CN108187676A - A kind of ester through hydrogenation synthesis of dibasic alcohol copper-based catalysts and its preparation method and application - Google Patents
A kind of ester through hydrogenation synthesis of dibasic alcohol copper-based catalysts and its preparation method and application Download PDFInfo
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- CN108187676A CN108187676A CN201711465582.0A CN201711465582A CN108187676A CN 108187676 A CN108187676 A CN 108187676A CN 201711465582 A CN201711465582 A CN 201711465582A CN 108187676 A CN108187676 A CN 108187676A
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- copper
- based catalysts
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- ester
- present
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- 239000010949 copper Substances 0.000 title claims abstract description 173
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 149
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 239000003054 catalyst Substances 0.000 title claims abstract description 125
- 150000002148 esters Chemical class 0.000 title claims abstract description 43
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 20
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 35
- 229910052710 silicon Inorganic materials 0.000 claims description 35
- 239000010703 silicon Substances 0.000 claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 230000009467 reduction Effects 0.000 claims description 17
- 239000012018 catalyst precursor Substances 0.000 claims description 15
- AHADSRNLHOHMQK-UHFFFAOYSA-N methylidenecopper Chemical compound [Cu].[C] AHADSRNLHOHMQK-UHFFFAOYSA-N 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 239000000908 ammonium hydroxide Substances 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000005751 Copper oxide Substances 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 229910000431 copper oxide Inorganic materials 0.000 claims description 4
- 239000008246 gaseous mixture Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 241001502050 Acis Species 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 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 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 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
- 239000002585 base Substances 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 99
- 230000003197 catalytic effect Effects 0.000 abstract description 31
- 230000000694 effects Effects 0.000 abstract description 16
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 abstract description 15
- 238000006555 catalytic reaction Methods 0.000 abstract description 10
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 55
- 229910003472 fullerene Inorganic materials 0.000 description 55
- 235000019441 ethanol Nutrition 0.000 description 29
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 18
- 238000001514 detection method Methods 0.000 description 15
- 239000000377 silicon dioxide Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 229910052681 coesite Inorganic materials 0.000 description 9
- 229910052906 cristobalite Inorganic materials 0.000 description 9
- 229910052682 stishovite Inorganic materials 0.000 description 9
- 229910052905 tridymite Inorganic materials 0.000 description 9
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 8
- 229910001431 copper ion Inorganic materials 0.000 description 8
- -1 polyethylene terephthalate Polymers 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 7
- 238000004445 quantitative analysis Methods 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229940057867 methyl lactate Drugs 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 241001269238 Data Species 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 241000530268 Lycaena heteronea Species 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- LOMVENUNSWAXEN-NUQCWPJISA-N dimethyl oxalate Chemical group CO[14C](=O)[14C](=O)OC LOMVENUNSWAXEN-NUQCWPJISA-N 0.000 description 1
- YAGHEUQOAPDHKS-UHFFFAOYSA-N dimethyl oxalate;methanol Chemical compound OC.COC(=O)C(=O)OC YAGHEUQOAPDHKS-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000003643 water by type Substances 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of ester through hydrogenation synthesis of dibasic alcohol copper-based catalysts and its preparation method and application, copper-based catalysts are in terms of mass percentage, including 0.1~50% C60, 0.5~60% Cu and the carrier S iO of surplus2；The C60The carrier S iO is carried on Cu2Surface.C of the present invention60Carrier S iO is carried on Cu2Surface, C60With Cu firm contacts, pass through C60Realize the balance to active copper surface charge, the activity for improving carrier surface copper causes copper-based catalysts, and higher catalytic activity can be still played under lower pressure.Embodiment the result shows that, copper-based catalysts provided by the invention, in catalysis ester through hydrogenation prepares the reaction of ethylene glycol, under low pressure and condition of high voltage, it is respectively provided with higher catalytic activity, so that the high conversion rate of dimethyl oxalate, up to 100%, the selectivity of ethylene glycol is above 80%, and the quality space-time yield of ethylene glycol is above 200mg/g.
Description
Technical field
The invention belongs to copper-based catalysts technical field more particularly to a kind of ester through hydrogenation synthesis of dibasic alcohol copper-based catalysts
And its preparation method and application.
Background technology
The dihydric alcohols such as ethylene glycol and propylene glycol are important Organic Chemicals, are that modern industry and social development largely need
A kind of chemicals asked.Such as ethylene glycol can react generation polyethylene terephthalate (PET) with terephthalic acid (TPA), PET is
The important source material in polyester industrial field.Ethylene glycol is commonly used to make anti-icing fluid, for automotive antifreezing agent and the conveying of industrial cold energy.
In addition, propylene glycol has similar structure with ethylene glycol, the poly terephthalic acid-propylene glycol ester (PTT) produced by propylene glycol
Alternative PET, can be as buffering market to the important industrial chemicals of PET demands.
