value, and is widely applied to gasoline engines to replace finished gasoline.
ICI company successfully realizes low-pressure methanol synthesis in the 60 th century, the system adopts a high-activity Cu/Zn/Al catalyst, and then the German Lurgi company still adopts a Cu-based catalyst and further improves the production process to successfully realize medium-pressure methanol synthesis. With the proposal of medium and low pressure process technology, the copper-based catalyst is also greatly applied and developed. However, despite the continued optimization of copper-based methanol catalysts, there are still major disadvantages: CO 22Low conversion rate, high selectivity of by-products, poor sulfur resistance, easy sintering at high temperature and the like. Therefore, optimizing the reaction conditions and improving the catalyst preparation process become the key points of attention of many experts and scholars.
The raw material gas component for reaction is the key technical condition in the methanol synthesis process, and currently, the industrial methanol is mainly synthesized from natural gas or coal through synthesis gas (H)2+ CO), while the industrial waste gas is generally rich in CO and CO2And H2Etc. can be utilized. Therefore, the reasonable utilization of the industrial waste gas can not only reduce the environmental pollution, but also realize the renewable recycling of carbon resources. In addition, the biomass-based gas source is also a multi-component mixed gas, and the main component of the mixed gas also comprises H2、CO2CO with some impurity components such as N2、CH4Therefore, the preparation of the methanol synthesis catalyst suitable for the components of the multi-component mixed gas has considerable application prospect and important practical significance for widening the source of the raw material gas and improving the economic benefit.
Because the copper-based catalyst is a structure sensitive reaction in the methanol synthesis process, different preparation methods directly or indirectly influence the phase composition and microstructure of the catalyst precursor, and further influence the reaction performance. The existing copper-based catalyst preparation method is commonly applied by a coprecipitation method, an impregnation method and a sol-gel method. Coprecipitation is the most widely used preparation method at present, and the method can enable reactants to achieve uniform dispersion and mixing in nanometer and molecular dimensions, and realize strong interaction among all components. However, the method has relatively complex operation flow and higher requirement on the precision of the control variable, and is not beneficial to industrialized large-scale operation; the impregnation method is mostly used for preparing the supported catalyst, and the effect of the impregnation method is not ideal for preparing the high-supported copper-based catalyst in the methanol synthesis reaction. The sol-gel method involves organic solvents during the manufacturing process, which may be harmful to human health. Therefore, it is necessary to find a method for preparing a catalyst with simple operation, easily controllable reaction condition variables, clean and cheap raw materials, and the method is used for preparing a novel copper-based catalyst for methanol synthesis applicable to multi-component mixed gas as a raw material.
Disclosure of Invention
The invention aims to provide a catalyst for preparing methanol from mixed gas, a preparation method and application thereof. The prepared catalyst is applied to multi-component mixed gas with different proportions to catalyze methanol synthesis reaction, namely is suitable for different CO/CO2Raw material gas is proportioned, so that the source of the raw material gas for methanol synthesis is widened, and the high-efficiency utilization of carbon resources is realized.
In order to achieve the above objects and other related objects, the present invention is achieved by the following technical solutions:
the first aspect of the invention provides a preparation method of a catalyst for preparing methanol from mixed gas, which comprises the following steps:
1) dropwise adding a mixed salt solution of copper salt, zinc salt and aluminum salt and ammonia water into water simultaneously to keep a constant pH value, and stirring to obtain a precursor solution;
2) carrying out ammonia evaporation aging treatment on the precursor solution obtained in the step 1) to obtain a precursor precipitate;
3) carrying out suction filtration and drying on the precursor precipitate obtained in the step 2) to obtain a catalyst precursor;
4) grinding, roasting and cooling the catalyst precursor obtained in the step 3), tabletting, forming and sieving to obtain a catalyst matrix;
5) reducing the catalyst parent body obtained in the step 4) in a reducing atmosphere to obtain the catalyst.
