CN107866224A - Catalyst and its production and use - Google Patents
Catalyst and its production and use Download PDFInfo
- Publication number
- CN107866224A CN107866224A CN201610852900.8A CN201610852900A CN107866224A CN 107866224 A CN107866224 A CN 107866224A CN 201610852900 A CN201610852900 A CN 201610852900A CN 107866224 A CN107866224 A CN 107866224A
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- China
- Prior art keywords
- catalyst
- reaction
- ethylene glycol
- dimethyl oxalate
- copper
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- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000010949 copper Substances 0.000 claims abstract description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 8
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 8
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 94
- 238000006243 chemical reaction Methods 0.000 claims description 39
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 claims description 38
- 239000001257 hydrogen Substances 0.000 claims description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 28
- 238000002360 preparation method Methods 0.000 claims description 17
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 230000009467 reduction Effects 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000008119 colloidal silica Substances 0.000 claims description 7
- 239000003517 fume Substances 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 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
- 150000001879 copper Chemical class 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims 2
- 244000025254 Cannabis sativa Species 0.000 claims 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims 1
- 229960001826 dimethylphthalate Drugs 0.000 claims 1
- 239000012808 vapor phase Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 230000008569 process Effects 0.000 description 15
- 238000005984 hydrogenation reaction Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 12
- 229910021529 ammonia Inorganic materials 0.000 description 11
- 229910002651 NO3 Inorganic materials 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229910001868 water Inorganic materials 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000013049 sediment Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 229910016344 CuSi Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- -1 BDO 1,2- butanediols Chemical class 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 241000692870 Inachis io Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 150000003901 oxalic acid esters Chemical class 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000013456 study Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater 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
- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of catalyst and its methods and applications processed, and the catalyst comprises at least the component of following parts by weight：Copper 10 ~ 60, SiO2 40 ~ 90.The catalyst prepared using the present invention has efficient catalytic performance, meets industrialized production needs.
Description
Technical field
The present invention relates to a kind of catalyst and its production and use, belong to chemical field.
Background technology
Ethylene glycol (EG) is a kind of important Elementary Chemical Industry Organic Ingredients, can be generated with terephthaldehyde's acid reaction poly- to benzene two
Formic acid second diester, it is the raw material for producing polyester resin and polyester fiber monomer, is also widely used for plasticizer, lubricant, antifreeze
The industries such as agent, adhesive and surfactant.
The method of production ethylene glycol is mainly oil-ethylene-ethylene oxide route, and the technological process is grown, high energy consumption, second two
Alcohol is selectively low and the technique depends on petroleum resources unduly.Due to China's oil resource-constrained, and natural gas, coal resource are relatively rich
Richness, therefore, develop with natural gas, coal resource producing synthesis gas so as to prepare ethylene glycol process route, to reducing ethene energy consumption, section
About petroleum-based energy has very great meaning.Wherein, synthesis gas (CO+H2) through oxalate method ethylene glycol route is prepared because its is anti-
Mild condition is answered, glycol selectivity is high and turns into the focus studied at present.Oxalate, oxalate are first generated by CO oxidative couplings
Further catalytic hydrogenation generation ethylene glycol.In the technological process, it is committed step that oxalate, which is further hydrogenated to ethylene glycol,.By
Intermediate product, target product can be produced in hydrogenation process in oxalate and crosses hydrogenation products, so improving ethylene glycol product choosing
Selecting property is the key of the preparation process.And the ethylene glycol product selectivity and catalyst long-term operation of the current process catalyst
Stability can not still meet the requirement of industrial applications, so, the research emphasis of the technological process is the exploitation of catalyst.
Lot of domestic and international company and research institution, such as E.I.Du Pont Company, Xue Fulong companies, Arco companies, the emerging production in space portion, the U.S.
