CN110947382B - Catalyst for preparing methanol and co-producing ethylene glycol by ethylene carbonate hydrogenation and preparation method thereof - Google Patents
Catalyst for preparing methanol and co-producing ethylene glycol by ethylene carbonate hydrogenation and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 119
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 114
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000010949 copper Substances 0.000 claims abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 230000032683 aging Effects 0.000 claims description 20
- 239000012266 salt solution Substances 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000012018 catalyst precursor Substances 0.000 claims description 16
- 239000012691 Cu precursor Substances 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000002071 nanotube Substances 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 15
- FRIKWZARTBPWBN-UHFFFAOYSA-N [Si].O=[Si]=O Chemical compound [Si].O=[Si]=O FRIKWZARTBPWBN-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 5
- 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 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 239000002699 waste material Substances 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 238000011156 evaluation Methods 0.000 description 21
- 230000009467 reduction Effects 0.000 description 13
- 229910004298 SiO 2 Inorganic materials 0.000 description 11
- 230000008859 change Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- -1 hydrogen ester Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 210000000080 chela (arthropods) Anatomy 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000002735 gasoline substitute Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- B01J35/615—
-
- 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
- B01J23/72—Copper
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- B01J35/40—
-
- 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
- C07C29/132—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 an oxygen containing functional group
- C07C29/136—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a catalyst for preparing methanol and co-producing ethylene glycol by hydrogenating ethylene carbonate and a preparation method thereof, wherein the catalyst comprises copper, a carrier and an auxiliary agent, wherein the copper accounts for 5-59.9 wt% of the weight of the catalyst, the carrier accounts for 40-94.9 wt% of the weight of the catalyst, and the auxiliary agent accounts for 0.1-5 wt% of the mass of the catalyst. The invention adopts the catalyst with the characteristic of a special nano-tubular structure, and can highly disperse the active component copper or the oxide thereof, thereby improving the conversion rate of the ethylene carbonate and the selectivity of methanol, and simultaneously showing excellent stability in the hydrogenation process.
Description
Technical Field
The invention belongs to the technical field of catalysts, and relates to a gas-phase ester hydrogenation catalyst, in particular to a catalyst for preparing methanol and co-producing ethylene glycol by hydrogenating ethylene carbonate and a preparation method thereof.
Background
Methanol is used as an important basic chemical raw material or solvent, has important application in the industries of medicine, dye, plastic, synthetic fiber and the like, and is also used as an energy source with excellent performance and a gasoline substitute fuel due to the advantages of safety, sufficient combustion, high utilization rate and the like. CO 2 2 The hydrogenation for producing the methanol is not only an option for the production and the utilization of the methanol as an industrial product, but also brings a new solution to the global energy and environment problemsThe solution is decided. But due to CO 2 The method has the advantages of thermodynamic stability and kinetic inertia, harsh reaction conditions for preparing methanol by direct hydrogenation, low equilibrium conversion rate and poor selectivity of target products. By introducing CO 2 The process for synthesizing Ethylene Carbonate (EC) by reacting with ethylene oxide and further hydrogenating to prepare methanol has the advantages of mild reaction conditions, high conversion rate and 100% atomic utilization rate, and has good technical and economic advantages and market application potential as the ethylene glycol is co-produced while the methanol is produced.
Although organic noble metal catalysts such as a Pincer type ruthenium complex and the like show good activity and selectivity in a hydrogenation reaction of ethylene carbonate, the preparation process is complex, the price is high and the catalysts are difficult to recover. Copper-based catalysts are widely used in ester hydrogenation systems due to their good C-O/C = O bond selective hydrogenation capability. However, in the hydrogenation of ethylene carbonate, there is still a hydrogen-to-ester ratio (i.e., the molar ratio of hydrogen to ethylene carbonate, H) required for the reaction feed 2 the/EC) is higher, the selectivity of the product methanol is lower, the stability of the catalyst is poorer, and the like. At present, in a fixed bed reactor, a large excess of hydrogen (H) is required in the feed to the ethylene carbonate hydrogenation reaction 2 the/EC is generally above 200) to maintain a higher conversion of ethylene carbonate. However, in industrial applications, such a high hydrogen-to-ester ratio leads to an increase in hydrogen gas circulation, increases the requirements on equipment parameters such as compressors, and greatly increases the equipment cost and power cost required for the process. Therefore, the high-activity copper-based catalyst is designed, so that the ethylene carbonate hydrogenation reaction has higher ethylene carbonate conversion rate and methanol selectivity under lower hydrogen-ester ratio, has good stability and realizes CO 2 The key point of the efficient utilization of the methanol is to produce the methanol.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a high-activity high-selectivity ethylene carbonate hydrogenation catalyst and a preparation method thereof, aiming at the problems of high hydrogen ester ratio and low methanol selectivity in the technology of preparing methanol and ethylene glycol by hydrogenating ethylene carbonate.