Preferably, in the step 1), the molar ratio of copper, zinc and aluminum elements in the mixed salt solution is (0.5-2): 1: (0.5-2), such as the molar ratio of copper to zinc elements is (0.5-1): 1. (1-1.5): 1 or (1.5-2): 1, the molar ratio of zinc and aluminum elements is 1: (0.5-1), 1: (1-1.2) or 1: (1.2-2). More preferably, the molar ratio of the copper, zinc and aluminium elements in the mixed salt solution is 1:1:0.5, 1.5:1: 1. 2:1:1.2, 2:1: 2.
preferably, in the step 1), the total molar concentration of the metal elements in the mixed salt solution is 0.5-2 mol/L, such as 0.5-1 mol/L, 1-1.5 mol/L or 1.5-2 mol/L. More preferably, the molar concentration of the total metal elements in the mixed salt solution is 0.5-1 mol/L.
Preferably, in step 1), the pH is kept constant at 6 to 11, such as 6 to 8, 8 to 9, 9 to 10 or 10 to 11. More preferably, the pH value kept constant is 8 to 10.
The water amount in the step 1) is determined according to the volume of the selected container, and can be stirred, and can usually account for 5-10% of the volume of the container.
Preferably, in the step 2), the temperature of the ammonia evaporation aging treatment is 80-120 ℃, such as 80-90 ℃, 90-95 ℃, 95-100 ℃ or 100-120 ℃, and more preferably 80-100 ℃.
Preferably, in the step 2), the ammonia evaporation aging treatment time is 12-20 hours, such as 12-18 hours or 18-20 hours.
Preferably, in the step 3), the drying temperature is 45-65 ℃, such as 45-50 ℃, 50-60 ℃ or 60-65 ℃.
Preferably, in the step 4), the roasting temperature is 400-800 ℃, such as 400-450 ℃, 450-500 ℃, 500-550 ℃, 550-600 ℃ or 600-800 ℃, and more preferably 400-600 ℃.
Preferably, in step 4), the sieving is: sieving the mixture with a 40-60 mesh sieve.
Preferably, in the step 5), the reduction temperature is 100-400 ℃, such as 100-200 ℃, 200-250 ℃, 250-300 ℃ or 300-400 ℃, and more preferably 200-300 ℃.
Preferably, in step 5), the reducing atmosphere is a hydrogen atmosphere.
Preferably, the preparation method further comprises: and (3) distilling ammonia from the filtrate obtained in the step 3).
More preferably, the ammonia evaporation temperature is 50-80 deg.C, such as 50-60 deg.C, 60-70 deg.C or 70-80 deg.C.
The invention provides a catalyst for preparing methanol from mixed gas, which is prepared by adopting the preparation method of any one of the above.
The third aspect of the invention provides the application of the catalyst, which is used for preparing methanol from mixed gas.
Preferably for the production of methanol from mixed gas in a fixed bed reactor.
Preferably, the reaction conditions for preparing methanol from the mixed gas are as follows: the reaction temperature is 200-300 ℃, such as 200-210 ℃, 210-230 ℃, 230-250 ℃ or 250-300 ℃, and the reaction space velocity is 1000-20000 h-1E.g. 1000 to 4000h-1Or 4000 to 20000h-1The reaction pressure is 2-6 MPa, such as 2-5 MPa or 5-6 MPa, more preferably 5MPa, H in the mixed gas2/(CO+CO2) The molar ratio of (A) to (B) is 2.95 to 3.05, such as 2.95 to 3 or 3 to 3.05. The reaction temperature is more preferably 200 to 300 ℃. The reaction space velocity is more preferably 4000h-1。
Preferably, CO in the mixed gas accounts for CO2The volume percentage of the + CO is x, x is more than or equal to 0 and less than or equal to 0.85, and x is more than or equal to 0 and less than or equal to 0X is more than or equal to 0.1 and less than or equal to 0.25, x is more than or equal to 0.25 and less than or equal to 0.5 or x is more than or equal to 0.5 and less than or equal to 0.85.
Compared with the prior art, the invention has at least one of the following characteristics:
(1) the preparation method of the catalyst for preparing methanol from mixed gas is simple, overcomes the technical problem that pH is difficult to control due to strong alkaline precipitator, and is simple in operation steps and easy for industrial amplification.
(2) The catalyst is prepared without washing, thereby reducing sewage discharge, saving water consumption, and reducing resource and time cost.
(3) The production cost is low, ammonia in the filtrate can be recycled, and the loss of raw materials is reduced.
