CN109248682A - A kind of catalyst and preparation method thereof for oxalic acid ester through hydrogenation - Google Patents
A kind of catalyst and preparation method thereof for oxalic acid ester through hydrogenation Download PDFInfo
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- CN109248682A CN109248682A CN201710571590.7A CN201710571590A CN109248682A CN 109248682 A CN109248682 A CN 109248682A CN 201710571590 A CN201710571590 A CN 201710571590A CN 109248682 A CN109248682 A CN 109248682A
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- Prior art keywords
- catalyst
- hydrogenation
- oxalic acid
- acid ester
- nanotube
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- 239000003054 catalyst Substances 0.000 title claims abstract description 107
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 150000003901 oxalic acid esters Chemical class 0.000 title claims abstract description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 31
- 239000002071 nanotube Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000000694 effects Effects 0.000 claims abstract description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 33
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 27
- 229910052710 silicon Inorganic materials 0.000 claims description 27
- 239000010703 silicon Substances 0.000 claims description 27
- 239000010949 copper Substances 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 230000009467 reduction Effects 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000012691 Cu precursor Substances 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 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 4
- 238000001035 drying Methods 0.000 claims description 4
- 150000002431 hydrogen Chemical group 0.000 claims description 4
- 239000002086 nanomaterial Substances 0.000 claims description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 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
- 239000011148 porous material Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 230000005484 gravity Effects 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 abstract description 27
- 238000000034 method Methods 0.000 abstract description 14
- -1 hydrogen ester Chemical class 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000010276 construction Methods 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000004434 industrial solvent Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000010792 warming 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
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The catalyst and preparation method thereof that the invention discloses a kind of for oxalic acid ester through hydrogenation, synthesis for the first time has the catalyst of the tiny balloon special construction of nanotube assembling and is used for Hydrogenation of Dimethyl Oxalate system, its special construction is enriched with hydrogen in reaction process in catalytic inner, to solve the problems, such as required higher hydrogen partial pressure or high hydrogen ester ratio in hydrogenation reaction；In addition, hydrogenation reaction depth can be regulated and controled by the length for changing nanotube on catalyst, so that the distribution situation of product is controlled, highly selective acquisition target product.Catalyst prepared by this method is in lower H2Excellent Hydrogenation of Dimethyl Oxalate activity and glycol selectivity are still shown under/DMO charge ratio, are reduced hydrogen circulation amount, have been saved power cost and equipment cost；Meanwhile can flexibly modulation ethylene glycol and methyl glycollate selectivity, long service life, preparation cost is low, have very high industrial prospect and application value.
Description
Technical field
The invention belongs to gas phase esters hydrogenation catalyst technical fields, more particularly to a kind of urging for oxalic acid ester through hydrogenation
Agent and preparation method thereof.
Background technique
Ethylene glycol is widely used in polyester and its downstream product, prevents as a kind of important industrial chemicals or solvent
Freeze in the production such as agent, lubricating oil, wide market.With synthesis gas through carbon monoxide coupling dimethyl oxalate, oxalic acid diformazan
Ester and the technique for adding hydrogen preparing ethylene glycol, have that Atom economy is high, reaction condition is mild, product selectivity is high, environmentally protective etc.
Feature is one of the important path with Non oil-based route synthesizing glycol.Wherein, preparing ethylene glycol by using dimethyl oxalate plus hydrogen is the work
The core link of skill.
Copper-based catalysts achieve preferable activity and selectivity in the reaction system, but the ratio of hydrogen ester needed for reaction feed
The difficult problem of higher and product distribution regulation is still difficult to obtain effective solution.Currently, dimethyl oxalate (DMO) hydrogenation reaction into
Large excess of hydrogen (H is needed in material2/ DMO molar feed ratio is generally between 80 to 200) to obtain higher activity and second two
Alcohol yield.However in industrial application, excessively high hydrogen ester ratio will lead to hydrogen circulation amount increasing, improves and joins to equipment such as compressors
Several requirement, so that equipment cost needed for the technique and power cost greatly increase.Therefore, it is copper-based to design novel high activity
Catalyst makes Hydrogenation of Dimethyl Oxalate reaction also can achieve the highly selective of ethylene glycol under conditions of low hydrogen ester ratio and receive
Rate is the key that optimum synthesis gas preparing ethylene glycol technology.
