CN108654617A - Hydrogenation of oxalate for preparing ethylene glycol catalyst carrier method of modifying and catalyst and application - Google Patents
Hydrogenation of oxalate for preparing ethylene glycol catalyst carrier method of modifying and catalyst and application Download PDFInfo
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- CN108654617A CN108654617A CN201710191223.4A CN201710191223A CN108654617A CN 108654617 A CN108654617 A CN 108654617A CN 201710191223 A CN201710191223 A CN 201710191223A CN 108654617 A CN108654617 A CN 108654617A
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- catalyst
- solution
- oxalate
- carrier
- ethylene glycol
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000010949 copper Substances 0.000 claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012670 alkaline solution Substances 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052681 coesite Inorganic materials 0.000 claims description 12
- 229910052906 cristobalite Inorganic materials 0.000 claims description 12
- 229910052682 stishovite Inorganic materials 0.000 claims description 12
- 229910052905 tridymite Inorganic materials 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- -1 hydrogen ester Chemical class 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- KIZFHUJKFSNWKO-UHFFFAOYSA-M calcium monohydroxide Chemical compound [Ca]O KIZFHUJKFSNWKO-UHFFFAOYSA-M 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- OSNIIMCBVLBNGS-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(dimethylamino)propan-1-one Chemical compound CN(C)C(C)C(=O)C1=CC=C2OCOC2=C1 OSNIIMCBVLBNGS-UHFFFAOYSA-N 0.000 claims 1
- JRMAQQQTXDJDNC-UHFFFAOYSA-N 2-ethoxy-2-oxoacetic acid Chemical compound CCOC(=O)C(O)=O JRMAQQQTXDJDNC-UHFFFAOYSA-N 0.000 claims 1
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 229910003978 SiClx Inorganic materials 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 150000001879 copper Chemical class 0.000 claims 1
- 238000000227 grinding Methods 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- 238000002715 modification method Methods 0.000 claims 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- 235000010215 titanium dioxide Nutrition 0.000 claims 1
- 229910002012 Aerosil® Inorganic materials 0.000 abstract description 19
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000047 product Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 230000008859 change Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical class CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- ZZBBCSFCMKWYQR-UHFFFAOYSA-N copper;dioxido(oxo)silane Chemical compound [Cu+2].[O-][Si]([O-])=O ZZBBCSFCMKWYQR-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000003901 oxalic acid esters Chemical class 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000010850 salt effect Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B01J35/394—
-
- B01J35/613—
-
- 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
Abstract
The present invention relates to a kind of method of modifying of hydrogenation of oxalate for preparing ethylene glycol catalyst carrier and catalyst and application, mainly solves the problems, such as that hydrogenation products glycol selectivity is low present in conventional art, catalyst life is short and catalyst carrier is required high, of high cost.The catalyst of the present invention is using metallic copper as active component, using aerosil as carrier, is modified to catalyst carrier by the way that a certain amount of alkaline solution is added.Catalyst carrier has higher selectivity and stability by modified.
Description
Technical field
The present invention relates to a kind of catalyst carrier method of modifying of hydrogenation of oxalate for preparing ethylene glycol, especially with regard to oxalic acid two
The catalyst carrier method of modifying of methyl esters and diethy-aceto oxalate Hydrogenation ethylene glycol.
Background technology
China is powerful to polyester product demand, and ethylene glycol is the primary raw material of PET industry, this makes China become EG
Maximum country of consumption.But the main production of current ethylene glycol is that epoxyethane water is legal, and this method relies on petroleum resources.And
In the energy resource structure in China, coal relative abundance causes that synthesis gas is more easy to get and cost is relatively low, therefore in recent years by synthesizing
Gas prepares ethylene glycol and is just paid close attention to by more and more researchers.This method generates oxalic acid by CO oxidative couplings first
Ester, the further catalytic hydrogenation of oxalate generate ethylene glycol.The technique mesoxalic acid ester through hydrogenation preparing ethylene glycol is considered as its industrialization
Where the bottleneck of application.This process mainly occurs to react as follows:(1) oxalate is hydrogenated to intermediate product methyl glycollate；
(2) methyl glycollate is further hydrogenated to mesh glycol product；(3) ethylene glycol continues to be hydrogenated to ethyl alcohol or other dihydric alcohols
By-product；(4) ethylene glycol is reacted with other single methanols generates ether.There it can be seen that target product ethylene glycol is in hydrogenation process
In intermediate steps, therefore it is crucial for how improving product selectivity.The ethylene glycol purity that traditional technology is generated in this step compared with
It is low, it is difficult to which large-scale application is in PET industry.So it is always the process to research and develop highly selective hydrogenation of oxalate for preparing EG catalyst
A research hotspot.