UCC companies, the domestic Chemical Engineering Laboratory of University Of Tianjin's carbon one, structure of matter research institute of the Fujian Chinese Academy of Sciences and East China University of Science etc. are all
To hydrogenation of oxalate for preparing ethylene glycol, this project is studied, and has delivered Patents.Ube company proposes oxalic acid
This route of ester gas phase hydrogenation preparing ethylene glycol, clear 57-122938, clear 57-122939, clear 57-122940 and clear 57-1870432
Etc. describing different method for preparing catalyst；ARCO companies of the U.S. report a kind of containing Cr's in European patent 0060787
Copper Si catalyst.Domestic also more on preparing ethylene glycol by using dimethyl oxalate plus hydrogen patent, Fujian thing structure institute of the Chinese Academy of Sciences was in 90 years
In generation, also develops Cu-Cr catalyst, completes the 200ml model studys work of diethy-aceto oxalate hydrogenation preparing ethylene glycol,
Hydrogenation of Dimethyl Oxalate catalyst is mainly two big system of CuSi and CuCr.It is harmful to environment, dirty due to Cr severe toxicity
Dye is big, and at present, domestic industry or pilot-plant largely use CuSi series hydrocatalysts, and catalyst employs ammonia still process substantially
Or the homogeneous precipitation technology such as hydrolysis of urea.For example, East China University of Science by the use of ammoniacal liquor as precipitating reagent co-precipitation prepare it is a variety of
CuSi catalyst, oxalic acid ester conversion rate 95% or so, glycol selectivity 90% or so；Fudan University, Xiamen University and Tianjin
University develops a variety of CuSi series catalysts using ammonia still process method, document report DMO conversion ratios 99% or so, EG yields 90% with
On.The hydrogenation catalyst prepared although with ammonia still process method or urea law technology has preferable catalytic performance, but due to preparing
Precipitating reagent, which consumes, in journey exceeds well over theory measurement ratio, and processing cost height, the environmental protection pressure of waste water or waste gas are big.
The content of the invention
In view of the above the shortcomings that prior art, it is an object of the invention to provide a kind of catalyst and preparation method thereof
And purposes, for solving weak point in the prior art.
In order to achieve the above objects and other related objects, the present invention provides a kind of catalyst, and the catalyst comprises at least
The component of following parts by weight：
Copper 10~60
SiO240~90.
SiO in above-mentioned catalyst2It is carrier.
Preferably, copper and silica containing effective dose in the catalyst.
Preferably, the parts by weight of the copper are 20~40.
Preferably, the SiO2Any one or two kinds in Ludox or fume colloidal silica, preferably gas phase
Method white carbon, it is highly preferred that the fume colloidal silica is hydrophilic fume colloidal silica.
The chemical composition of the fume colloidal silica refers to Nano-meter SiO_22。
Another aspect provides the preparation method of above-mentioned catalyst, including at least following steps：
(1) copper salt solution is prepared by above-mentioned formula, adds SiO2, stir, heating, obtain mixed liquor；Copper in the mantoquita
Amount and SiO2Amount meet the ratio of above-mentioned formula；
(2) mixed liquor for adding ammoniacal liquor in step (1), must be precipitated；
(3) by the washing of precipitate in step (2), dry, roasting.
Preferably, the preparation method of catalyst, in addition to any one or a few in following characteristics：
A. the temperature of heating is 80~100 DEG C in the step (1)；
B. the concentration of the ammoniacal liquor is 1%~10%；
C. the ammoniacal liquor is added by the way of being added dropwise, and the pH value for being added dropwise to solution is 6~8；
D. the washing specially first uses temperature to be washed for 40-60 DEG C of ethanol or methanol, then washes；
E. the temperature of drying is 80~120 DEG C in the step (3)；
F. the temperature of roasting is 300~600 DEG C in the step (3), and the time is 3~8 hours.
Preferably, the concentration of copper is 1~2mol/l in the mantoquita, and copper sulphate and/or nitric acid are selected from selected from mantoquita
Copper, preferably copper nitrate.
Another aspect of the present invention additionally provides catalyst prepared by the preparation method of above-mentioned catalyst.