Summary of the invention
The purpose of the present invention is being directed to the deficiencies in the prior art, a kind of catalyst for oxalic acid ester through hydrogenation is provided
And preparation method thereof.Synthesis for the first time has the catalyst of the hollow sphere special construction of nanotube assembling and is used for oxalic acid diformazan
Ester through hydrogenation system, special construction is enriched with hydrogen in reaction process in catalytic inner, to solve in hydrogenation reaction
The problem of required higher hydrogen partial pressure or high hydrogen ester ratio；In addition, can regulate and control to add hydrogen by the length for changing nanotube on catalyst
Reaction depth, so that the distribution situation of product is controlled, highly selective acquisition target product.Catalyst prepared by this method exists
Lower H2Excellent Hydrogenation of Dimethyl Oxalate activity and glycol selectivity are still shown under/DMO charge ratio, reduce hydrogen
Internal circulating load has saved power cost and equipment cost；Meanwhile can flexibly modulation ethylene glycol and methyl glycollate selectivity, make
Long with the service life, preparation cost is low, has very high industrial prospect and application value.
The present invention is achieved by the following technical solutions:
Catalyst for oxalic acid ester through hydrogenation of the invention, main chemical compositions are as follows: copper and silica, wherein copper accounts for catalysis
The 5-60wt.% of agent weight, silica account for the 40-95wt.% of catalyst weight；Structure is hollow sphere over-assemble nanotube,
The specific surface area of the catalyst is 450-500m2/ g, average Kong Rongwei 0.5-1cm3/ g, average pore size 5-6nm；The sky
The diameter of bulbus cordis is 50-450nm, wall thickness 10-20nm；The nanotube is vertically set on hollow ball surface, caliber 3-
5nm, pipe range 40-300nm.
The specific surface area of the catalyst is preferably 460-470m2/ g, it is preferably 0.7-0.8cm that average hole, which holds,3/ g, it is average
Aperture is preferably 5.1-5.5nm；
The diameter of the hollow sphere is preferably 200-350nm, and wall thickness is preferably 10-15nm.
The nanotube is vertically set on hollow ball surface, and caliber is preferably 3.5-4nm, and pipe range is preferably 180-230nm.
Another aspect of the present invention, a kind of preparation method of the catalyst for oxalic acid ester through hydrogenation, comprising the following steps:
Step 1, it using silicon source as raw material, is mixed with the alkaline agent of different volumes ratio and water, the body of alkaline agent and water
Product ratio is 0.13-1.9, the hyperpure silicon ball material that preparation has well-regulated geometry, partial size is 50-450nm, temperature 30-
80 DEG C, pH 8.5-13.5.
The silicon source is sodium metasilicate, silica solution or ethyl orthosilicate.
The alkaline agent is ammonium hydroxide, ammonium chloride or sodium hydroxide.
Step 2, obtained hyperpure silicon ball material is uniformly mixed with copper precursor salt solution, adding in terms of metal oxide
The content for entering copper is 5-60wt.%, and microballoon constantly dissolves under alkaline environment, and copper precursor salt solution is reacted and gradually sunk
Product curls to form tubular structure, carries out hydro-thermal process 5-30h under alkaline condition, hydro-thermal process temperature is 120-180 DEG C, dry
The hollow sphere nano material that group is filled with nanotube is obtained after roasting.
The copper precursor salt solution is copper acetate or copper nitrate.
Step 3, the hollow sphere nano material that obtained group is filled with nanotube is dried into 4-12h at 50-120 DEG C；Then
3-12h is roasted at 300-700 DEG C, the atmosphere of roasting is air, and air mass flow needed for every gram of catalyst roasts is 6-150mL/
min；It finally restores to obtain the catalyst in a manner of online in-situ reducing, reduction temperature is 150-400 DEG C, and reducing atmosphere is
Hydrogen, hydrogen flowing quantity needed for every gram of catalyst reduction are 40-200mL/min.