In the eighties in last century, Ube patent (US 4,229,591) uses Cu/SiO prepared by ammonia still process method2Catalysis
Agent because it shows preferably performance in the reaction of catalysis hydrogenation of oxalate for preparing EG, and obtains more concern.In recent years, such as
Numerous units such as Fujian object structure institute, Xiamen University, University Of Tianjin, East China University of Science, Fudan University, Zhejiang University, to Cu/
SiO2The preparation method of catalyst and auxiliary agent etc. have carried out a large amount of research work, and make some progress.Especially
It is effect etc. played in the ratio and its reaction of two kinds of different activities valence states of catalytic metal copper component, it has also become the catalyst
Research hotspot.But how to make Cu/SiO2It is always that this is urged that catalyst obtains higher selectivity in oxalate hydrogenation
The important goal of agent research.Because the ethylene glycol product ethylene glycol prepared by this technique still cannot be satisfied downstream polyester and use
The standard of ethylene glycol, in product more impurity on the ultraviolet permeability of ethylene glycol product have it is apparent influence, and this is urged
The problems such as agent is poor there is also stability.SiO in Cu bases catalyst preparation process reported in the literature simultaneously2Carrier uses mostly
Be Ludox, using Ludox as carrier source, although more excellent effect can be achieved, but if catalyst is advised greatly
Mould amplifies, and can undoubtedly increase production cost and environmental pressure.Aerosil (also known as white carbon) is a kind of large industry
Material is widely used in rubber product, coating, weaving, papermaking, pesticide and food additives etc..The gas phase two in China
Silica volume of production and marketing ranks the first in the world.Aerosil is a kind of Nano-meter SiO_22Powder, with even particle size distribution, surface
Strong adsorption force, dispersion performance are good, it is cheap and easy to get the features such as, be used as the carrier of catalyst, can obviously reduce the life of catalyst
At cost.But simultaneously because its preparation process is complicated, it is more to influence product qualitative factor so that the chemistry of aerosil
Nature difference is larger, and especially its surface group is numerous, containing a large amount of polarity group, and differs greatly, this all limits its work
For the application of catalyst carrier.
Invention content
Due to the additive that the main application of aerosil is rubber, so for the method for its modification, it is main to collect
In in the modification (CN 103113761A) to the abundant polarity group in its surface, it is therefore an objective to change its hydrophily, make it organic
There is preferable mobility in medium, while making it be not easy to reunite by replacing its surface hydroxyl, it is smaller to obtain
Powder, and modifying agent also uses silane and its derivative mostly.
The technical problem to be solved by the present invention is to the characteristics of for aerosil as catalyst carrier, not
It is hydrophilic simultaneously to change its, its surface portion hydroxyl is eliminated by modified, makes modified aerosil carrier system
Standby catalyst has higher glycol selectivity and stability.Aerosil surface contains because of its synthesis technology feature
There are a large amount of polar hydroxyl groups, [Zheng Lihua, Liu Qinfu, Cheng Hong fly white carbons surface and change since these hydroxyls have different connection form
Journal of Sex Research present situation [J] China non-metallic mineral industry guide, 2008 (1):12-15.], and there are different chemical property, and can shadow
The performance of catalyst when ringing it as carrier.Which part hydroxyl can occur strong because its activity is higher with catalyst activity metal
Interaction to reduce the activity of catalyst, therefore by certain method, eliminates part of hydroxyl, to improving catalyst performance
With positive effect.
The present invention utilizes salt effect, and amount of activated higher hydroxyl in aerosil is made to ionize, then sharp again
It is neutralized with highly basic, to achieve the purpose that eliminate the higher hydroxyl of its surface-active.Carrier can suitably reduce and urge by modified
Action intensity in agent between active metal copper and carrier, and then the metal dispersity of catalyst is made to increase, the second of catalyst
Glycol is selectively improved.
The catalyst is using Cu as active component, SiO2For carrier, preferably aerosil carrier and change through alkaline solution
Aerosil carrier after property, uses alkaline solution KOH, NaOH, CaOH of a concentration of 0.01mol/L~1mol/L etc. couple
Carrier is modified, preferably KOH and NaOH solution.