The technical scheme adopted by the invention is as follows:
the catalyst for preparing methanol and ethylene glycol by hydrogenating ethylene carbonate mainly comprises copper, oxides thereof and silicon dioxide, wherein the copper accounts for 5-59.9 wt% of the weight of the catalyst; silica in 40-94.9wt.% of the catalyst weight; the auxiliary agent accounts for 0.1-5 wt% of the weight of the catalyst.
The catalyst structure is a nano tubular structure, and the specific surface area is 450-500m 2 (ii)/g; the diameter of the nanotube is 3-5nm, and the length of the nanotube is 40-300nm.
More preferred embodiments are: the copper content of the catalyst is 30-48wt.%, the silicon oxide content of the catalyst is 50-68wt.%, the assistant content of the catalyst is 0.1-2wt.%, and the specific surface area of the catalyst is 460-470m 2 /g。
The invention also aims to provide a preparation method of the catalyst for preparing methanol and ethylene glycol by hydrogenating ethylene carbonate, which comprises the following steps:
step 1, mixing copper precursor salt (copper acetate or copper nitrate) with deionized water (the water temperature is 30-50 ℃), adding 5-59.9 wt% of copper in terms of metal oxide, and uniformly stirring to obtain a clarified solution, wherein the clarified solution is the copper precursor salt solution.
And 2, adding an alkaline agent (ammonia water, ammonium carbonate or sodium hydroxide) into the copper precursor salt solution, and stirring for 0.5-5h under an alkaline condition. Keeping the temperature of the solution at 30-80 ℃ during stirring, and keeping the pH value of the solution at 8.5-13.5 during stirring. To avoid a large change in pH, the reaction system may be placed in a sealed environment.
And 3, dropwise adding a silicon dioxide silicon source (sodium silicate, silicon dioxide sol or tetraethoxysilane) into the product obtained in the step 2 (1 drop per second), continuously dissolving the silicon dioxide silicon source in an alkaline environment, reacting the copper precursor salt solution with the silicon dioxide silicon source, gradually depositing and curling to form a nanotube structure, and keeping the pH value of the solution at 11-12 in the dropwise adding process. To avoid a large change in pH, the reaction system may be placed in a sealed environment.
After the dropwise addition is finished, the solution is stirred and aged in a water bath (the system is kept sealed or a reflux mode is adopted during aging), the temperature of the solution is kept between 30 and 90 ℃ during aging, the aging time is 4 to 30 hours, and the pH value of the solution is 8.5 to 13.5. To avoid a large change in pH, the reaction system may be placed in a sealed environment.
When the alkaline agent is ammonia water: and after aging, adjusting the temperature to 80 ℃ or above, and distilling ammonia until the pH value is 7-8 to finish the removal of the alkaline agent.
When the alkaline agent is ammonium carbonate or sodium hydroxide: and after aging, adding dilute nitric acid into the solution for neutralization until the pH value is 7-8 to complete the removal of the alkaline agent.
And 4, filtering the product obtained in the step 3, washing the obtained precipitate with deionized water (filtering washing or centrifugal washing) to remove copper ions, and washing until the pH value of the washing waste liquid is 6.4-7.
Drying the washed precipitate at 50-120 deg.c for 4-12 hr to obtain the catalyst precursor with nanotube structure.