(4) The catalyst prepared by the invention is applied to multi-component mixed gas with different proportions to catalyze methanol synthesis reaction, namely is suitable for different CO/CO2The raw material gas is proportioned, the raw material gas separation cost is reduced, the purification process is reduced, the source of the raw material gas for methanol synthesis is widened, and the high-efficiency utilization of carbon resources is realized.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Example 1
The molar composition of the metal salt solution of the catalyst adopted by the invention is that Cu/Zn/Al is 1:1:0.5, the metal salt solution is dissolved in deionized water to prepare 0.5mol/L mixed solution, ammonia water and precursor salt solution are simultaneously and slowly dripped into a three-mouth flask containing deionized water accounting for 10% of the volume of the container under the condition of stirring at room temperature, and the pH value is kept at 8 +/-0.2. Aging at 80 deg.C for 18h under stirring after precipitation, vacuum filtering the precipitate at room temperature, distilling the filtrate at 60 deg.C, drying the filter cake in oven at 45 deg.C for 12h to obtain catalyst precursor, grinding the dried catalyst precursor, calcining at 400 deg.C in high temperature muffle furnace, and calcining at 400 deg.CHeating to roasting temperature, keeping the temperature for 4H, cooling, tabletting, molding, and sieving with 40-60 mesh sieve to obtain catalyst matrix, which is filled in the fixed bed reactor with a catalyst loading of 1.5ml, diluted with 1.5ml of fine quartz sand and in a reducing atmosphere of H2The reduction temperature is 200 ℃, and the reduction time is 5 h. After the reduction process is finished, the temperature is raised to the target reaction temperature of 200 ℃, the mixed gas is subjected to back pressure until the working pressure is 5.0MPa, and the synthesis gas H2/(CO+CO2) At a molar ratio of 3, CO/(CO)2+ CO) ═ 0, and the reaction space velocity is 20000h-1The reaction results are shown in Table 1.
Example 2
The molar composition of the metal salt solution of the catalyst adopted by the invention is that Cu/Zn/Al is 1.5:1:1, the metal salt solution is dissolved in deionized water to prepare 1mol/L mixed solution, ammonia water and precursor salt solution are simultaneously and slowly dripped into a three-mouth flask containing deionized water accounting for 5% of the volume of the container under the condition of stirring at room temperature, and the pH value is kept at 9 +/-0.2. Aging at 120 ℃ for 12H under a stirring state after precipitation is finished, filtering the precipitate at room temperature, distilling the filtrate at 50 ℃, drying the filter cake in a drying oven at 50 ℃ for 12H to obtain a catalyst precursor, grinding the obtained dried catalyst precursor, roasting at 450 ℃ in a high-temperature muffle furnace, setting a program to heat up to the roasting temperature, keeping the temperature for 4H, cooling, tabletting, forming, sieving with a 40-60-mesh sieve to obtain a catalyst matrix, filling the catalyst matrix into a fixed bed reactor, wherein the catalyst filling amount is 1.5ml, diluting with 1.5ml of fine quartz sand, and the reducing atmosphere is H2The reduction temperature is 100 ℃, and the reduction time is 5 h. After the reduction process is finished, the temperature is raised to the target reaction temperature of 210 ℃, the mixed gas is subjected to back pressure until the working pressure is 6.0MPa, and the synthesis gas H2/(CO+CO2) At a molar ratio of 2.95, CO/(CO)2+ CO) is 0.1, and the reaction space velocity is 4000h-1The reaction results are shown in Table 1.
Example 3
The molar composition of the metal salt solution of the catalyst adopted by the invention is that Cu/Zn/Al is 2:1:1.2, the metal salt solution is dissolved in deionized water to prepare 1mol/L mixed solution, ammonia water and precursor salt solution are simultaneously and slowly dripped into a three-mouth flask containing deionized water accounting for 8% of the volume of the container under the condition of stirring at room temperature, and the pH value is kept at 10 +/-0.2. After the precipitation is finished, stirring the mixture at 80 DEG CAging for 18H, carrying out suction filtration on the precipitate at room temperature, distilling the filtrate at 70 ℃, drying the filter cake for 12H in a 65 ℃ oven to obtain a catalyst precursor, grinding the obtained dried catalyst precursor, then putting the ground dried catalyst precursor into a high-temperature muffle furnace for roasting at 500 ℃, setting the program for heating to the roasting temperature and keeping the temperature for 4H, cooling, tabletting, forming, and sieving with a 40-60-mesh sieve to obtain a catalyst precursor, filling the catalyst precursor into a fixed bed reactor, wherein the catalyst filling amount is 1.5ml, diluting with 1.5ml of fine quartz sand, and the reducing atmosphere is H2The reduction temperature is 250 ℃, and the reduction time is 5 h. After the reduction process is finished, the temperature is raised to the target reaction temperature of 250 ℃, the mixed gas is subjected to back pressure until the working pressure is 5.0MPa, and the synthesis gas H2/(CO+CO2) At a molar ratio of 3, CO/(CO)2+ CO) is 0.25, and the reaction space velocity is 4000h-1The reaction results are shown in Table 1.