The technical solution adopted by the present invention is：
A kind of method of modified aerosil carrier.It is characterized in that：First, a certain amount of gas phase titanium dioxide is weighed
Silicon sample is dissolved in 10%~50% KCl or NaCl solution, is sufficiently stirred；Secondly, extremely with hydrochloric acid conditioning solution pH
4.0；Then, the KOH of a certain amount of a concentration of 0.01mol/L~1mol/L or NaOH solution are added in above-mentioned solution, are filled
Divide mixing 10min~60min；Finally, above-mentioned suspension is filtered washing, is washed till after filtrate is neutral, then through 60 DEG C~
120 DEG C of drying.
A kind of catalyst of hydrogenation of oxalate for preparing ethylene glycol, using Ni metal as active component, it is characterised in that：Above-mentioned catalysis
Agent is using modified aerosil as carrier；The mass percentage of each component is in the catalyst：Active metal Cu
It is 10~70%, surplus is carrier silicas.
The preparation process of catalyst of the present invention is：Mantoquita and ammonium hydroxide are mixed first, obtain the complexing of uniform copper
Object solution；Then modified aerosil is added in above-mentioned solution and is sufficiently stirred；Then it is heated up again except deammoniation；Finally
It is fired, mill and tabletting obtain catalyst.
The reactivity worth evaluation of programme of catalyst of the present invention is：In continuous fixed bed reactors, 1.0g. catalysis is loaded
Agent.Using 230 DEG C of reducing catalysts of pure hydrogen normal pressure, flow velocity 100mL/min, with the rate of 1~2 DEG C/min from room temperature to
230 DEG C, and 4h is kept, it is passed through H after being down to reaction temperature2, with constant-flux pump conveying dimethyl oxalate, diethy-aceto oxalate or the two
Methanol solution reacted.Product is analyzed with gas-chromatography, and chromatographic column is FFAP type polarity capillary columns, hydrogen flame detection
Device (FID) detects reaction raw materials and product.
Catalyst Conversion and selective computational methods are as follows：
Conversion ratio (%)：
Selectivity (%)：M refers to reaction product in above formula, such as
Ethylene glycol (EG), methyl glycollate (MG), 2- methyl ethyl ethers (2-MEO), 1,2- propylene glycol (1,2-POD), 1,2- butanediols
(1,2-BOD) etc..
For the present invention using aerosil as catalyst carrier, catalyst preparation process and manufacturing cost have been lacked in letter,
Especially raw material is easy to get, it is easier to industrialization large-scale production.By being modified to aerosil, it can be made to prepare
Catalyst has higher glycol selectivity and stability.
The present invention relates to a kind of method of modifying of hydrogenation of oxalate for preparing ethylene glycol catalyst carrier, mainly solve conventional art
Present in hydrogenation products glycol selectivity is low, catalyst life is short and requires high, of high cost ask to catalyst carrier
Topic.The catalyst of the present invention is using metallic copper as active component, using aerosil as carrier, by the way that a certain amount of alkalinity is added
Solution is modified catalyst carrier.Catalyst carrier has higher selectivity and stability by modified.
The technology of the present invention details is subject to detailed description by following embodiments.It should be noted that for embodiment, make
With the only technical characteristic that further illustrates the present invention, rather than limit the present invention.