Another aspect of the present invention additionally provides above-mentioned catalyst and is used to be catalyzed the anti-of preparing ethylene glycol by using dimethyl oxalate plus hydrogen
The purposes answered.
Hydrogenation of Dimethyl Oxalate reaction is primarily referred to as：Dimethyl oxalate catalytic hydrogenation generates ethylene glycol.Key reaction formula is such as
Under：
Overall reaction equation is as follows：
(COOCH3)2+4H2=(CH2OH)2+2CH3OH
Its preparation method is prior art, is specifically：
Catalyst after reduction is produced into ethylene glycol applied to dimethyl oxalate gas phase hydrogenation, hydrogenation technique parameter is：With
Dimethyl oxalate is raw material, 175~250 DEG C of the reaction temperature of preparing ethylene glycol by using dimethyl oxalate plus hydrogen, reaction pressure 1.5~
3.5MPa。
Preferably, the catalyst uses 5~100v%'s before the reaction for preparing ethylene glycol by using dimethyl oxalate plus hydrogen
Hydrogen reducing, reduction temperature are 120~300 DEG C.
Preferably, the hydrogen in reaction of the preparing ethylene glycol by using dimethyl oxalate plus hydrogen and the mol ratio of oxalate be 40~
200: 1, dimethyl oxalate mass space velocity is 0.4~2.0g/g.h.
Mass space velocity：Refer to certain reaction mass (or overall reaction material) passed through in the unit interval on unit mass catalyst
Quality.
As described above, catalyst of the present invention and its production and use, has the advantages that：
The conversion ratio of raw material dimethyl oxalate is close to 100%, and ethylene glycol space-time yield is high, and target product selectivity is 95%
More than, accessory substance is few, long lifespan, meets industrialization production requirements.Catalyst service life can meet industrialized production up to 1 year
Needs.The preparation process preparation time is short, and efficiency high, energy consumption are low.Ammoniacal liquor utilization rate is high and environmentally friendly.Made using ammoniacal liquor
For precipitating reagent, for consumption of raw materials substantially close to theory measurement ratio, three waste discharge is few, and environmental protection treatment cost is low, and uses ammoniacal liquor
Precipitation process contributes to copper to form class peacock stone structure with silicon, can improve the decentralization of active ingredient copper and the anti-sintering energy of copper
Power, improve the reactivity worth and stability of catalyst.
Embodiment
Illustrate embodiments of the present invention below by way of specific instantiation, those skilled in the art can be by this specification
Disclosed content understands other advantages and effect of the present invention easily.The present invention can also pass through specific realities different in addition
The mode of applying is embodied or practiced, the various details in this specification can also be based on different viewpoints with application, without departing from
Various modifications or alterations are carried out under the spirit of the present invention.
It should be clear that in the following example not specifically dated process equipment or device using conventional equipment in the art or
Device.
In addition, it is to be understood that one or more method and steps mentioned in the present invention do not repel before and after the combination step
There can also be other method step or other method step can also be inserted between the step of these are specifically mentioned, unless separately
It is described；It should also be understood that the combination annexation between one or more equipment/devices mentioned in the present invention is not repelled
Can also have other equipment/device before and after the unit equipment/device or two equipment/devices specifically mentioning at these it
Between can also insert other equipment/device, unless otherwise indicated.Moreover, unless otherwise indicated, the numbering of various method steps is only
Differentiate the convenient tool of various method steps, rather than ordering or the enforceable model of the restriction present invention for limitation various method steps
Enclose, its relativeness is altered or modified, and in the case where changing technology contents without essence, when being also considered as, the present invention is enforceable
Category.
NH in the following embodiments3·H2O refers to the industrial ammonia that mass fraction is ammonia 25%~28%.
Embodiment 1
Weigh 52gNH3·H2O, add 117g deionized waters and be made into ammonia aqueous solution.
With deionized water by Cu (NO3)2·3H2O is configured to the 1mol/l aqueous solution, measures the 175ml solution and is placed in three mouthfuls of burnings
In bottle.Weigh 46g white carbons and add and above-mentioned fill Cu (NO3)2·3H2In the three-necked flask of O solution, stirred in room-temperature water bath
1h, be warming up to 100 DEG C, under stirring condition, ammonia spirit be added dropwise in three-necked flask, 5 hours, to pH value be 7.8 when stop.