The industrial process of ethylene glycol mainly has the epoxyethane water of petrochemical industry route legal, and not only the technology is basic
By three institute of company ridge of Shell Co. Ltd of the U.S. (Shell), American Association Carbide (UCC) and American science Chevron Research Company (CRC) (SD)
It is disconnected；And legal epoxyethane water is a kind of mode for the direct hydration that pressurizes, and process units need to set multiple evaporators, disappear simultaneously
It consumes big energy to detach for product, there are long flow path, equipment is more, the concentration of high energy consumption and glycol product aqueous solution is low asks
Topic.Similarly, the key industry production method of propylene glycol equally faces the problem of similary.
In recent years, ester through hydrogenation prepares the production line of dihydric alcohol, and with it, low energy consumption and the short advantage of flow, by dihydric alcohol
The extensive concern of preparation field, for example, hydrogenation of dimethyl oxalate to synthesizing ethylene glycol can be passed through；Dimethyl malenate or lactate add
Hydrogen synthesizes glycerine.But the process of ester through hydrogenation generation dihydric alcohol, it needs to carry out under the action of high activated catalyst.It is common
Catalyst has copper Si catalyst and Cu-Cr catalyst, and traditional catalyst activity is low, and higher reaction pressure is needed just to can guarantee
Catalytic activity limits the industrial development of dihydric alcohol.
Invention content
In view of this, the purpose of the present invention is to provide a kind of ester through hydrogenation synthesis of dibasic alcohol copper-based catalysts and its preparations
Methods and applications, copper-based catalysts provided by the invention have compared with high reaction activity so that can be catalyzed ester in atmospheric conditions
Hydrogenation synthesis dihydric alcohol.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme：
The present invention provides a kind of ester through hydrogenation synthesis of dibasic alcohol copper-based catalysts, in terms of mass percentage, including 0.1
~50% C60, 0.5~60% Cu and the carrier S iO of surplus2；The C60The carrier S iO is carried on Cu2Surface.
Preferably, the copper-based catalysts include 5~20% C60, 20~40% Cu and the carrier S iO of surplus2。
The present invention also provides the preparation sides of the ester through hydrogenation synthesis of dibasic alcohol copper-based catalysts described in above-mentioned technical proposal
Method includes the following steps：
(1) by cupric ammine complex aqueous solution, C60And precipitant mix, deposition reaction is carried out, obtains copper-carbon mix；Institute
Cupric ammine complex aqueous solution is stated in terms of copper content, with C60Mass ratio be (0.5~60)：(0.1~50)；
(2) copper-carbon mix that the step (1) obtains with silicon source is mixed, carries out burin-in process, obtain aging object；
The silicon source is with the equal siliceous gauge of the amount of institute's silicon-containing material, with C60Mass ratio be (2~80)：(0.1~50)；
(3) the aging object for obtaining the step (2) is dried and is roasted successively, obtains catalyst precursor；
(4) catalyst precursor for obtaining the step (3) carries out reduction treatment, obtains ester through hydrogenation synthesis of dibasic alcohol use
Copper-based catalysts.
Preferably, the preparation method of cupric ammine complex aqueous solution includes in the step (1)：Copper source is mixed with ammonium hydroxide,
Obtain cupric ammine complex aqueous solution；
Copper source includes one or more in copper nitrate, copper sulphate, copper acetate, copper chloride and copper oxide.
Preferably, precipitating reagent is alkali compounds in the step (1).
Preferably, in the step (2) silicon source include esters of silicon acis, Ludox, silicon ball and white carbon in it is one or more.
Preferably, burin-in process carries out under agitation in the step (2)；The temperature of burin-in process is 25~150
℃；The time of burin-in process is 1~30h.
Preferably, the temperature dried in the step (3) is 70~140 DEG C, and the time of drying is 6~12h；
The temperature roasted in the step (3) is 200~300 DEG C, and the time of roasting is 1~10h.
Preferably, reduction with reducing agent is hydrogen or gaseous mixture containing hydrogen in the step (4)；The reduction treatment
Temperature for 250~550 DEG C, the time of reduction treatment is 2~12h.
The present invention provides preparation methods described in copper-based catalysts described in above-mentioned technical proposal or above-mentioned technical proposal to prepare
Application of the obtained copper-based catalysts in the reaction of ester through hydrogenation synthesis of dibasic alcohol.
The present invention provides a kind of ester through hydrogenation synthesis of dibasic alcohol copper-based catalysts, in terms of mass percentage, including 0.1
~50% C60, 0.5~60% Cu and the carrier S iO of surplus2；The C60The carrier S iO is carried on Cu2Surface.
In the present invention, fullerene (C60) have stronger electronic action ability, to metal surface electronics can Effective Regulation, realize it is copper-based
The control of catalyst surface distribution of charges so that surface-active copper component increases, and fullerene and Cu are carried on carrier in the present invention
SiO2Surface, fullerene and Cu firm contacts, and then the balance to active copper surface charge is realized by fullerene, further carry
The activity of high carrier surface copper so that copper-based catalysts can still play higher catalytic activity under lower pressure.Embodiment
The result shows that, the fullerene promoted type copper-based catalysts of different component provided by the invention, catalysis ester through hydrogenation prepare second two
In the reaction of alcohol, under the conditions of low pressure reaction or under the conditions of reaction under high pressure, it is respectively provided with higher catalytic activity so that
The high conversion rate of dimethyl oxalate is up to 100%, and the selectivity of ethylene glycol is above 80%, and the quality space-time yield of ethylene glycol is high
In 200mg/g.