Embodiment 1
Aerosil is modified：
Two parts of the aerosil sample of 6g is weighed respectively, and the NaCl for being dissolved in 600mL mass concentrations 20% is molten
In liquid, it is sufficiently stirred；Then, the hydrochloric acid conditioning solution pH to 4.0 for being 5% with mass concentration；Then, by a concentration of 0.1mol/L
NaOH solution 25ml and 50ml be separately added into above-mentioned two parts of solution and carry out being sufficiently mixed 30min；Finally, by above-mentioned suspension
It is filtered washing, after being washed till filtrate as neutrality, then through 120 DEG C of drying, is respectively labeled as SiO2- A and SiO2-B。
Embodiment 2
With deionized water by Cu (NO3)20.3mol/L aqueous solutions are configured to, the measurement 157ml solution is placed in beaker, side
Ammonium hydroxide is slowly added dropwise in stirring side, stops when until pH value of solution being 9.5~10.5 in beaker.Weigh gas modified in 4g embodiments 1
Aerosil SiO2- A is added in the beaker of above-mentioned copper ammon solution, in 30 DEG C of stirred in water bath aging 4h, is warming up to 90 DEG C of steamings
Ammonia stops when the pH value of beaker solution is 7~8.Stop after being about 7 by the pH that the sediment of gained is filtered, washed to filtrate
Only.By the dry 12h of 120 DEG C of sediment after washing, 450 DEG C roast 4h, and tabletting is crushed to 20~40 mesh, and reaction pre reduction obtains
Catalyst A:20wt%Cu/SiO2。
Embodiment 3
Preparation process weighs aerosil SiO modified in 4g embodiments 1 with embodiment 22-B.It is prepared
Catalyst B：20wt%Cu/SiO2。
Comparative example 1
For preparation process with embodiment 1, the NaOH solution quantitative change of addition is 75ml.Carrier S iO is prepared in the embodiment2-
C。
Comparative example 2
Preparation process weighs aerosil SiO modified in 4g comparative examples 1 with embodiment 22- C is used as and urges
Agent carrier.Catalyst C is prepared in the embodiment：20wt%Cu/SiO2。
Comparative example 3
Preparation process weighs the non-modified aerosils of 4g as catalyst carrier with embodiment 2.The embodiment
Catalyst D is prepared：20wt%Cu/SiO2。
Embodiment 4：
Catalyst prepared by embodiment 2,3 and comparative example 2,3,190 DEG C, 3MPa, 80 hydrogen ester ratios, 0.5h- 1LHSVDMOUnder the conditions of, in preparing ethylene glycol by using dimethyl oxalate plus hydrogen reaction, performance to be listed in table 1.
The influence of catalyst prepared by 1. different carriers of table to oxalic acid ester through hydrogenation performance
Table 1 can be seen that carrier is through the modified catalyst of alkaline solution, hence it is evident that be better than the unmodified comparative example of carrier
3 catalyst D.Wherein use SiO2- A has as the catalyst of the embodiment 2 of carrier up to 94.5% optimal ethylene glycol
Selectivity, and close to 100% dimethyl oxalate conversion ratio.Simultaneously it can be seen that with the SiO of 25mlNaOH solution modifications2- A systems
Standby catalyst A is also significantly better than catalyst prepared by other two kinds modified carriers.Illustrate to change aerosil
Property needed for alkaline solution it is not The more the better, as modified alkaline solution additive amount increases from scratch, made by it
The glycol selectivity of standby catalyst is in normal distribution.
Embodiment 5：
The catalyst prepared to embodiment 2,3 and comparative example 2,3 carries out metallic copper dispersion degree test.The dispersion degree of copper
It is according to N2O and Cu0Reaction characteristics, carried out on chemical adsorption instrument.The data finally measured are listed in table 2.
The dispersion degree of the metallic copper of catalyst prepared by 2. different carriers of table
From Table 2, it can be seen that by the modified catalyst of alkaline solution, there is higher metallic copper dispersion degree and work
Property metallic copper specific surface area.Active component of the copper as catalyst, dispersion degree will influence the hydrogenation activity of catalyst, in conjunction with table
1 data, it can be seen that the copper dispersion degree of catalyst is higher, and glycol selectivity is higher under the conditions of equivalent responses.Generate this
The reason of one phenomenon may be that non-modified aerosil contains more activity hydroxy, have one to active metal copper
Fixed package action so that its dispersion degree and the active area of exposure are relatively low, and, carrier modified to its by alkaline solution
High activity hydroxyl lose activity due to being reacted with alkali, in catalyst copper package action weaken so that its prepare urge
The metal dispersity of agent is improved.But when the dosage of aqueous slkali is excessive, the hydroxyl of carrier can further decrease, to
The generation for affecting page cupric silicate in catalyst, the dispersion degree in turn resulting in catalyst do not rise anti-drop.
Embodiment 6：
Investigate the influence for the catalyst hydrogenation performance that reaction temperature prepares embodiment 2.Other reaction conditions are：Pressure
3MPa, hydrogen ester are than 80, LHSVDMO0.5h-1.Reaction result is listed in table 3.
Influence of 3. temperature of table to ethylene glycol catalyst prepared by dimethyl oxalate plus hydrogen reactivity worth
The experimental result of table 3 shows, reaction temperature to the conversion ratio of dimethyl oxalate and the selectivity of each product have compared with
Big influence.At 190 DEG C, the conversion ratio of dimethyl oxalate has reached~100%, and glycol selectivity has reached 94.5%,
But as the selectivity that temperature increases ethylene glycol continuously decreases, the selectivity of ethyl alcohol gradually rises.It will thus be seen that temperature is to grass
Dimethyl phthalate hydrogenation reaction is can to change point of Hydrogenation of Dimethyl Oxalate product by changing temperature with large effect
Cloth.