The sediment filtering of gained, temperature are washed laggard water-filling for 40 DEG C of ethanol and washed.Dried at 80 DEG C 24 hours, 300 DEG C of roastings 8 are small
When, obtain oxalate gas phase hydrogenation catalyst.
Use hydrogen of the procatalyst hydrogen volume content for 80%, nitrogen mixture reduction, reduction temperature 250
℃.Evaluated on the micro-reactor of 10 milliliters of loaded catalysts, using dimethyl oxalate as reaction raw materials, control reaction temperature
200 DEG C, reaction pressure 2.0MPa of degree, dimethyl oxalate mass space velocity is 0.7g/g.h, hydrogen and dimethyl oxalate mol ratio
For 70：1, evaluation result is shown in Table 1.
Embodiment 2
Weigh 66.5gNH3·H2O, add 1596g deionized waters and be made into ammonia aqueous solution.
With deionized water by Cu (NO3)2·3H2O is configured to the 2mol/l aqueous solution, measures the 95ml solution and is placed in three mouthfuls of burnings
In bottle.Weigh 26g white carbons and add and above-mentioned fill Cu (NO3)2·3H2In the three-necked flask of O solution, stirred in room-temperature water bath
1h, be warming up to 80 DEG C, under stirring condition, ammonia spirit be added dropwise in three-necked flask, after 12 hours, to pH value be 6.5 when stop
Only.The sediment filtering of gained, temperature are washed laggard water-filling for 60 DEG C of ethanol and washed.Dried at 120 DEG C 12 hours, 500 DEG C of roastings 6
Hour, obtain oxalate gas phase hydrogenation catalyst.
Using hydrogen of the procatalyst hydrogen volume content for 5%, nitrogen mixture reduction, reduction temperature is 250 DEG C.
Evaluated on the micro-reactor of 10 milliliters of loaded catalysts, using dimethyl oxalate as reaction raw materials, controlling reaction temperature
180 DEG C, reaction pressure 2.0MPa, dimethyl oxalate mass space velocity is 0.4g/g.h, and the mol ratio of hydrogen and dimethyl oxalate is
200:1, evaluation result is shown in Table 1.
Embodiment 3
Weigh 42gNH3·H2O, add 168g deionized waters and be made into ammonia aqueous solution.
With deionized water by Cu (NO3)2·3H2O is configured to the 1mol/l aqueous solution, measures the 150ml solution and is placed in three mouthfuls of burnings
In bottle.Weigh 15.4g white carbons and add and above-mentioned fill Cu (NO3)2·3H2In the three-necked flask of O solution, stirred in room-temperature water bath
Mix 1h, be warming up to 90 DEG C, under stirring condition, ammonia spirit is added dropwise in three-necked flask, after 8 hours, to pH value be 7.6 when stop
Only.The sediment filtering of gained, temperature are washed laggard water-filling for 50 DEG C of methanol and washed.Dried at 90 DEG C 20 hours, 600 DEG C of roastings 3
Hour, obtain oxalate gas phase hydrogenation catalyst.
Use hydrogen of the procatalyst hydrogen volume content for 80%, nitrogen mixture reduction, reduction temperature 250
℃.Evaluated on the micro-reactor of 10 milliliters of loaded catalysts, using dimethyl oxalate as reaction raw materials, control reaction temperature
190 DEG C, reaction pressure 3.0MPa of degree, dimethyl oxalate mass space velocity is 1.0g/g.h, hydrogen and dimethyl oxalate molecular proportion
For 110：1, evaluation result is shown in Table 1.
Embodiment 4
With deionized water by CuSO4The 1mol/l aqueous solution is configured to, measures 157ml, weighs the silicon that mass content is 25%
Colloidal sol 160g, other preparation process of catalyst are the same as embodiment 1.