Description of the drawings
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
The copper-based catalysts catalytic stability detection figure that Fig. 1 embodiment of the present invention 2 obtains.
Specific embodiment
The present invention provides a kind of ester through hydrogenation synthesis of dibasic alcohol copper-based catalysts, in terms of mass percentage, including 0.1
~50% C60, 0.5~60% Cu and the carrier S iO of surplus2；The C60The carrier S iO is carried on Cu2Surface.
In the present invention, the copper-based catalysts include carrier S iO2Be carried on the carrier S iO2The C on surface60With
Cu；The C60With Cu in carrier S iO2Surface is contacted with each other with physical form, has charge effect, and then regulate and control fullerene and Cu
Between carry out charge effect so that surface copper keeps charge stable in catalytic process, be not easy by reactant or product influence with
Activation reduces.
In the present invention, in terms of mass percentage, the copper-based catalysts include 0.1~50% C60, 0.5~60%
Cu and surplus carrier S iO2；Preferably include 5~20% C60, 20~40% Cu and the carrier S iO of surplus2.In this hair
In bright, on the basis of the gross mass of the copper-based catalysts, the C60Mass percentage for 0.1~50%, preferably 1~
45%, further preferably 5~35%, more preferably 10~25%；The mass percentage of the Cu is 0.5~60%, excellent
It is selected as 1~50%, further preferably 5~45%, more preferably 10~40%.
In the present invention, the fullerene (C60) there is stronger electronic action ability, can have to metal surface electronics
Effect regulates and controls, the control of realization copper-based catalysts surface charge distribution, and fullerene and Cu are carried on carrier S iO in the present invention2Surface,
Fullerene and Cu firm contacts, and then the balance to active copper surface charge is realized by fullerene, further improve carrier table
The activity of face copper so that copper-based catalysts can still play higher catalytic activity under the lower pressure of 0.1~1MPa.And
And copper-based catalysts provided by the invention, in carrier S iO2Surface, using fullerene as accelerating agent, copper is activating agent, for ester plus
During hydrogen synthesis of dibasic alcohol, catalytic stability is excellent.
The present invention provides the preparation methods of the copper-based catalysts described in above-mentioned technical proposal, include the following steps：
(1) by cupric ammine complex aqueous solution, C60And precipitant mix, deposition reaction is carried out, obtains copper-carbon mix；Institute
Cupric ammine complex aqueous solution is stated in terms of copper content, with C60Mass ratio be (0.5~60)：(0.1~50)；
(2) copper-carbon mix that the step (1) obtains with silicon source is mixed, carries out burin-in process, obtain aging object；
The silicon source is with the equal siliceous gauge of the amount of institute's silicon-containing material, with C60Mass ratio be (2~80)：(0.1~50)；
(3) the aging object for obtaining the step (2) is dried and is roasted successively, obtains catalyst precursor；
(4) catalyst precursor for obtaining the step (3) carries out reduction treatment, obtains ester through hydrogenation synthesis of dibasic alcohol use
Copper-based catalysts.
The present invention is by cupric ammine complex aqueous solution, C60And precipitant mix, deposition reaction is carried out, obtains copper-carbon mix.
In the present invention, the cupric ammine complex aqueous solution is in terms of copper content, with C60Mass ratio be (0.5~60)：(0.1~50),
Preferably (1~50)：(1~45), further preferably (5~45)：(5~35), more preferably (10~40)：(10~25).
The present invention is to the C60Specific source there is no particular/special requirement, using commercial goods well-known to those skilled in the art.
In the present invention, the deposition reaction is under cupric ammine complex effect, it is ensured that copper and C60Uniform sequential combination.In catalyst
In preparation process, cupric ammine complex in reaction solution with C60Uniform mixing, be beneficial to C60Phase interaction is generated with copper-containing substance
With particularly C60As the strong phase interaction between electronics donor or acceptor and copper ion or ammoniacal copper complex ion.
In the present invention, the mass concentration of the cupric ammine complex aqueous solution is preferably 25~28%.In the present invention, institute
The preparation method for stating cupric ammine complex aqueous solution preferably comprises：Copper source with ammonium hydroxide is mixed, complex reaction is carried out, obtains cuprammonium network
Close object aqueous solution；Copper source preferably includes one or more in copper nitrate, copper sulphate, copper acetate and copper chloride.In this hair
In bright, in copper source and ammonium hydroxide mixed process, realize dissolving of the copper source in ammonium hydroxide, form copper ion and ammonium ion network
It closes, forms cupric ammine complex.In the present invention, ammonium hydroxide is preferably added dropwise in copper source by the mixing of copper source and ammonium hydroxide；
In the present invention, the molar concentration of the ammonium hydroxide is preferably 25~28%；The dosage of the ammonium hydroxide is so that copper source is dissolved in ammonia
Subject in water；In the present invention, the ammonium hydroxide and the relative usage in copper source are become cloudy, then become subject to clarification with mixed liquor clarification.