The drying means is usual drying method or vacuum drying method.
Preferably, the silicon source is ethyl orthosilicate.
Preferably, the alkaline agent is ammonium hydroxide.
Preferably, the copper precursor salt solution is copper nitrate.
Preferably, the drying means is vacuum drying method.
Volume ratio in the step 1 by adjusting alkaline agent and water controls the size of ultrapure silicon ball.
By adjusting the length of hydrothermal conditions control nanotube in the step 2, hydrothermal conditions are preferred
For 20-30h.
Another aspect of the present invention, the catalyst for oxalic acid ester through hydrogenation are hydrogenated to second two in catalysis oxalate
Application on alcohol, in the case where guaranteeing that ethylene glycol yield is higher than 95%, feedstock mole charge ratio can be down to H2/DMO
=20, reaction temperature is 160-220 DEG C, reaction pressure 1.5-3MPa, and mass space velocity is 0.5-5h when liquid-1；When in catalyst
Primary product is methyl glycollate when nanotube length is 40-60nm, the master when nanotube length is 60-300nm in catalyst
Wanting product is ethylene glycol.
The invention has the advantages and beneficial effects that:
1, the present invention is in low hydrogen ester ratio (H2/ DMO=20) preparing ethylene glycol by using dimethyl oxalate plus hydrogen reaction in show Zhuo
Activity and selectivity more makes required hydrogen circulation amount decline 75%；
2, the hydrogenation catalyst with special construction of the invention can by change hollow sphere on nanotube length come
The product distribution of flexible modulation methyl glycollate, ethylene glycol, it can the synthesis condition of catalyst is adjusted according to target product；
3, the present invention has in the hydrogenation catalyst of special construction, nanotube of the active component uniform load on hollow sphere
At tube wall and hollow ball surface, therefore show excellent stability.
Detailed description of the invention
Transmission electron microscope picture before the reduction of Fig. 1 hydrogenation catalyst and after reduction, wherein A, B are transmission electron microscope picture before restoring, C, D
For transmission electron microscope picture after reduction；
Fig. 2 is the transmission electron microscope effect picture before the catalyst reduction synthesized under different hydrothermal conditions, wherein at hydro-thermal
The reason time is A:5h, B:10h, C:15h, D:20h, E:25h, F:30h；Scale: 100nm；
Fig. 3 is the transmission electron microscope effect picture after the catalyst reduction synthesized under different hydrothermal conditions, wherein at hydro-thermal
Manage time A:5h, B:10h, C:15h, D:20h, E:25h, F:30h；Scale: 20nm；
Fig. 4 is the nanotube caliber statistical chart of catalyst；
Fig. 5 is that the catalyst life of preparing ethylene glycol by using dimethyl oxalate plus hydrogen is observed；
Fig. 6 is the catalytic performance of catalyst of the present invention and existing catalyst under different hydrogen/dimethyl oxalate charge ratio
Evaluation；
Fig. 7 is X-ray diffraction (XRD) map of catalyst of the present invention.
Specific embodiment
Present invention is further described in detail with specific embodiment with reference to the accompanying drawing.Under it should be understood that
State embodiment be it is illustrative, be not restrictive, cannot be limited the scope of protection of the present invention with following embodiments.Following reality
It is water-soluble that apply required raw material in example and comparative example, which be commercially available, described alkaline agent (ammonium hydroxide, ammonium chloride, sodium hydroxide),
Liquid.
Embodiment 1:
The preparation of ultrapure silicon ball:
Ethyl orthosilicate 80g is weighed, with stirring and dissolving in 200mL ethyl alcohol, obtains clear solution A；Measure ammonium hydroxide 132mL with
98mL deionized water, 86mL ethyl alcohol are uniformly mixed, and obtain clear solution B；Two kinds of solution of A, B are mixed and stirred at 40 DEG C
5h, obtain surface uniformly, the ultrapure silicon ball solution of uniform particle diameter.