Use hydrogen of the procatalyst hydrogen volume content for 50%, nitrogen mixture reduction, reduction temperature 300
℃.Evaluated on the micro-reactor of 10 milliliters of loaded catalysts, using dimethyl oxalate as reaction raw materials, control reaction temperature
175 DEG C, reaction pressure 3.5MPa of degree, dimethyl oxalate mass space velocity is 0.4g/g.h, hydrogen and dimethyl oxalate molecular proportion
For 70：:1, evaluation result is shown in Table 1.
Embodiment 5
With deionized water by CuSO4The 1mol/l aqueous solution is configured to, measures 93ml, it is molten to weigh the silicon that mass content is 25%
Glue 120g, other preparation process of catalyst are the same as embodiment 2.
Use hydrogen of the procatalyst hydrogen volume content for 100%, nitrogen mixture reduction, reduction temperature 120
℃.Evaluated on the micro-reactor of 10 milliliters of loaded catalysts, using dimethyl oxalate as reaction raw materials, control reaction temperature
250 DEG C, reaction pressure 1.5MPa of degree, dimethyl oxalate mass space velocity is 0.7g/g.h, hydrogen and dimethyl oxalate molecular proportion
For 40:1, evaluation result is shown in Table 1.
Embodiment 6
With deionized water by Cu (NO3)23H2O is configured to the 1mol/l aqueous solution, measures 156ml, weighs white carbon
15.4g catalyst preparation process is the same as embodiment 3.
Use hydrogen of the procatalyst hydrogen volume content for 100%, nitrogen mixture reduction, reduction temperature 250
℃.Evaluated on the micro-reactor of 10 milliliters of loaded catalysts, using dimethyl oxalate as reaction raw materials, control reaction temperature
220 DEG C, reaction pressure 3.0MPa of degree, dimethyl oxalate mass space velocity is 2.0g/g.h, hydrogen and dimethyl oxalate molecular proportion
For 150:1, evaluation result is shown in Table 1.
Comparative example 1
With deionized water by Cu (NO3)2·3H2O is configured to the 1mol/l aqueous solution, measures the 175ml solution and is placed in three mouthfuls of burnings
In bottle.Add NH3·H2O196g, it is made into cupric ammine complex solution.Then white carbon 46g, mechanical agitation mixing are added.Raise water
Bath temperature ammonia still process 2~3 hours, the sediment of gained is filtered to 90 DEG C.Washing, dry, be calcined and check and rate the same embodiment of process
1, evaluation result is shown in Table 1.
Comparative example 2
With deionized water by Cu (NO3)2·3H2O is configured to the 2mol/l aqueous solution, measures the 95ml solution and is placed in three mouthfuls of burnings
In bottle.Add NH3·H2O186.2g, it is made into cupric ammine complex solution.Then white carbon 26g, mechanical agitation mixing are added.Rise
Bath temperature ammonia still process 5~6 hours, the sediment of gained is filtered to 90 DEG C.Wash, dry, being calcined and examination process is the same as implementation
Example 2, evaluation result is shown in Table 1.
Comparative example 3
With deionized water by Cu (NO3)2·3H2O is configured to the 1mol/l aqueous solution, measures the 150ml solution and is placed in three mouthfuls of burnings
In bottle.Add NH3·H2O165g, it is made into cupric ammine complex solution.Then white carbon 18g, mechanical agitation mixing are added.Raise water
Bath temperature ammonia still process 3~4 hours, the sediment of gained is filtered to 90 DEG C.Washing, dry, be calcined and check and rate the same embodiment of process
3, evaluation result is shown in Table 1.
The evaluating catalyst condition of table 1 and Activity Results
Note：DMO is dimethyl oxalate, and EG is ethylene glycol, and MG is methyl glycollate, and BDO 1,2- butanediols, ET is second
Alcohol.