The present invention provides copper source in the form of cupric ammine complex aqueous solution, helps to form the smaller nano copper particle of size, and then
Improve the catalytic activity of copper-based catalysts.
In the present invention, the precipitating reagent is preferably alkali compounds, further preferably including ammonia, carbonate, urea, methylamine
With it is one or more in ethamine；The dosage of the precipitating reagent is described with the content meter of copper in the cupric ammine complex aqueous solution
The quality of precipitating reagent is 1~5 times, further preferably 2~3 times of copper mass.In the present invention, the precipitating reagent and copper ion
After complexing, copper ion is more easy to and C60Combination, and then contribute to the raising of catalyst activity and stability.The present invention is to described heavy
The specific source of shallow lake agent does not have particular/special requirement, using commercial goods well-known to those skilled in the art.
In the present invention, under the action of precipitating reagent, amino can be tied simultaneously for the cupric ammine complex aqueous solution and fullerene
Copper ion and fullerene are closed, so as to which copper-carbon mix be promoted to be formed.
After obtaining copper-carbon mix, the present invention mixes the copper-carbon mix with silicon source, carries out burin-in process, obtains
Deposit.In the present invention, the silicon source is with the equal siliceous gauge of the amount of institute's silicon-containing material, the quality with fullerene
Than for (2~80)：(0.1~50), preferably (5~50)：(1~45), further preferably (20~30)：(5~35).At this
In invention, the silicon source preferably includes one or more in esters of silicon acis, Ludox, silicon ball and white carbon；The present invention is to described
The specific source of silicon source does not have particular/special requirement, using corresponding commercial goods well-known to those skilled in the art.
In the present invention, the copper-carbon mix is mixed with silicon source occurs aging, realizes copper ion in copper-carbon mix
Deposition on silicon source surface, obtains deposit.In the present invention, the copper-carbon mix includes cupric ammine complex and simultaneously
With reference to copper ion and the cupric ammine complex of fullerene；When silicon source is silicon ball or white carbon, cupric ammine complex is to silicon ball in silicon source
Or white carbon is decomposed, and forms the basic groups of Si-OH, and then promote silicon source and Cu again2+And C60Chemical bond cooperation occurs
With forming the catalyst activity phase of high activity, avoid the SiO of unformed accumulation2It cannot directly and Cu or C60What is be bonded asks
Topic.In the present invention, the burin-in process preferably carries out under agitation, and copper-carbon mix is promoted to be come into full contact with silicon source,
So that uniform deposition of the ionic state copper on silicon source surface.The present invention does not have particular/special requirement to the specific embodiment of the stirring,
Using agitating mode well-known to those skilled in the art.
In the present invention, the temperature of the burin-in process is preferably 25~150 DEG C, further preferably 30~120 DEG C, more
Preferably 50~100 DEG C；The time of the burin-in process is preferably 1~30h, further preferably 5~20h, and more preferably 10
~15h.
After the burin-in process, the deposit that the present invention obtains the burin-in process is dried and is roasted successively, is obtained
To catalyst precursor.In the present invention, the temperature of the drying is preferably 70~140 DEG C, further preferably 100~120
℃；The time of the drying is preferably 6~12h, further preferably 8~10h.In the present invention, the drying is realized to heavy
The removal of residual moisture in product object.
After the drying, the present invention roasts the deposit after drying, obtains catalyst precursor.In the present invention
In, the temperature of the roasting is preferably 200~300 DEG C, further preferably 220~280 DEG C, more preferably 230~250 DEG C；
The time of the roasting is preferably 1~10h, further preferably 2~7h, more preferably 5~6h.The present invention was roasted described
Cheng Zhong, the copper ion for being deposited on silicon source surface are changed into copper oxide nanometer particle, and silicon-containing material is broken down into silica, fowler
Alkene keeps stablizing.
After the calcination process, the product of roasting is preferably carried out micronization processes, the catalyst refined by the present invention
Precursor.In the present invention, the grain size of the catalyst precursor of the refinement is preferably 40~60 mesh, further preferably 50~
55 mesh.In the present invention, the mode of the micronization processes is preferably tabletting sieving；The specific reality that the present invention is sieved to the tabletting
The mode of applying does not have particular/special requirement, can obtain the catalyst precursor of target grain size.
After obtaining catalyst precursor, the catalyst precursor is carried out reduction treatment by the present invention, obtains ester through hydrogenation conjunction
Into dihydric alcohol copper-based catalysts.In the present invention, the reduction is preferably hydrogen or gaseous mixture containing hydrogen with reducing agent.