Example 4
The molar composition of the metal salt solution of the catalyst adopted by the invention is that Cu/Zn/Al is 2:1:2, the metal salt solution is dissolved in deionized water to prepare 2mol/L mixed solution, ammonia water and precursor salt solution are simultaneously and slowly dripped into a three-neck flask containing deionized water accounting for 5% of the volume of a container under the condition of stirring at room temperature, and the pH value is kept at 11 +/-0.2. Aging at 95 ℃ for 18H under a stirring state after precipitation is finished, filtering the precipitate at room temperature, distilling the filtrate at 80 ℃, drying the filter cake in a 60 ℃ oven for 12H to obtain a catalyst precursor, grinding the obtained dried catalyst precursor, roasting at 550 ℃ in a high-temperature muffle furnace, setting a program to heat up to the roasting temperature, keeping the temperature for 4H, cooling, tabletting, forming, sieving with a 40-60 mesh sieve to obtain a catalyst matrix, filling the catalyst matrix into a fixed bed reactor, wherein the catalyst filling amount is 1.5ml, diluting with 1.5ml of fine quartz sand, and the reducing atmosphere is H2The reduction temperature is 250 ℃, and the reduction time is 5 h. After the reduction process is finished, the temperature is raised to the target reaction temperature of 250 ℃, the mixed gas is subjected to back pressure until the working pressure is 5.0MPa, and the synthesis gas H2/(CO+CO2) At a molar ratio of 3, CO/(CO)2+ CO) is 0.5, and the reaction space velocity is 4000h-1The reaction results are shown in Table 1.
Example 5
The molar composition of the metal salt solution of the catalyst adopted by the invention is that Cu/Zn/Al is 1:1:0.5 and is dissolved in deionized waterAnd (3) preparing a mixed solution of 1.5mol/L, slowly dripping ammonia water and precursor salt solution into a three-neck flask containing deionized water accounting for 9% of the volume of the container at the same time under the condition of stirring at room temperature, and keeping the pH value at 6 +/-0.2. Aging for 18H at 100 ℃ under a stirring state after precipitation is finished, filtering the precipitate at room temperature, distilling the filtrate at 70 ℃, drying the filter cake for 12H in a 65 ℃ oven to obtain a catalyst precursor, grinding the obtained dried catalyst precursor, roasting in a high-temperature muffle furnace at 800 ℃, setting the program to heat up to the roasting temperature and keeping the temperature for 4H, cooling, tabletting, forming, sieving with a 40-60 mesh sieve to obtain a catalyst matrix, filling the catalyst matrix into a fixed bed reactor, wherein the catalyst filling amount is 1.5ml, diluting with 1.5ml of fine quartz sand, and the reducing atmosphere is H2The reduction temperature is 300 ℃, and the reduction time is 5 h. After the reduction process is finished, the temperature is raised to the target reaction temperature of 300 ℃, the mixed gas is subjected to back pressure until the working pressure is 2.0MPa, and the synthesis gas H2/(CO+CO2) At a molar ratio of 3, CO/(CO)2+ CO) is 0.85, and the reaction space velocity is 1000h-1The reaction results are shown in Table 1.