Catalyst preparation:
Gerhardite 18g is weighed, dissolution is uniformly mixing to obtain with 200mL deionized water together with ammonium hydroxide 80mL
Then ultrapure silicon ball solution is added dropwise (1 drop per second), and stirs 1h at 60 DEG C by clear solution, obtain evenly dispersed
Solution.Solution is placed in closed container, the hydro-thermal process 30h at 150 DEG C, isolates solid matter and vacuum is dry at 80 DEG C
Dry 6h roasts 6h at 500 DEG C, obtains catalyst.
Evaluating catalyst:
The reaction of gas phase Hydrogenation of Dimethyl Oxalate carries out in fixed bed reactors in the present invention.The catalyst that roasting is finished
Tabletting, and it is sieved into the particle of 40-60 mesh size, it weighs 0.58g and is placed in isothermal reactor, and be passed through 10%H2/N2In atmosphere
It is restored at 300 DEG C, the recovery time 4 hours.190 DEG C of reaction temperature are cooled to after reduction, simultaneously by dimethyl oxalate vaporization
It is mixed into reaction tube with pure hydrogen, hydrogen ester ratio is 20, and dimethyl oxalate liquid phase quality air speed is 3h-1, carried out at 3MPa
Reaction.Product is analyzed using gas-chromatography to obtain dimethyl oxalate (DMO), ethylene glycol (EG), methyl glycollate (MG)
With the ingredient of ethyl alcohol (EtOH), and analyze obtain dimethyl oxalate conversion ratio and each product selectivity.Evaluating catalyst
It the results are shown in Table 1.Have from X-ray diffraction (XRD) map of Fig. 7 catalyst of the present invention it can be seen that 2 θ=22 ° one wider
Diffraction maximum, which is attributed to unformed SiO2Characteristic diffraction peak.Characteristic diffraction peak at 2 θ=37.0 ° is Cu2O(111)
Diffraction maximum (JCPDS 34-1354), and it is metallic copper (Cu) that 2 θ, which are characteristic diffraction peak at 43.3 °, 50.6 ° and 74.1 °,
Diffraction maximum (JCPDS 65-9743), these peaks are weaker and wide in range, illustrate Cu and Cu2O highly divides in reduction rear catalyst
It dissipates, good catalyst activity.
Comparative example 1:
The preparation of ultrapure silicon ball:
The preparation method is the same as that of Example 1 for ultrapure silicon ball.
Catalyst preparation:
Copper dichloride dihydrate 13g is weighed, dissolution is uniformly mixing to obtain with 200mL deionized water together with ammonium hydroxide 80mL
Then ultrapure silicon ball solution is added dropwise (1 drop per second), and stirs 1h at 60 DEG C by clear solution, obtain evenly dispersed
Solution.Solution is placed in closed container, the hydro-thermal process 30h at 150 DEG C, isolates solid matter and vacuum is dry at 80 DEG C
Dry 6h roasts 6h at 500 DEG C, obtains catalyst.
Evaluating catalyst:
Evaluating catalyst method the results are shown in Table 1 with embodiment 1.
Comparative example 2:
The preparation of ultrapure silicon ball:
The preparation method is the same as that of Example 1 for ultrapure silicon ball.
Catalyst preparation:
Three hydration copper acetate 22g are weighed, dissolution is uniformly mixing to obtain with 200mL deionized water together with ammonium hydroxide 80mL
Then ultrapure silicon ball solution is added dropwise (1 drop per second), and stirs 1h at 60 DEG C by clear solution, obtain evenly dispersed
Solution.Solution is placed in closed container, the hydro-thermal process 30h at 150 DEG C, isolates solid matter and vacuum is dry at 80 DEG C
Dry 6h roasts 6h at 500 DEG C, obtains catalyst.
Evaluating catalyst:
Evaluating catalyst method the results are shown in Table 1 with embodiment 1.
Comparative example 3:
The preparation of ultrapure silicon ball:
The preparation method is the same as that of Example 1 for ultrapure silicon ball.