The present invention does not have particular/special requirement to the other components of the gaseous mixture containing hydrogen, using the arbitrary gas that can be coexisted with hydrogen
.In the present invention, the reduction treatment preferably carries out under argon atmosphere；When using hydrogen as reducing agent, institute
Reduction treatment is stated preferably to carry out under the mixed atmosphere of hydrogen and argon gas；In the mixed atmosphere of the hydrogen and argon gas, hydrogen is excellent
Choosing accounts for the 5%~80% of volume of gas, further preferably 20~50%.
In the present invention, the temperature of the reduction is preferably 250~550 DEG C, further preferably 300~500 DEG C, more excellent
It is selected as 350~400 DEG C；The temperature of the reduction is preferably reached by the way of heating, and the rate of the heating is preferably 2~10
DEG C/min, the initial temperature of the heating is preferably room temperature.In the present invention, the time of the reduction is preferably 2~12h, into
One step is preferably 5~10h.In the present invention, in the reduction process, copper oxide particle is reduced to metal copper nano granules.
In the present invention, the silicon source contributes to the dispersion of copper, and drying roasting is played the role of enhancing metallic carrier, these
It provides safeguard for catalytic activity and catalytic stability.
The present invention also provides preparation method systems described in copper-based catalysts described in above-mentioned technical proposal or above-mentioned technical proposal
Application of the standby obtained copper-based catalysts in the reaction of ester through hydrogenation synthesis of dibasic alcohol.In the present invention, the application preferably will
After the copper-based catalysts are mixed with the organic solution of ester, hydrogen is passed through, synthetic reaction is carried out, obtains dihydric alcohol.In the present invention
In, the synthetic reaction can carry out under lower pressure, can also carry out under high pressure.In the present invention, it is described low
The pressure of pressure is preferably 0.1~1MPa, further preferably 0.15~0.8MPa, more preferably 0.2~0.5MPa；In low-pressure section
When synthetic reaction is carried out under part, for the intake of the hydrogen preferably with hydrogen ester molar ratio computing, the hydrogen ester molar ratio is preferably 80
~300, further preferably 250~280.In the present invention, the pressure of the high pressure is preferably 2~5MPa；In condition of high voltage
During lower progress synthetic reaction, the hydrogen ester molar ratio is preferably 80~220, and further preferably 100~150.
In the present invention, solute is preferably dimethyl oxalate, dimethyl malenate or lactic acid in the organic solution of the ester
Ester；When the solute is dimethyl oxalate, obtained dihydric alcohol is ethylene glycol, when the solute is dimethyl malenate or breast
During acid esters, obtained dihydric alcohol is propylene glycol.In the present invention, organic solvent is preferably methanol in the organic solution of the ester
And/or ethyl alcohol；The mass concentration of the organic solution of the ester is preferably 0.1~1g/mL, further preferably 0.5~0.8g/
mL.In the present invention, the usage amount of the copper-based catalysts is described copper-based preferably in terms of the quality of solute in the organic solution of ester
The mass ratio of catalyst and the solute is preferably 0.2~1：1, further preferably 0.5:1.In the present invention, the synthesis
The temperature of reaction is preferably 170 DEG C~240 DEG C, further preferably 180~220 DEG C, more preferably 200 DEG C.
With reference to embodiment to a kind of ester through hydrogenation synthesis of dibasic alcohol copper-based catalysts provided by the invention and its preparation
Methods and applications are described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
4.5g Gerhardites are weighed, are dissolved in 50mL deionized waters, 28wt% ammonium hydroxide is added dropwise under stirring
Solution obtains the blue copper ammon solution of clear, obtains transparent blue copper ammon solution.It is transferred to and is preinstalled with 0.30g fowlers
In the round-bottomed flask of alkene, under mechanical agitation state, the aqueous solution of 10mL20wt% ureas is added in, is warming up to 80 DEG C with 500rpm's
Rotating speed stirs 1h.Then the 40wt% Ludox of 11g is added in, continues to be stirred aging 8h with the rotating speed of 500rpm.After cooling,
Sediment is filtered, is washed to neutrality, 12h is dried at 110 DEG C, is placed in Muffle furnace with the heating rate liter of 4 DEG C/min
To 350 DEG C, 4h is roasted, obtains catalyst precursor.
Obtained catalyst precursor is subjected to tabletting screening, 40~60 mesh particles is obtained, catalyst precursor is loaded
Enter in reactor, in normal pressure 5%H2Under/Ar atmosphere, 350 DEG C of reduction 4h are warming up to 2 DEG C/min, fullerene promoted type copper is made
Base catalyst, fullerene are the 5wt% of copper-based catalysts, and Cu is the 20% of copper-based catalysts, is denoted as 5%C60- 20%Cu/
SiO2。
Fullerene promoted type copper-based catalysts and comparative example 1 that embodiment 1 obtains are obtained into catalyst and are respectively used to oxalic acid
Dimethyl ester hydrogenation reaction prepares ethylene glycol.Concrete operations are that, using straight pipe type high-pressure micro-device, loaded catalyst is
0.1g makes catalyst bed be warming up to 190 DEG C with 2 DEG C/min, and reaction pressure is for 0.1MPa and with high pressure constant flow pump to reactor
In be pumped into dimethyl oxalate-methanol solution of a concentration of 0.1g/mL, flow rate of liquid 0.02mL/min, dimethyl oxalate at this time
Mass space velocity is 0.6h-1, control hydrogen flow rate that hydrogen ester molar ratio is made to be 200, reactant collection liquid after gas-liquid separator separates
Body product, interval 1h samplings carry out quantitative analysis in gas-chromatography.