And 5, mixing the auxiliary agent precursor salt (nitrate or acetate) with deionized water to obtain a salt solution with the concentration of 0.002-1.5mol/L. Dripping the assistant precursor salt solution into the catalyst precursor powder, uniformly stirring, and drying at 25-100 ℃ for 10-60h.
And 6, roasting the product obtained in the step 5 at the temperature of 300-700 ℃ for 3-12h to obtain a catalyst finished product.
The catalyst needs to be subjected to online reduction before use, and specifically comprises the following steps: the reduction temperature is 150-400 ℃, the reduction atmosphere is hydrogen, and the hydrogen flow required by the reduction of each gram of catalyst is 40-400mL/min.
More preferred embodiments are: the copper precursor salt is copper nitrate, the auxiliary agent precursor salt is nitrate, the silicon dioxide silicon source is silica sol, the alkaline agent is ammonia water, and the drying method is a common drying method.
The invention also aims to provide a using method of the catalyst, in the reaction of synthesizing methanol and ethylene glycol by hydrogenating ethylene carbonate, the reaction pressure is 2-5MPa, the reaction temperature is 150-240 ℃, the hydrogen-ester ratio is 20-200, and the liquid hourly space velocity is 0.1-4h -1 Wherein the liquid hourly space velocity refers to the space velocity of ethylene carbonate.
Among the above methods of use, the more preferred embodiment is: the promoter precursor salt contained platinum, which accounted for 0.2wt.% of the catalyst weight. The hydrogen-to-ethylene carbonate ratio of hydrogen to vaporized ethylene carbonate is 160 to 190, preferably 180.
The invention has the advantages and positive effects that:
1. the catalyst adopts metal copper as an active component, and the prepared catalyst has the characteristics of high catalytic activity, readily available preparation raw materials, low cost, easy industrial production and the like by utilizing a special nano tubular structure.
2. The catalyst adopts trace noble metal as an auxiliary agent, the prepared catalyst is used for the gas-solid phase reaction of ethylene carbonate, is easy to recover, greatly reduces the using amount of the noble metal compared with the catalyst made of organic noble metal, effectively improves the reaction activity and the methanol selectivity of the catalyst on the premise of economy and environmental protection, simultaneously reduces the proportion of hydrogen and ethylene carbonate, can greatly reduce the circulation amount of the hydrogen in industry, saves the power consumption of a gas compressor and improves the processing capacity of a reactor with unit volume.
3. The invention adopts the catalyst with the characteristic of a special nano-tubular structure, and can highly disperse the active component copper or the oxide thereof, thereby improving the conversion rate of the ethylene carbonate and the selectivity of methanol, and simultaneously showing excellent stability in the hydrogenation process.
Drawings
Fig. 1 is a transmission electron microscope image of a nanotube-shaped catalyst used in the present invention, wherein a is a transmission electron microscope image before reduction of the catalyst, and B is a transmission electron microscope image after reduction of the catalyst.
FIG. 2 is an X-ray powder diffraction pattern of a reduced nanotubular catalyst useful in the present invention.
FIG. 3 shows the evaluation results of catalyst stability in the preparation of methanol and ethylene glycol by hydrogenation of ethylene carbonate.
Detailed Description
The present invention is further illustrated by the following examples, but is not limited to these examples. The experimental methods not specified in the examples are generally commercially available according to the conventional conditions and the conditions described in the manual, or according to the general-purpose equipment, materials, reagents and the like used under the conditions recommended by the manufacturer, unless otherwise specified.
The invention relates to a catalyst for preparing methanol and ethylene glycol by hydrogenating ethylene carbonate, which is characterized in that: the main chemical components of the catalyst are copper and oxides thereof and silicon dioxide, wherein the copper accounts for 5-59.9 wt% of the weight of the catalyst; silica in 40-94.9wt.% of the catalyst weight; the promoter is present in an amount of 0.1 to 5wt.% based on the weight of the catalyst.
The catalyst structure is a nano tubular structure, and the specific surface area is 450-500m 2 (iv) g; the diameter of the nanotube is 3-5nm, and the length of the nanotube is 40-300nm.