Catalyst preparation:
Salzburg vitriol 19g is weighed, dissolution is uniformly mixing to obtain with 200mL deionized water together with ammonium hydroxide 80mL
Then ultrapure silicon ball solution is added dropwise (1 drop per second), and stirs 1h at 60 DEG C by clear solution, obtain evenly dispersed
Solution.Solution is placed in closed container, the hydro-thermal process 30h at 150 DEG C, isolates solid matter and vacuum is dry at 80 DEG C
Dry 6h roasts 6h at 500 DEG C, obtains catalyst.
Evaluating catalyst:
Evaluating catalyst method the results are shown in Table 1 with embodiment 1.
Comparative example 4
The preparation of ultrapure silicon ball:
The preparation method is the same as that of Example 1 for ultrapure silicon ball.
Catalyst preparation:
Gerhardite 18g is weighed, dissolution is uniformly mixing to obtain with 200mL deionized water together with ammonium hydroxide 80mL
Then ultrapure silicon ball solution is rapidly joined and (is added at continuous water column), and stirs 1h at 60 DEG C by clear solution, obtain uniformly
The solution of dispersion.Solution is placed in closed container, the hydro-thermal process 30h at 150 DEG C isolates solid matter and at 80 DEG C
It is dried in vacuo 6h, 6h is roasted at 500 DEG C, obtains catalyst.
Evaluating catalyst:
Evaluating catalyst method the results are shown in Table 1 with embodiment 1, it will thus be seen that using copper nitrate as mantoquita presoma, and
The high conversion rate of dimethyl oxalate (DMO) is up to 100% when ultrapure silicon ball solution to be added dropwise to (1 drop per second), ethylene glycol (EG)
Selectivity be 98%.The estimation of stability of embodiment 1 is shown in Fig. 5, it can be seen that catalyst of the invention shows excellent steady
It is qualitative.
Table 1 uses the evaluating catalyst of distinct methods and precursor preparation
Embodiment 2-5:
Method for preparing catalyst and evaluation condition are same as Example 1, by the additional amount point for changing Gerhardite
The catalyst (5wt%, 10wt.%, 30wt.%, 40wt.%) of different Cu load capacity is not obtained, and catalyst evaluation of result is shown in Table
2, it can be seen that when Cu load capacity is greater than 20wt.%, the selectivity of ethylene glycol is higher than 90%.
The catalyst performance evaluation of 2 different loads amount of table
Embodiment 6-10:
Method for preparing catalyst and evaluation condition are same as Example 1, and the time by changing hydro-thermal process respectively obtains
Group is filled with the hollow ball catalyst of different length nanotube, and the length of nanotube is determined by TEM, sees Fig. 2 and Fig. 3, nanotube
Caliber is shown in Fig. 4.Catalyst evaluation of result is shown in Table 3, it can be seen that the primary product when nanotube length is 40-60nm in catalyst
For methyl glycollate, when nanotube length is 60-300nm in catalyst, primary product is ethylene glycol.
The catalyst performance evaluation of the different nanotube lengths of table 3
Embodiment 11-14:
The catalyst evaluated is identical as the catalyst in embodiment 1, changes the reaction temperature in reaction condition, other are anti-
It answers condition constant, obtains embodiment 11-14, catalyst evaluation of result is shown in Table 4, it can be seen that when reaction temperature is 190-200 DEG C,
Catalyst is up to 95% or more to the selectivity of ethylene glycol.
Catalyst performance evaluation at a temperature of 4 differential responses of table
Comparative example 5
It weighs Gerhardite 18g and deionized water stirring and dissolving is added, be slowly added to 28% ammonia of appropriate amount later
Water is made into copper ammon solution and adds a certain amount of deionized water.Then 30% silicon sol solution 77g is added into copper ammon solution,
Persistently stir aging 4 hours.The ammonia in 80 DEG C of removal solution is warming up to pH=6-7.Filter to isolate solid matter and 80
It is dried in vacuo 6h at DEG C, roasts 6h at 500 DEG C, the document of obtaining over (Gong J, et al.Synthesis of Ethanol
via Syngas on Cu/SiO2Catalysts with Balanced Cu0-Cu+Sites.Journal Of the
American Chemical Society 134,13922-13925(2012)；Chen L,et al.Cu/SiO2Catalysts
Prepared by the Ammonia-Evaporation Method:Texture,Structure,and Catalytic
Performance in Hydrogenation of Dimethyl Oxalate to Ethylene Glycol.Journal
Of Catalysis 257,172-180 (2008)) and patent reported in cross existing catalyst.