Chromatographiccondition：Chromatographic column is KB-Wax 30m × 0.25mm × 0.32 μm, with the heating rate of 20 DEG C/min,
200 DEG C are warming up to from 50 DEG C.According to the ratio of each component in product, dimethyl oxalate is calculated using correction factor normalization method
Conversion ratio and various products selectivity, the results are shown in Table 1.
As shown in Table 1, under the action of the fullerene promoted type catalyst obtained in embodiment 1, dimethyl oxalate conversion ratio
It is 83.2%, ethylene glycol (EG) is selectively 81.9%, and quality of glycol space-time yield is 215mg/g-cat/h.It is right from table 1
Than it is found that yield of the selectivity of product and space-time yield limited on the catalyst containing fullerene is all far longer than without richness
Strangle the catalyst of alkene.
By obtained fullerene promoted type copper-based catalysts ester through hydrogenation prepare the catalytic performance detection mode of ethylene glycol into
The detection of the catalyst stability of row 300h, testing result are as shown in Figure 1.As shown in Figure 1, fullerene provided by the invention promotes
Type copper-based catalysts, catalytic stability is high, and during the catalysis through being up to 300h prepares ethylene glycol, activity still keeps stable.
Embodiment 2
Fullerene promoted type copper-based catalysts are prepared in the way of embodiment 1, difference lies in fullerene and Ludox add
Dosage is respectively 0.6g and 10.5g, and the 10wt% that fullerene in fullerene promoted type copper-based catalysts is copper-based catalysts is made,
Cu is the 20% of copper-based catalysts, is denoted as 10%C60- 20%Cu/SiO2Catalyst shows copper through ICP-MS quantitative analysis results
Content is in the error range of theoretical load capacity.
By obtained fullerene promoted type copper-based catalysts according in embodiment 1, catalyst prepares ethylene glycol in ester through hydrogenation
Catalytic performance detection mode carry out 300h catalyst stability detection, testing result is as shown in Figure 1.
As shown in Figure 1, fullerene promoted type copper-based catalysts provided by the invention, catalytic stability is high, through being up to 300h
Catalysis prepare ethylene glycol during, activity still keep stable.
Embodiment 3
Fullerene promoted type copper-based catalysts are prepared in the way of embodiment 1, difference lies in fullerene and Ludox add
Dosage is respectively 0.9g and 9.8g, and the 15wt% that fullerene in fullerene promoted type copper-based catalysts is copper-based catalysts is made,
Cu is the 20% of copper-based catalysts, is denoted as 15%C60- 20%Cu/SiO2Catalyst shows copper through ICP-MS quantitative analysis results
Content is in the error range of theoretical load capacity.
Embodiment 4
Fullerene promoted type copper-based catalysts are prepared in the way of embodiment 1, difference lies in fullerene and Ludox add
Dosage is respectively 1.2g and 9g, and 20wt%, Cu that fullerene in fullerene promoted type copper-based catalysts is copper-based catalysts is made
It is the 20% of copper-based catalysts, is denoted as 20%C60- 20%Cu/SiO2Catalyst shows that copper contains through ICP-MS quantitative analysis results
Amount is in the error range of theoretical load capacity.
Embodiment 5
Fullerene promoted type copper-based catalysts are prepared in the way of embodiment 1, difference lies in fullerene and Ludox add
Dosage is respectively 1.5g and 8.3g, and the 25wt% that fullerene in fullerene promoted type copper-based catalysts is copper-based catalysts is made,
Cu is the 20% of copper-based catalysts, is denoted as 25%C60- 20%Cu/SiO2Catalyst shows copper through ICP-MS quantitative analysis results
Content is in the error range of theoretical load capacity.
Comparative example 1
Copper-based catalysts are prepared in the way of embodiment 1, difference lies in be added without fullerene and Ludox additive amount
For 12g, it is the 20% of copper-based catalysts that Cu in copper-based catalysts, which is made, is denoted as 20%Cu/SiO2Catalyst is quantified through ICP-MS
Analysis result shows copper content in the error range of theoretical load capacity.
By the copper-based catalysts that embodiment 2~5 and comparative example 1 obtain according in embodiment 1, catalyst is prepared in ester through hydrogenation
The catalytic performance detection mode of ethylene glycol carries out performance detection, and the results are shown in Table 1.