The preferred scheme is as follows: the copper content of the catalyst is 30-48wt.%, the silicon oxide content of the catalyst is 50-68wt.%, the assistant content of the catalyst is 0.1-2wt.%, and the specific surface area of the catalyst is 460-470m 2 /g。
The preparation method of the catalyst for preparing methanol and co-producing ethylene glycol by hydrogenating ethylene carbonate comprises the following steps:
step 1, mixing copper precursor salt (copper acetate or copper nitrate) with deionized water (the water temperature is 30-50 ℃), adding 5-59.9 wt% of copper in terms of metal oxide, and uniformly stirring to obtain a clarified solution, wherein the clarified solution is the copper precursor salt solution.
And 2, adding an alkaline agent (ammonia water, ammonium carbonate or sodium hydroxide) into the copper precursor salt solution, and stirring for 0.5-5h under an alkaline condition. Keeping the temperature of the solution at 30-80 ℃ during stirring, and keeping the pH value of the solution at 8.5-13.5 during stirring. To avoid a large change in pH, the reaction system may be placed in a sealed environment.
And 3, dropwise adding a silicon dioxide silicon source (sodium silicate, silicon dioxide sol or tetraethoxysilane) into the product obtained in the step 2 (1 drop per second), continuously dissolving the silicon dioxide silicon source in an alkaline environment, reacting the copper precursor salt solution with the silicon dioxide silicon source, gradually depositing and curling to form a nanotube structure, and keeping the pH value of the solution at 11-12 in the dropwise adding process. To avoid a large change in pH, the reaction system may be placed in a sealed environment.
After the dropwise addition is finished, stirring and aging the solution in a water bath (keeping the system sealed or adopting a reflux mode during aging), wherein the temperature of the solution is kept at 30-90 ℃ during aging, the aging time is 4-30h, and the pH value of the solution is 8.5-13.5. To avoid a large change in pH, the reaction system may be placed in a sealed environment.
When the alkaline agent is ammonia water: after aging, adjusting the temperature to 80 ℃ or above, and evaporating ammonia until the pH value is 7-8 to finish the removal of the alkaline agent.
When the alkaline agent is ammonium carbonate or sodium hydroxide: after aging, dilute nitric acid is added into the solution for neutralization until the pH value is 7-8, and the removal of the alkaline agent is completed.
And 4, filtering the product obtained in the step 3, washing the obtained precipitate with deionized water (filtering washing or centrifugal washing) to remove copper ions, and washing until the pH value of the washing waste liquid is 6.4-7.
Drying the washed precipitate at 50-120 deg.c for 4-12 hr to obtain the catalyst precursor with nanotube structure.
And 5, mixing the auxiliary agent precursor salt (nitrate or acetate) with deionized water to obtain a salt solution with the concentration of 0.002-1.5mol/L. Dripping the assistant precursor salt solution into the catalyst precursor powder, uniformly stirring, and drying at 25-100 ℃ for 10-60h.
And 6, roasting the product obtained in the step 5 at the temperature of 300-700 ℃ for 3-12h to obtain a finished catalyst.
More preferred embodiments are: the copper precursor salt is copper nitrate, the auxiliary agent precursor salt is nitrate, the silicon dioxide silicon source is silica sol, the alkaline agent is ammonia water, and the drying method is a common drying method.
The use method of the catalyst comprises the following steps: in the reaction of synthesizing methanol and ethylene glycol by hydrogenating ethylene carbonate, the reaction pressure is 2-5MPa, the reaction temperature is 150-240 ℃, the hydrogen-ester ratio is 20-200, and the liquid hourly space velocity is 0.1-4h -1 Wherein the liquid hourly space velocity refers to the space velocity of ethylene carbonate. The more preferable scheme is as follows: the promoter precursor salt contains platinum which is in the presence of the catalyst0.2wt.% of the agent weight. The hydrogen-to-ethylene carbonate ratio of hydrogen to vaporized ethylene carbonate was 180.
Example 1
Preparation of the catalyst:
40g of copper nitrate trihydrate was weighed and dissolved in 100mL of deionized water (water temperature 30 ℃) and stirred uniformly to obtain a clear solution.