Embodiment 7：
It investigates embodiment 2 and prepares stability of the catalyst A in the reaction of preparing ethylene glycol by using dimethyl oxalate plus hydrogen.190
DEG C, 3MPa, 0.5h-1LHSVDMOUnder the conditions of, reaction result is listed in table 4.
The catalyst stability test of 4. preparing ethylene glycol by using dimethyl oxalate plus hydrogen of table
It can be seen that in embodiment 1 by urging prepared by the modified carrier of alkaline solution according to the experimental data of table 4
Agent A has preferable stability.Above-mentioned catalyst is within the scope of the 1000h investigated, and the conversion ratio of dimethyl oxalate is always
About 100% is kept, the selectivity of ethylene glycol is also always held at 94% or so.
Claims (9)
1. a kind of catalyst carrier method of modifying of hydrogenation of oxalate for preparing ethylene glycol, it is characterised in that：The catalyst is with SiO2For
Carrier, carrier are modified through alkaline solution.
2. catalyst carrier method of modifying according to claim 1, it is characterised in that：Its carrier S iO2For Ludox and gas phase
One kind in silica or two kinds.
3. catalyst carrier method of modifying according to claim 1, it is characterised in that：Its carrier preferred hydrophilic gas phase dioxy
SiClx.
4. according to the catalyst carrier method of modifying of claim 1,2 or 3, it is characterised in that：The alkalinity of its support modification is molten
Liquid is one or two or more kinds of solution in KOH, NaOH, CaOH etc., one kind in preferably KOH, NaOH solution or two kinds with
On solution, a concentration of 0.01mol/L~1mol/L.
5. according to the catalyst carrier method of modifying of claim 1,2,3 or 4, it is characterised in that：
Support modification method is：Weigh carrier S iO2, by SiO2It is put into NaCl the or KCl solution that mass concentration is 10%~50%
In, it is sufficiently stirred；Then the hydrochloric acid that mass concentration is 5%~30% is used to adjust above-mentioned suspension pH to 3.5~4.5；Then, will
The alkaline solution that molar concentration is 0.01~1mol/L, which is added in above-mentioned solution, to carry out being sufficiently mixed 10~60min, alkaline solution
Refer to one or two or more kinds of solution in KOH, NaOH, CaOH, every 5~50g SiO2Alkaline solution usage amount be 10
~1000ml；Finally, above-mentioned suspension is filtered washing, after being washed till filtrate as neutrality, then through 60~120 DEG C of drying.
6. a kind of catalyst of hydrogenation of oxalate for preparing ethylene glycol, it is characterized in that：The catalyst using Ni metal as active component, with
SiO2For carrier, the mass percentage of each component is in the catalyst：Active metal Cu is 10%~70%, and surplus is to carry
Body SiO2；
Preparation process is to mix copper salt solution for 10%~35% ammonium hydroxide with mass concentration, to obtain pH value as 9~10
Copper ammon solution；It states then up and any modified gas phase titanium dioxides of claim 1-5 is added in copper ammon solution
Silicon is sufficiently stirred 3~6h of aging；Then obtained suspension is warming up to 60~90 DEG C, to remove ammonia in solution；Most afterwards through washing
It washs, roast, grinding, tabletting obtains catalyst；Calcination temperature is：300~600 DEG C.
7. application of the catalyst in hydrogenation of oxalate for preparing ethylene glycol described in a kind of claim 6.
8. application according to claim 7, it is characterised in that：The oxalate, refer to oxalic acid methyl monoester, oxalic acid mono ethyl ester,
Dimethyl oxalate, the one or two or more kinds in diethy-aceto oxalate, it is excellent refer to dimethyl oxalate and one kind in diethy-aceto oxalate or
Two kinds.
9. application according to claim 7 or 8, it is characterised in that：The hydrogenation of oxalate for preparing ethylene glycol reaction, 150
It carries out, is carried out at 0.5~6MPa or preferably 2~3Mpa pressure, 10 at a temperature of~260 DEG C or preferably 160~200 DEG C
It is carried out under~200 or preferably 50~120 hydrogen ester molar ratio.
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