The catalyst that 1 Examples 1 to 5 of table and comparative example 1 obtain is in the catalytic performance of preparing ethylene glycol by using dimethyl oxalate plus hydrogen
As shown in Table 1, the fullerene promoted type copper-based catalysts of different component prepare the anti-of ethylene glycol in catalysis ester through hydrogenation
Ying Zhong under the conditions of low pressure reaction, is respectively provided with higher catalytic activity so that the high conversion rate of dimethyl oxalate is up to 100%, second two
The selectivity of alcohol is above 80%, and the quality space-time yield of ethylene glycol is above 200mg/g.From the data of table 1, it was confirmed that fowler
The addition of alkene, which has catalytic performance, significantly to improve, and the most notable with 10~20% additive amounts.
Embodiment 6
Fullerene promoted type copper-based catalysts are prepared in the way of embodiment 1, difference lies in fullerene and Ludox add
Dosage is respectively 0.6g and 10.5g, and the 10wt% that fullerene in fullerene promoted type copper-based catalysts is copper-based catalysts is made,
Cu is the 20% of copper-based catalysts, is denoted as 10%C60- 20%Cu/SiO2Catalyst shows copper through ICP-MS quantitative analysis results
Content is in the error range of theoretical load capacity.
By the copper-based catalysts that embodiment 6 and comparative example 1 obtain according in embodiment 1, catalyst prepares second in ester through hydrogenation
The catalytic performance detection mode of glycol carries out performance detection, is 3MPa difference lies in, the pressure for being catalyzed reaction, testing result such as table
Shown in 2.
Embodiment 7
Fullerene promoted type copper-based catalysts are prepared in the way of embodiment 1, difference lies in fullerene and Ludox add
Dosage is respectively 0.6g and 10.5g, and the 10wt% that fullerene in fullerene promoted type copper-based catalysts is copper-based catalysts is made,
Cu is the 20% of copper-based catalysts, is denoted as 10%C60- 20%Cu/SiO2Catalyst shows copper through ICP-MS quantitative analysis results
Content is in the error range of theoretical load capacity.
By the copper-based catalysts that embodiment 7 and comparative example 1 obtain according in embodiment 1, catalyst prepares second in ester through hydrogenation
The catalytic performance detection mode of glycol carries out performance detection, and difference lies in the pressure for being catalyzed reaction is 3MPa, and reaction velocity is
8.4h-1, testing result is as shown in table 2.
The catalyst that 2 embodiment 6,7 of table and comparative example 1 obtain is in the catalytic performance of preparing ethylene glycol by using dimethyl oxalate plus hydrogen
As shown in Table 2, under the conditions of different liquid hourly space velocity (LHSV)s, in catalysis ester through hydrogenation prepares the reaction of ethylene glycol, this hair
The catalytic activity of the fullerene promoted type catalyst of bright offer is high so that the high conversion rate of dimethyl oxalate is up to 100%, ethylene glycol
Selectivity be above 90%, the quality space-time yield of ethylene glycol is even as high as 4158mg/g, show the catalyst can and
Under its harsh reaction condition, efficient catalytic result is still obtained.
Embodiment 8
Embodiment 2 is prepared into fullerene promoted type copper-based catalysts according in embodiment 1, catalyst prepares second in ester through hydrogenation
The catalytic performance detection mode of glycol carries out performance detection, and difference lies in dimethyl oxalate replaces with methyl lactate, catalysis reaction
Temperature for 180 DEG C, reaction 2~3h rear catalyst activity datas reach stable state.At this point, methyl lactate conversion ratio 100%, the third two
Alcohol is selectively 83.2%.
Embodiment 9
Embodiment 2 is prepared into fullerene promoted type copper-based catalysts according in embodiment 1, catalyst prepares second in ester through hydrogenation
The catalytic performance detection mode of glycol carries out performance detection, and difference lies in dimethyl oxalate replaces with dimethyl malenate, reaction
Pressure is 3MPa, and reaction 2~3h rear catalyst activity datas reach stable state.At this point, methyl lactate conversion ratio 85.1%, propylene glycol
Selectivity is 74.2%.
By the result of embodiment 2,8 and 9 it is found that the present invention obtains fullerene promoted type copper-based catalysts in ester through hydrogenation preparation
In the reaction process of dihydric alcohol, there is higher catalytic activity, catalytic activity can not only be played under high pressure, also had
Catalytic activity during low pressure reaction shows that the catalyst has certain universality.
Above example the result shows that, the fullerene promoted type copper-based catalysts of different component provided by the invention,
Catalysis ester through hydrogenation is prepared in the reaction of ethylene glycol, under the conditions of low pressure reaction or under the conditions of reaction under high pressure, is respectively provided with
Higher catalytic activity so that the high conversion rate of dimethyl oxalate is up to 100%, and the selectivity of ethylene glycol is above 80%, second two
The quality space-time yield of alcohol is above 200mg/g.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of ester through hydrogenation synthesis of dibasic alcohol copper-based catalysts, in terms of mass percentage, including 0.1~50% C60、0.5
~the 60% Cu and carrier S iO of surplus2；The C60The carrier S iO is carried on Cu2Surface.