Adding 139mL ammonia water, stirring at 30 deg.C for half an hour, and keeping the pH value of the solution at 8.5-13.5 during stirring. In order to avoid large changes of the pH value, the reaction system is placed in a sealed environment.
44.5mL of 30wt.% silica sol was metered in (1 drop per second) dropwise, the pH being maintained at 11-12 during the addition. After the dropwise addition, stirring and aging are carried out in a water bath at 50 ℃ for 4 hours (the system is kept sealed during aging), and the pH value of the solution is 8.5-13.5. Heating to 80 deg.C, and distilling ammonia until pH is 7-8.
After filtering, the obtained precipitate is subjected to common washing, and the washing is finished when the pH value of the washing waste liquid is about 6.4-7. And drying the washed precipitate at 110 ℃ for 4h to obtain the catalyst precursor with the nanotube structure.
And roasting the catalyst precursor at 450 ℃ for 4h to obtain the catalyst.
Catalyst on-line reduction and catalytic effect evaluation:
the gas-phase ethylene carbonate hydrogenation reaction is carried out in a fixed bed reactor.
Sieving the calcined catalyst tablet to 40-60 mesh, filling 0.5g catalyst, and keeping the catalyst in H of 3MPa 2 Reducing at 300 ℃ in atmosphere, wherein the gas flow rate is 100mL/min, raising the temperature from room temperature to 300 ℃ at the speed of 2 ℃/min, keeping the temperature for 4h, reducing the temperature to 180 ℃, gasifying ethylene carbonate, mixing the ethylene carbonate with hydrogen, and introducing the ethylene carbonate into a reaction tube, wherein the hydrogen-ester ratio is 200, and the mass space velocity of the ethylene carbonate is 0.5h -1 The reaction was carried out at 3 MPa. Analysis of the product by gas chromatography gave ethylene carbonate, ethylene Glycol (EG), methanol (MeOH) and ethanol (EtOH). The results of the catalyst performance evaluation are shown in Table 1.
Comparative example 1
Cu/SiO 2 Preparation of a catalyst precursor:
40g of copper nitrate trihydrate is weighed and dissolved in 100mL of deionized water (water temperature 50 ℃), and the solution is stirred uniformly to obtain a clear solution.
139mL of ammonia water is added, the mixture is stirred for 2 hours at 50 ℃, and the pH value of the solution is kept between 8.5 and 13.5 in the stirring process. In order to avoid large changes of the pH value, the reaction system is placed in a sealed environment.
44.5mL of 30wt.% silica sol was metered in (1 drop per second) dropwise, the pH being maintained at 11-12 during the addition. After the dropwise addition, stirring and aging in a water bath at 70 ℃ for 20 hours (in the aging process, a reflux mode is adopted), wherein the pH value of the solution is 8.5-13.5. Heating to 80 deg.C, and distilling ammonia until pH is 7-8.
After filtering, the obtained precipitate is subjected to common washing, and the washing is finished when the pH value of the washing waste liquid is about 6.4-7. And drying the washed precipitate for 12h at 80 ℃ to obtain the catalyst precursor with the nanotube structure.
Preparation of the catalyst:
0.0385g of Ru (NH) was weighed out 3 ) 6 (NO 3 ) 3 Dissolved in 4.5g of deionized water and added dropwise to 2g of Cu/SiO 2 And (2) uniformly stirring the precursor powder, drying at room temperature (the modification that the drying at 30-100 ℃ for 10-60h in the step 5 is modified to be drying at 25-100 ℃ for 10-60 h) for 48h, and roasting at 300 ℃ for 10h to obtain the catalyst.
Evaluation of catalyst:
the catalyst on-line reduction and catalyst evaluation methods were the same as in example 1, and the results of catalyst performance evaluation are shown in Table 1.
Comparative example 2
Cu/SiO 2 Preparation of a catalyst precursor:
Cu/SiO 2 the catalyst precursor was prepared as in comparative example 1.