Embodiment above is to illustrate embodiment disclosed by the invention, can not be interpreted as the limit to the present invention
System.In addition, in various modifications and invention listed herein method, composition change, do not departing from the scope of the present invention
Be obvious for those skilled in the art on the premise of spirit.Although a variety of specific of the present invention has been combined
Preferred embodiment has carried out specific description to the present invention, it is to be understood that, the present invention should not be limited only to these specific embodiments.
In fact, various, obvious modification should all include to obtain invention for those skilled in the art as described above
Within the scope of the invention.
Claims (11)
1. a kind of catalyst, it is characterised in that the catalyst comprises at least the component of following parts by weight：
Copper 10~60
SiO240~90.
2. catalyst according to claim 1, it is characterised in that：The parts by weight of the copper are 20~40.
3. catalyst according to claim 1, it is characterised in that：The SiO2Selected from Ludox or fume colloidal silica
In any one or two kinds, preferably fume colloidal silica, more preferably described fume colloidal silica are hydrophilic vapor phase method
White carbon.
4. the preparation method of the catalyst as described in claim 1-3 any one claims, it is characterised in that the preparation
Method comprises at least following steps：
(1) copper salt solution is prepared by formula, adds SiO2, stir, heating, obtain mixed liquor；
(2) mixed liquor for adding ammoniacal liquor in step (1), must be precipitated；
(3) by the washing of precipitate in step (2), dry, roasting.
5. the preparation method of catalyst according to claim 4, it is characterised in that the preparation method includes following characteristics
In any one or a few：
A. the temperature of heating is 80~100 DEG C in the step (1)；
B. the concentration of the ammoniacal liquor is 1%~10%；
C. the ammoniacal liquor is added by the way of being added dropwise, and the pH value for being added dropwise to solution is 6~8；
D. step (3) washing specially first uses temperature to be washed for 40-60 DEG C of ethanol or methanol, then washes；
E. the temperature of drying is 80~120 DEG C in the step (3)；
F. the temperature of roasting is 300~600 DEG C in the step (3), and the time is 3~8 hours.
6. the preparation method of catalyst according to claim 4, it is characterised in that：The concentration of copper is in the mantoquita
1~2mol/l, mantoquita are selected from copper sulphate and/or copper nitrate, preferably copper nitrate.
7. catalyst prepared by the preparation method of the catalyst as described in claim 4-6 any one.
8. the catalyst as described in claim 1-3 any one claims is used to be catalyzed preparing ethylene glycol by using dimethyl oxalate plus hydrogen
Reaction purposes.
9. catalyst according to claim 8 is used for the purposes for being catalyzed the reaction of preparing ethylene glycol by using dimethyl oxalate plus hydrogen, its
It is characterised by：The catalyst uses hydrogen reducing, reduction temperature before the reaction for preparing ethylene glycol by using dimethyl oxalate plus hydrogen
For 120~300 DEG C.
10. catalyst according to claim 8 is used for the purposes for being catalyzed the reaction of preparing ethylene glycol by using dimethyl oxalate plus hydrogen, its
It is characterised by：175~250 DEG C of the reaction temperature of the preparing ethylene glycol by using dimethyl oxalate plus hydrogen, 1.5~3.5MPa of reaction pressure.
11. catalyst according to claim 8 is used for the purposes for being catalyzed the reaction of preparing ethylene glycol by using dimethyl oxalate plus hydrogen, its
It is characterised by：The hydrogen in reaction of the preparing ethylene glycol by using dimethyl oxalate plus hydrogen and the mol ratio of oxalate are 40~200: 1, grass
Dimethyl phthalate mass space velocity is 0.4~2.0g/g.h.
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Cited By (2)
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| CN109433205A (en) * | 2018-11-28 | 2019-03-08 | 中触媒新材料股份有限公司 | A kind of copper-based catalysts of Hydrogenation of Dimethyl Oxalate and the preparation method and application thereof |
| CN115414934A (en) * | 2022-07-21 | 2022-12-02 | 朱义峰 | Solid copper-based catalyst, preparation method and application thereof, hydrogen storage system for storing and releasing hydrogen and method for storing and releasing hydrogen |
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