2. copper-based catalysts according to claim 2, which is characterized in that the copper-based catalysts include 5~20% C60、
20~40% Cu and carrier S iO of surplus2。
3. the preparation method of the copper-based catalysts described in claims 1 or 2, includes the following steps：
(1) by cupric ammine complex aqueous solution, C60And precipitant mix, deposition reaction is carried out, obtains copper-carbon mix；The copper
Ammino-complex aqueous solution is in terms of copper content, with C60Mass ratio be (0.5~60)：(0.1~50)；
(2) copper-carbon mix that the step (1) obtains with silicon source is mixed, carries out burin-in process, obtain aging object；It is described
Silicon source is with the equal siliceous gauge of the amount of institute's silicon-containing material, with C60Mass ratio be (2~80)：(0.1~50)；
(3) the aging object for obtaining the step (2) is dried and is roasted successively, obtains catalyst precursor；
(4) catalyst precursor obtained the step (3) carries out reduction treatment, obtains ester through hydrogenation synthesis of dibasic alcohol with copper-based
Catalyst.
4. preparation method according to claim 3, which is characterized in that cupric ammine complex aqueous solution in the step (1)
Preparation method includes：Copper source with ammonium hydroxide is mixed, complex reaction is carried out, obtains cupric ammine complex aqueous solution；
Copper source includes one or more in copper nitrate, copper sulphate, copper acetate, copper chloride and copper oxide.
5. preparation method according to claim 3 or 4, which is characterized in that precipitating reagent is alkaline chemical combination in the step (1)
Object.
6. preparation method according to claim 3, which is characterized in that it is molten to include esters of silicon acis, silicon for silicon source in the step (2)
It is one or more in glue, silicon ball and white carbon.
7. the preparation method according to claim 3 or 6, which is characterized in that burin-in process is in stirring bar in the step (2)
It is carried out under part；The temperature of burin-in process is 25~150 DEG C；The time of burin-in process is 1~30h.
8. preparation method according to claim 3, which is characterized in that the temperature dried in the step (3) is 70~140
DEG C, the time of drying is 6~12h；
The temperature roasted in the step (3) is 200~300 DEG C, and the time of roasting is 1~10h.
9. preparation method according to claim 3, which is characterized in that reduction is hydrogen with reducing agent in the step (4)
Or the gaseous mixture containing hydrogen；The temperature of the reduction treatment is 250~550 DEG C, and the time of reduction treatment is 2~12h.
10. the copper that any one of copper-based catalysts described in claims 1 or 2 or claim 3~9 preparation method are prepared
Application of the base catalyst in the reaction of ester through hydrogenation synthesis of dibasic alcohol.
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| WO2019128914A1 (en) * | 2017-12-28 | 2019-07-04 | 厦门福纳新材料科技有限公司 | Copper-based catalyst for synthesizing dihydric alcohol by means of ester hydrogenation and preparation method therefor and use thereof |
| CN113209976A (en) * | 2021-05-21 | 2021-08-06 | 厦门大学 | Catalyst for methanol steam reforming hydrogen production, preparation method and application thereof, and methanol steam reforming hydrogen production reaction |
| CN113842916A (en) * | 2021-10-28 | 2021-12-28 | 厦门大学 | Cuprous functional material with stable fullerene, and preparation method and application thereof |
| CN115532260A (en) * | 2022-10-24 | 2022-12-30 | 厦门大学 | Cyclic carbonate low-pressure hydrogenation catalyst, and preparation method and application thereof |
| CN116116410A (en) * | 2023-02-24 | 2023-05-16 | 湘潭大学 | Copper-based catalyst and preparation method and application thereof |
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| CN114558602B (en) * | 2022-01-26 | 2023-08-01 | 天津大学 | Copper-loaded porous boron nitride nanorod catalyst and preparation method and application thereof |
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| CN101757915A (en) * | 2010-01-08 | 2010-06-30 | 厦门大学 | Catalyst used for preparing glycol from hydrogenation of oxalates and preparation method thereof |
| CN102451687A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof and synthesis method of ethylene glycol |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019128914A1 (en) * | 2017-12-28 | 2019-07-04 | 厦门福纳新材料科技有限公司 | Copper-based catalyst for synthesizing dihydric alcohol by means of ester hydrogenation and preparation method therefor and use thereof |
| CN113209976A (en) * | 2021-05-21 | 2021-08-06 | 厦门大学 | Catalyst for methanol steam reforming hydrogen production, preparation method and application thereof, and methanol steam reforming hydrogen production reaction |
| CN113842916A (en) * | 2021-10-28 | 2021-12-28 | 厦门大学 | Cuprous functional material with stable fullerene, and preparation method and application thereof |
| CN115532260A (en) * | 2022-10-24 | 2022-12-30 | 厦门大学 | Cyclic carbonate low-pressure hydrogenation catalyst, and preparation method and application thereof |
| CN116116410A (en) * | 2023-02-24 | 2023-05-16 | 湘潭大学 | Copper-based catalyst and preparation method and application thereof |
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| WO2019128914A1 (en) | 2019-07-04 |
| CN108187676B (en) | 2019-09-13 |
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