Existing catalyst in catalyst of the present invention in embodiment 1 and comparative example 5 is evaluated under different hydrogen ester ratios,
It is identical in his reaction condition and embodiment 1, as a result as shown in Fig. 6 in attached drawing, it can be seen that guaranteeing that ethylene glycol yield is higher than
In the case where 95%, feedstock mole charge ratio can be down to H2/ DMO=20.
It is the advantages of catalyst in the present invention, in low hydrogen ester ratio (H2/ DMO=20) prepared by dimethyl oxalate plus hydrogen second two
Brilliant activity and selectivity is shown in alcohol reaction, makes required hydrogen circulation amount decline 75%；Of the invention has special knot
The hydrogenation catalyst of structure can be by changing the length of nanotube on hollow sphere come the production of flexible modulation methyl glycollate, ethylene glycol
Object distribution, it can the synthesis condition of catalyst is adjusted according to target product；The present invention has the hydrogenation catalyst of special construction
In agent, active component (copper particle) uniform load is shown at the nanometer tube wall on hollow sphere and hollow ball surface
Excellent stability.
Illustrative description has been done to the present invention above, it should explanation, the case where not departing from core of the invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent replacement of creative work equal
Fall into protection scope of the present invention.
Claims (10)
1. a kind of catalyst for oxalic acid ester through hydrogenation, it is characterised in that: main chemical compositions are as follows: copper and silica, wherein copper
The 5-60wt.% of catalyst weight is accounted for, silica accounts for the 40-95wt.% of catalyst weight；Structure is received for hollow sphere over-assemble
Mitron, the specific surface area of the catalyst are 450-500m2/ g, average Kong Rongwei 0.5-1cm3/ g, average pore size 5-6nm；Institute
The diameter for stating hollow sphere is 50-450nm, wall thickness 10-20nm；The nanotube is vertically set on hollow ball surface, and caliber is
3-5nm, pipe range 40-300nm.
2. a kind of catalyst for oxalic acid ester through hydrogenation according to claim 1, it is characterised in that: the copper is being catalyzed
The specific gravity accounted in agent is preferably 10-40wt.%, and silica accounts for the 60-90wt.% of catalyst weight.
3. a kind of catalyst for oxalic acid ester through hydrogenation according to claim 1, it is characterised in that: the ratio of the catalyst
Surface area is preferably 460-470m2/ g, it is preferably 0.7-0.8cm that average hole, which holds,3/ g, average pore size are preferably 5.1-5.5nm.
4. a kind of catalyst for oxalic acid ester through hydrogenation according to claim 1, it is characterised in that: the hollow sphere it is straight
Diameter is preferably 200-350nm, and wall thickness is preferably 10-15nm.
5. a kind of catalyst for oxalic acid ester through hydrogenation according to claim 1, it is characterised in that: the nanotube is vertical
It is arranged in hollow ball surface, caliber is preferably 3.5-4nm, and pipe range is preferably 180-230nm.
6. a kind of preparation method of the catalyst for oxalic acid ester through hydrogenation as described in claim 1, it is characterised in that: including with
Lower step,
Step 1, it using silicon source as raw material, is mixed with the alkaline agent of different volumes ratio and water, the volume ratio of alkaline agent and water
Example is 0.13-1.9, prepares the well-regulated geometry of tool, the hyperpure silicon ball material that partial size is 50-450nm, 30-80 DEG C of temperature,
PH is 8.5-13.5；
The silicon source is sodium metasilicate, silica solution or ethyl orthosilicate；
The alkaline agent is ammonium hydroxide, ammonium chloride or sodium hydroxide；
Step 2, obtained hyperpure silicon ball material is uniformly mixed with copper precursor salt solution, the addition copper in terms of metal oxide
Content be 5-60wt.%, microballoon constantly dissolves under alkaline environment, and copper precursor salt solution, which is reacted and gradually deposited, curls up
Curved to carry out hydro-thermal process 5-30h under alkaline condition at tubular structure, hydro-thermal process temperature is 120-180 DEG C, drying and roasting
The hollow sphere nano material that group is filled with nanotube is obtained afterwards；
The copper precursor salt solution is copper acetate or copper nitrate；
Step 3, the hollow sphere nano material that obtained group is filled with nanotube is dried into 4-12h at 50-120 DEG C；Then exist
3-12h is roasted at 300-700 DEG C, the atmosphere of roasting is air, and air mass flow needed for every gram of catalyst roasts is 6-150mL/
min；It finally restores to obtain the catalyst in a manner of online in-situ reducing, reduction temperature is 150-400 DEG C, and reducing atmosphere is
Hydrogen, hydrogen flowing quantity needed for every gram of catalyst reduction are 40-200mL/min.