Preparation of the catalyst:
0.0380g of Rh (NH) was weighed out 3 ) 6 (NO 3 ) 3 Dissolved in 4.5g of deionized water and added dropwise to 2g of Cu/SiO 2 And uniformly stirring the precursor powder, drying for 14h at 100 ℃, and roasting for 3h at 700 ℃ to obtain the catalyst.
Evaluation of catalyst:
the catalyst on-line reduction and catalyst evaluation methods were the same as in example 1, and the catalyst performance evaluation results are shown in Table 1.
Comparative example 3
Cu/SiO 2 Preparation of a catalyst precursor:
Cu/SiO 2 the catalyst precursor was prepared as in comparative example 1.
Preparation of the catalyst:
weighing 0.0281g Pd (NH) 3 ) 4 (NO 3 ) 2 Dissolved in 4.5g of deionized water and added dropwise to 2g of Cu/SiO 2 And uniformly stirring the precursor powder, drying for 50h at 60 ℃, and roasting for 4h at 450 ℃ to obtain the catalyst.
Evaluation of catalyst:
the catalyst on-line reduction and catalyst evaluation methods were the same as in example 1, and the catalyst performance evaluation results are shown in Table 1.
Example 2
Cu/SiO 2 Preparation of a catalyst precursor:
Cu/SiO 2 the catalyst precursor was prepared as in comparative example 1.
Preparation of the catalyst:
0.0198g of Pt (NH) was weighed 3 ) 4 (NO 3 ) 2 Dissolved in 4.5g of deionized water and added dropwise to 2g of Cu/SiO 2 And (3) uniformly stirring the precursor powder, drying at room temperature for 48h, and roasting at 450 ℃ for 4h to obtain the catalyst.
Evaluation of catalyst:
the catalyst on-line reduction and catalyst evaluation methods were the same as in example 1, and the catalyst performance evaluation results are shown in Table 1. It can be seen that the catalyst with the addition of suitable minor amounts of noble metal promoter shows higher conversion of ethylene carbonate and selectivity to methanol. Among them, the catalyst added with the platinum promoter shows the best catalytic performance.
TABLE 1 ethylene carbonate hydrogenation performance of different promoter catalysts
Examples 3 to 5
The catalyst was prepared in the same manner as in example 2 by changing Pt (NH) 3 ) 4 (NO 3 ) 2 The addition amounts of (a) and (b) respectively give catalysts of different Pt loadings: (0.1 wt.%,0.2wt.%,1.0 wt.%), the catalyst on-line reduction and catalyst performance evaluation methods were the same as in example 1, and the ethylene carbonate mass space velocity was changed to 1.0h -1 . The results of the catalyst performance evaluation are shown in Table 2. It can be seen that the addition of a suitable content of auxiliary agent can increase the conversion of ethylene carbonate and the selectivity of methanol. The catalyst performance was best when the platinum promoter addition was 0.2wt.%.
TABLE 2 ethylene carbonate hydrogenation performance of different Pt loading catalysts
Examples 6 to 9
The catalyst preparation method, the catalyst on-line reduction and evaluation conditions were the same as in example 4, the hydrogen-ester ratios for the catalyst performance evaluation were changed to 190, 180, 170 and 160, respectively, and the other were unchanged, and the catalyst performance evaluation results are shown in table 3.
As can be seen from Table 3, the platinum modified Cu/SiO of the present invention 2 The catalyst can still show higher conversion rate of the ethylene carbonate and product selectivity under the condition of lower hydrogen-ester ratio. When the hydrogen-ester ratio is 180, the selectivity of methanol can reach 79.5 percent, and the selectivity of glycol can reach 99.5 percent. The stability evaluation of example 7 is shown in figure 3, and it can be seen that the catalyst of the present invention exhibits excellent stability.