Example 6
The molar composition of the metal salt solution of the catalyst adopted by the invention is that Cu/Zn/Al is 1.5:1:1, the metal salt solution is dissolved in deionized water to prepare 1mol/L mixed solution, ammonia water and precursor salt solution are simultaneously and slowly dripped into a three-mouth flask containing deionized water accounting for 10% of the volume of the container under the condition of stirring at room temperature, and the pH value is kept at 9 +/-0.2. Aging at 80 ℃ for 18H under a stirring state after precipitation is finished, filtering the precipitate at room temperature, distilling the filtrate at 70 ℃, drying the filter cake in a 60 ℃ oven for 12H to obtain a catalyst precursor, grinding the obtained dried catalyst precursor, roasting in a high-temperature muffle furnace at 400 ℃, setting the program to heat up to the roasting temperature and keeping the temperature for 4H, cooling, tabletting, forming, sieving with a 40-60 mesh sieve to obtain a catalyst matrix, filling the catalyst matrix into a fixed bed reactor, wherein the catalyst filling amount is 1.5ml, diluting with 1.5ml of fine quartz sand, and the reducing atmosphere is H2The reduction temperature is 250 ℃, and the reduction time is 5 h. After the reduction process is finished, the temperature is raised to the target reaction temperature of 200 ℃, the mixed gas is subjected to back pressure until the working pressure is 5.0MPa, and the synthesis gas H2/(CO+CO2) At a molar ratio of 3, CO/(CO)2+ CO) is 0.5 and the reaction space velocity is4000h-1The reaction results are shown in Table 1.
Example 7
The molar composition of the metal salt solution of the catalyst adopted by the invention is that Cu/Zn/Al is 2:1:1.2, the metal salt solution is dissolved in deionized water to prepare 1mol/L mixed solution, ammonia water and precursor salt solution are simultaneously and slowly dripped into a three-mouth flask containing deionized water accounting for 5% of the volume of the container under the condition of stirring at room temperature, and the pH value is kept at 10 +/-0.2. Aging at 80 ℃ for 18H under a stirring state after precipitation is finished, filtering the precipitate at room temperature, distilling the filtrate at 70 ℃, drying the filter cake in a drying oven at 65 ℃ for 12H to obtain a catalyst precursor, grinding the obtained dried catalyst precursor, roasting in a high-temperature muffle furnace at 500 ℃, setting the program to heat up to the roasting temperature, keeping the temperature for 4H, cooling, tabletting, forming, sieving with a 40-60-mesh sieve to obtain a catalyst matrix, filling the catalyst matrix into a fixed bed reactor, wherein the catalyst filling amount is 1.5ml, diluting with 1.5ml of fine quartz sand, and the reducing atmosphere is H2The reduction temperature is 250 ℃, and the reduction time is 5 h. After the reduction process is finished, the temperature is raised to the target reaction temperature of 250 ℃, the mixed gas is subjected to back pressure until the working pressure is 5.0MPa, and the synthesis gas H2/(CO+CO2) At a molar ratio of 3, CO/(CO)2+ CO) is 0.5, and the reaction space velocity is 4000h-1The reaction results are shown in Table 1.
Example 8
The molar composition of the metal salt solution of the catalyst adopted by the invention is that Cu/Zn/Al is 2:1:2, the metal salt solution is dissolved in deionized water to prepare 2mol/L mixed solution, ammonia water and precursor salt solution are simultaneously and slowly dripped into a three-neck flask containing deionized water accounting for 10% of the volume of a container under the condition of stirring at room temperature, and the pH value is kept at 11 +/-0.2. Aging at 90 ℃ for 20H under a stirring state after precipitation is finished, filtering the precipitate at room temperature, distilling the filtrate at 70 ℃, drying the filter cake in a drying oven at 50 ℃ for 12H to obtain a catalyst precursor, grinding the obtained dried catalyst precursor, roasting in a high-temperature muffle furnace at 600 ℃, setting the program to heat up to the roasting temperature, keeping the temperature for 4H, cooling, tabletting, forming, sieving with a 40-60-mesh sieve to obtain a catalyst matrix, filling the catalyst matrix into a fixed bed reactor, wherein the catalyst filling amount is 1.5ml, diluting with 1.5ml of fine quartz sand, and the reducing atmosphere is H2The reduction temperature is 400 ℃ and the reduction time isAnd 5 h. After the reduction process is finished, the temperature is raised to the target reaction temperature of 230 ℃, the mixed gas is subjected to back pressure until the working pressure is 5.0MPa, and the synthesis gas H2/(CO+CO2) The molar ratio of (A) to (B) is 3.05, CO/(CO)2+ CO) is 0.1, and the reaction space velocity is 4000h-1The reaction results are shown in Table 1.