7. a kind of preparation method of catalyst for oxalic acid ester through hydrogenation according to claim 6, it is characterised in that: pass through
Adjust the length of hydrothermal conditions control nanotube.
8. a kind of preparation method of catalyst for oxalic acid ester through hydrogenation according to claim 7, it is characterised in that: described
Hydrothermal conditions be preferably 20-30h.
9. being hydrogenated to answering on ethylene glycol in catalysis oxalate for the catalyst of oxalic acid ester through hydrogenation as described in claim 1
With.
10. the catalyst according to claim 9 for oxalic acid ester through hydrogenation is hydrogenated to ethylene glycol in catalysis oxalate
Application, it is characterised in that: in the case where guaranteeing that ethylene glycol yield is higher than 95%, feedstock mole charge ratio can be down to
H2/ DMO=20, reaction temperature are 160-220 DEG C, reaction pressure 1.5-3MPa, and mass space velocity is 0.5-5h when liquid-1；When urging
Primary product is methyl glycollate when nanotube length is 40-60nm in agent, when nanotube length is 60- in catalyst
Primary product is ethylene glycol when 300nm；Copper in catalyst is with Ni metal and Cu2The form high uniformity of O is scattered in catalyst
In, improve the activity of catalyst.
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| CN201710571590.7A CN109248682B (en) | 2017-07-13 | 2017-07-13 | Catalyst for oxalate hydrogenation and preparation method thereof |
| US16/628,986 US10894756B2 (en) | 2017-07-13 | 2018-03-26 | Method for catalytically hydrogenating oxalates |
| PCT/CN2018/080544 WO2019011005A1 (en) | 2017-07-13 | 2018-03-26 | Method for catalytically hydrogenating oxalate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114433130A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Embedded copper oxide nanotube catalyst and preparation method and application thereof |
| CN116060024A (en) * | 2021-10-31 | 2023-05-05 | 中国石油化工股份有限公司 | Ester hydrogenation catalyst, preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101856615A (en) * | 2010-06-04 | 2010-10-13 | 天津大学 | Catalyst used for hydrogenation of oxalate for preparing ethylene glycol and preparation method thereof |
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2017
- 2017-07-13 CN CN201710571590.7A patent/CN109248682B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101856615A (en) * | 2010-06-04 | 2010-10-13 | 天津大学 | Catalyst used for hydrogenation of oxalate for preparing ethylene glycol and preparation method thereof |
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| Title |
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| YUAN SHENG 等: "Structured Assemblages of Single-Walled 3d Transition Metal Silicate Nanotubes as Precursors for Composition-Tailorable Catalysts", 《CHEMISTRY OF MATERIALS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114433130A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Embedded copper oxide nanotube catalyst and preparation method and application thereof |
| CN114433130B (en) * | 2020-10-31 | 2023-07-28 | 中国石油化工股份有限公司 | Embedded copper oxide nanotube catalyst and preparation method and application thereof |
| CN116060024A (en) * | 2021-10-31 | 2023-05-05 | 中国石油化工股份有限公司 | Ester hydrogenation catalyst, preparation method and application thereof |
| CN116060024B (en) * | 2021-10-31 | 2024-05-10 | 中国石油化工股份有限公司 | Ester hydrogenation catalyst, preparation method and application thereof |
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