TABLE 3 hydrogenation reaction performance of ethylene carbonate at different hydrogen-ester ratios
Claims (6)
1. A catalyst for preparing methanol and ethylene glycol by hydrogenating ethylene carbonate is characterized in that: the catalyst comprises copper, a carrier and an auxiliary agent, wherein the copper accounts for 30-48 wt% of the weight of the catalyst, the carrier accounts for 50-68 wt% of the weight of the catalyst, and the auxiliary agent accounts for 0.1-2 wt% of the mass of the catalyst;
the specific surface area of the catalyst is 450-500m 2 (ii)/g; the catalyst has a nanotube structure, the diameter of the nanotube is 3-5nm, and the length of the nanotube is 40-300 nm;
the carrier is silicon dioxide, and the auxiliary agent is platinum;
the preparation method of the catalyst comprises the following steps:
step 1, mixing copper precursor salt with deionized water, wherein the content of added copper in terms of metal oxide is 5-59.9 wt%, and uniformly stirring to obtain a clear solution, namely the copper precursor salt solution;
step 2, adding an alkaline agent into the copper precursor salt solution, stirring for 0.5-5h under an alkaline condition, keeping the temperature of the solution at 30-80 ℃ in the stirring process, and keeping the pH value of the solution at 8.5-13.5 in the stirring process;
step 3, dropwise adding a silicon dioxide silicon source into the product obtained in the step 2, wherein the silicon dioxide silicon source is continuously dissolved in an alkaline environment, a copper precursor salt solution reacts with the silicon dioxide silicon source and gradually deposits and curls to form a nanotube structure, and the pH value of the solution is kept to be 11-12 in the dropwise adding process;
after the dropwise addition is finished, stirring and aging the solution in a water bath, wherein the temperature of the solution is kept at 30-90 ℃ in the aging process, the aging time is 4-30h, and the pH value of the solution is 8.5-13.5;
when the alkaline agent is ammonia water: after aging, adjusting the temperature to 80 ℃ or above, and distilling ammonia until the pH value is 7-8 to finish the removal of the alkaline agent;
when the alkaline agent is ammonium carbonate or sodium hydroxide: after aging, adding dilute nitric acid into the solution for neutralization until the pH value is 7-8, and finishing the removal of the alkaline agent;
step 4, filtering the product obtained in the step 3, washing the obtained precipitate with deionized water to remove copper ions, and finishing washing until the pH value of the washing waste liquid is 6.4-7;
drying the washed precipitate at 50-120 ℃ for 4-12h to obtain a catalyst precursor with a nanotube structure;
step 5, mixing the auxiliary agent precursor salt with deionized water to obtain a salt solution with the concentration of 0.002-1.5 mol/L; dripping the assistant precursor salt solution into the catalyst precursor powder, uniformly stirring, and drying at 25-100 ℃ for 10-60 h;
and 6, roasting the product obtained in the step 5 at the temperature of 300-700 ℃ for 3-12h to obtain a finished catalyst.
2. The catalyst for preparing methanol and co-producing ethylene glycol by hydrogenating ethylene carbonate according to claim 1 is characterized in that: the copper precursor salt solution is a copper acetate salt solution or a copper nitrate salt solution; the silicon dioxide silicon source is sodium silicate, silica sol or ethyl orthosilicate.
3. The catalyst for preparing methanol and ethylene glycol by hydrogenating the ethylene carbonate according to claim 1 or 2 is characterized in that: the assistant precursor salt solution is a nitrate solution or an acetate solution.
4. The use method of the catalyst for preparing methanol and ethylene glycol by hydrogenating the ethylene carbonate according to claim 1 is characterized by comprising the following steps: in the reaction of synthesizing methanol and ethylene glycol by hydrogenating ethylene carbonate, the reaction pressure is 2-5MPa, the reaction temperature is 150-240 ℃, the hydrogen-ester ratio is 20-200, and the liquid hourly space velocity is 0.1-4h -1 Wherein the liquid hourly space velocity refers to the space velocity of ethylene carbonate; the platinum comprises 0.2wt.% of the catalyst weight.
5. The use method of the catalyst for preparing methanol and ethylene glycol by hydrogenating the ethylene carbonate according to claim 4 is characterized in that: the hydrogen-ester ratio of the hydrogen to the gasified ethylene carbonate is 160-190.
6. The use method of the catalyst for preparing methanol and co-producing ethylene glycol by hydrogenating ethylene carbonate according to claim 5 is characterized in that: the hydrogen to vaporized ethylene carbonate hydrogen-to-ester ratio is 180.
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