Example 9
The molar composition of the metal salt solution of the catalyst adopted by the invention is that Cu/Zn/Al is 2:1:1.2, the metal salt solution is dissolved in deionized water to prepare 1mol/L mixed solution, ammonia water and precursor salt solution are simultaneously and slowly dripped into a three-mouth flask containing deionized water accounting for 7% of the volume of a container under the condition of stirring at room temperature, and the pH value is kept at 10 +/-0.2. Aging at 80 ℃ for 18H under a stirring state after precipitation is finished, filtering the precipitate at room temperature, distilling the filtrate at 70 ℃, drying the filter cake in a drying oven at 65 ℃ for 12H to obtain a catalyst precursor, grinding the obtained dried catalyst precursor, roasting in a high-temperature muffle furnace at 500 ℃, setting the program to heat up to the roasting temperature, keeping the temperature for 4H, cooling, tabletting, forming, sieving with a 40-60-mesh sieve to obtain a catalyst matrix, filling the catalyst matrix into a fixed bed reactor, wherein the catalyst filling amount is 1.5ml, diluting with 1.5ml of fine quartz sand, and the reducing atmosphere is H2The reduction temperature is 250 ℃, and the reduction time is 5 h. After the reduction process is finished, the temperature is raised to the target reaction temperature of 250 ℃, the mixed gas is subjected to back pressure until the working pressure is 5.0MPa, and the synthesis gas H2/(CO+CO2) At a molar ratio of 3, CO/(CO)2+ CO) is 0.85, and the reaction space velocity is 4000h-1The reaction results are shown in Table 1.
Table 1 results of catalyst reactions of example 1 to example 9
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention. Those skilled in the art can make various changes, modifications and equivalent arrangements, which are equivalent to the embodiments of the present invention, without departing from the spirit and scope of the present invention, and which may be made by utilizing the techniques disclosed above; meanwhile, any changes, modifications and variations of the above-described embodiments, which are equivalent to those of the technical spirit of the present invention, are within the scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of a catalyst for preparing methanol from mixed gas is characterized by comprising the following steps:
1) dropwise adding a mixed salt solution of copper salt, zinc salt and aluminum salt and ammonia water into water simultaneously to keep a constant pH value, and stirring to obtain a precursor solution;
2) carrying out ammonia evaporation aging treatment on the precursor solution obtained in the step 1) to obtain a precursor precipitate;
3) carrying out suction filtration and drying on the precursor precipitate obtained in the step 2) to obtain a catalyst precursor;
4) grinding, roasting and cooling the catalyst precursor obtained in the step 3), tabletting, forming and sieving to obtain a catalyst matrix;
5) reducing the catalyst parent body obtained in the step 4) in a reducing atmosphere to obtain the catalyst.
2. The method according to claim 1, wherein the step 1) further comprises at least one of the following technical features:
1) the molar ratio of copper, zinc and aluminum elements in the mixed salt solution is (0.5-2): 1: (0.5 to 2);
2) the total metal element molar concentration of the mixed salt solution is 0.5-2 mol/L;
3) keeping the constant pH value at 6-11.
3. The method of claim 1, further comprising at least one of the following technical features:
1) in the step 2), the ammonia evaporation aging treatment temperature is 80-120 ℃;
2) in the step 2), the ammonia evaporation aging treatment time is 12-20 h;
3) in the step 3), the drying temperature is 45-65 ℃.
4. The method according to claim 1, wherein the step 4) further comprises at least one of the following technical features:
1) the roasting temperature is 400-800 ℃;
2) the sieving is as follows: sieving the mixture with a 40-60 mesh sieve.
5. The method according to claim 1, wherein the step 5) further comprises at least one of the following technical features:
1) the reduction temperature is 100-400 ℃;
2) the reducing atmosphere is a hydrogen atmosphere.
6. The method of claim 1, further comprising: and (3) distilling ammonia from the filtrate obtained in the step 3).
7. The method according to claim 6, wherein the ammonia distillation temperature is 50 to 80 ℃.
8. A catalyst for preparing methanol from mixed gas by the method of any one of claims 1 to 7.
9. The catalyst of claim 8 used for preparing methanol from mixed gas.
10. Use according to claim 9, characterised in that it further comprises at least one of the following technical features:
1) the method is used for preparing methanol from mixed gas in a fixed bed reactor;
2) the reaction conditions for preparing methanol from the mixed gas are as follows: reaction ofThe temperature is 200-300 ℃, and the reaction space velocity is 1000-20000 h-1The reaction pressure is 2-6 MPa, and H is contained in the mixed gas2/(CO+CO2) The molar ratio of (A) to (B) is 2.95-3.05;
3) CO in the mixed gas accounts for CO2The volume percentage of the + CO is x, and x is more than or equal to 0 and less than or equal to 0.85.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010088734.5A CN111167459A (en) | 2020-02-12 | 2020-02-12 | A kind of catalyst for making methanol from mixed gas and its preparation method and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010088734.5A CN111167459A (en) | 2020-02-12 | 2020-02-12 | A kind of catalyst for making methanol from mixed gas and its preparation method and use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111167459A true CN111167459A (en) | 2020-05-19 |
Family
ID=70624660
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010088734.5A Pending CN111167459A (en) | 2020-02-12 | 2020-02-12 | A kind of catalyst for making methanol from mixed gas and its preparation method and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111167459A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112264026A (en) * | 2020-11-18 | 2021-01-26 | 西南化工研究设计院有限公司 | Preparation method of high-activity high-selectivity methanol synthesis catalyst |
| CN112517012A (en) * | 2020-12-01 | 2021-03-19 | 大连理工大学 | CO (carbon monoxide)2Preparation method and application of catalyst for preparing methanol by hydrogenation |
| CN115364863A (en) * | 2021-05-18 | 2022-11-22 | 中国科学院大连化学物理研究所 | A bifunctional catalyst, preparation method and application in methanol synthesis and reforming hydrogen production |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102451695A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工集团公司 | Preparation method of copper-based methanol synthesis catalyst |
| CN103433046A (en) * | 2013-09-18 | 2013-12-11 | 上海中科高等研究院 | Copper-cobalt-based composite oxide catalyst for preparing mixed alcohol and particularly high alcohol by using synthesis gas as well as preparation method and application of copper-cobalt-based composite oxide catalyst |
| CN104722305A (en) * | 2013-12-23 | 2015-06-24 | 中国科学院上海高等研究院 | Catalyst applicable to synthesis of methanol by multi-component mixed gas as well as preparation method and application of methanol catalyst |
| US20150375209A1 (en) * | 2014-06-26 | 2015-12-31 | University Of Wyoming | Methods of catalytic hydrogenation for ethylene glycol formation |
| CN105536802A (en) * | 2015-12-17 | 2016-05-04 | 中国科学院上海高等研究院 | Micro-nano structure copper-based catalyst and preparation method and application thereof |
| CN108499566A (en) * | 2017-02-28 | 2018-09-07 | 中国科学院上海高等研究院 | A kind of preparation method and application of CuNi bases catalyst |
| CN110327933A (en) * | 2019-07-25 | 2019-10-15 | 常州北化澳联环保科技有限公司 | Hydrogenation of carbon dioxide prepares catalyst of methanol and its preparation method and application |
-
2020
- 2020-02-12 CN CN202010088734.5A patent/CN111167459A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102451695A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工集团公司 | Preparation method of copper-based methanol synthesis catalyst |
| CN103433046A (en) * | 2013-09-18 | 2013-12-11 | 上海中科高等研究院 | Copper-cobalt-based composite oxide catalyst for preparing mixed alcohol and particularly high alcohol by using synthesis gas as well as preparation method and application of copper-cobalt-based composite oxide catalyst |
| CN104722305A (en) * | 2013-12-23 | 2015-06-24 | 中国科学院上海高等研究院 | Catalyst applicable to synthesis of methanol by multi-component mixed gas as well as preparation method and application of methanol catalyst |
| US20150375209A1 (en) * | 2014-06-26 | 2015-12-31 | University Of Wyoming | Methods of catalytic hydrogenation for ethylene glycol formation |
| CN105536802A (en) * | 2015-12-17 | 2016-05-04 | 中国科学院上海高等研究院 | Micro-nano structure copper-based catalyst and preparation method and application thereof |
| CN108499566A (en) * | 2017-02-28 | 2018-09-07 | 中国科学院上海高等研究院 | A kind of preparation method and application of CuNi bases catalyst |
| CN110327933A (en) * | 2019-07-25 | 2019-10-15 | 常州北化澳联环保科技有限公司 | Hydrogenation of carbon dioxide prepares catalyst of methanol and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 王丹君 等: "Cu/ZnO/Al2O3催化剂的共沉淀-蒸氨法制备及其对二氧化碳加氢制甲醇的研究", 《分子催化》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112264026A (en) * | 2020-11-18 | 2021-01-26 | 西南化工研究设计院有限公司 | Preparation method of high-activity high-selectivity methanol synthesis catalyst |
| CN112517012A (en) * | 2020-12-01 | 2021-03-19 | 大连理工大学 | CO (carbon monoxide)2Preparation method and application of catalyst for preparing methanol by hydrogenation |
| CN112517012B (en) * | 2020-12-01 | 2022-01-04 | 大连理工大学 | A kind of preparation method and application of CO2 hydrogenation to methanol catalyst |
| CN115364863A (en) * | 2021-05-18 | 2022-11-22 | 中国科学院大连化学物理研究所 | A bifunctional catalyst, preparation method and application in methanol synthesis and reforming hydrogen production |
| CN115364863B (en) * | 2021-05-18 | 2024-03-26 | 中国科学院大连化学物理研究所 | A bifunctional catalyst, preparation method and application in methanol synthesis and reforming hydrogen production |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105126845B (en) | Catalyst and preparation method for preparing ethanol by oxalate hydrogenation | |
| CN111167459A (en) | A kind of catalyst for making methanol from mixed gas and its preparation method and use | |
| CN111617771A (en) | Preparation method of composite metal material catalyst and its application in the preparation of 5-HMF | |
| CN109985626B (en) | Method for preparing ethyl furfuryl ether by furfural liquid phase hydrogenation, catalyst and preparation method of catalyst | |
| CN110694656A (en) | Hydrotalcite-based nickel phosphide catalyst and application thereof in preparation of cyclane through guaiacol conversion | |
| CN114160143B (en) | CO (carbon monoxide) 2 Catalyst for preparing methanol by hydrogenation and preparation method and application thereof | |
| CN110801840A (en) | Cu-Ni bimetallic catalyst with biochar as carrier and application thereof | |
| CN106278816A (en) | A kind of method that cellulose two-step method prepares ethanol and normal propyl alcohol | |
| CN114011415A (en) | A kind of preparation method of high-load layered cobalt catalyst for preparing green diesel oil by hydrodeoxygenation of oil | |
| CN104877762A (en) | Method for catalyzing esterification reaction by means of high-stable-acidity mesoporous-microporous molecular sieve | |
| CN114085136B (en) | A kind of method that catalytic furfural prepares cyclopentanone | |
| CN114029081B (en) | A kind of bimetallic copper cobalt azacarbon material catalyst and its preparation method and application | |
| CN108212197B (en) | Catalyst for preparing polymethoxy dimethyl ether from dimethyl ether and preparation and application thereof | |
| CN110721671A (en) | Amorphous SiO2-Al2O3 supported metal catalyst and preparation method and application thereof | |
| CN110882716B (en) | Preparation method of solid acid catalyst for one-pot multi-step catalytic conversion of biomass-derived furfural into γ-valerolactone | |
| CN113649017A (en) | Preparation method and application of vegetable oil hydrodeoxygenation water-resistant core-shell type catalyst | |
| CN103372444B (en) | A kind of preparation method of copper-based catalysts | |
| CN114602477B (en) | For CO 2 Double-shell hollow copper-zinc-based catalyst for preparing methanol at low temperature and preparation method thereof | |
| CN110093179A (en) | A kind of method that the upgrading of lignin mink cell focus prepares biological oxygenated fuel | |
| CN112062673B (en) | Method for directionally synthesizing methyl lactate by catalytically converting fructose by one-pot method | |
| CN114345358A (en) | Bifunctional catalyst for catalyzing condensation-hydrodeoxygenation of cyclopentanone to prepare high-density aviation fuel | |
| CN115254175A (en) | Method for preparing alkane by catalyzing guaiacol hydrogenation and deoxidation through nickel-based bifunctional catalyst | |
| CN107282049A (en) | Al2O3The preparation method and applications of the Cu ZnO interfacial catalysis agent of load | |
| CN117563600B (en) | NiCoAl/C catalyst and application thereof in furfural conversion | |
| CN116571263B (en) | Preparation method of silicon dioxide-supported nickel-based catalyst and application in 5-hydroxymethylfurfural 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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200519 |