CN108654616A - The modification of hydrogenation of oxalate for preparing ethylene glycol catalyst carrier and catalyst and application - Google Patents
The modification of hydrogenation of oxalate for preparing ethylene glycol catalyst carrier and catalyst and application Download PDFInfo
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- CN108654616A CN108654616A CN201710191221.5A CN201710191221A CN108654616A CN 108654616 A CN108654616 A CN 108654616A CN 201710191221 A CN201710191221 A CN 201710191221A CN 108654616 A CN108654616 A CN 108654616A
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- catalyst
- carrier
- oxalate
- hydrogenation
- ethylene glycol
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 24
- 230000004048 modification Effects 0.000 title claims description 8
- 238000012986 modification Methods 0.000 title claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910002012 Aerosil® Inorganic materials 0.000 claims abstract description 22
- 239000010949 copper Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 229910052682 stishovite Inorganic materials 0.000 claims description 8
- 229910052905 tridymite Inorganic materials 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000004448 titration Methods 0.000 claims description 6
- -1 hydrogen ester Chemical class 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000012266 salt solution Substances 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical class CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229960004063 propylene glycol Drugs 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- OFNKLDDSWHOKLQ-UHFFFAOYSA-N N=NC=NN.N=NC=NN.C(C(=O)O)(=O)O Chemical compound N=NC=NN.N=NC=NN.C(C(=O)O)(=O)O OFNKLDDSWHOKLQ-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 150000003901 oxalic acid esters Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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, 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, using aerosil as carrier, is modified carrier by heat-treating methods using metallic copper as active component.The carrier of catalyst 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
The purposes of ethylene glycol is very extensive, is important industrial chemicals, is mainly used for PET industry, while still production tree
The important raw and processed materials of all multi-products such as fat, lubricant, plasticizer, paint, adhesive, surfactant.It main of ethylene glycol
Production technology is that epoxyethane water is legal, this method is to makethe oxidation of ethylene to ethylene oxide, the rehydrated generation second of ethylene oxide
Glycol, this method are larger to petroleum resources dependency degree.But in China due to the source relative abundance of synthesis gas, in recent years, by closing
Ethylene glycol is prepared at gas to have gradually developed, and is paid close attention to by more and more researchers.
It includes two steps to prepare ethylene glycol mainly by synthesis gas, is that oxalate is made in synthesis gas first, then will be careless
Acid esters Hydrogenation is at ethylene glycol.Wherein hydrogenation of oxalate for preparing ethylene glycol the step for the qualitative effects of final products ethylene glycol compared with
Greatly.This is because hydrogenation of oxalate for preparing ethylene glycol, is a cascade reaction, oxalate adds hydrogen to obtain methyl glycollate, connects first
Plus hydrogen obtain ethylene glycol, and ethylene glycol can further plus hydrogen obtains ethyl alcohol, while excessive hydrogenation also generate 1,2 propylene glycol and
Other by-products such as 1,2 butanediols.So catalyst plays highly important role in this step.
The ammonia still process method that more early proposes of Yu Bu companies of Japan prepare using silicon as carrier Cu bases catalyst (US 4,229,
591) performance, showed in the reaction of hydrogenation of oxalate for preparing ethylene glycol is more excellent, thus obtains a large amount of concern.In recent years,
Everybody is to Cu in catalyst0And Cu+The ratio of two kinds of activated centres position and respective effect are to catalyst activity, selective shadow
It rings, the selection of the carrier of catalyst, the preparation method of catalyst, and adds the influence etc. of auxiliary agent, all done a large amount of research
Work.But certain problem is still had during commercial Application to the catalyst, the glycol selectivity of catalyst is still
It is so relatively low, its application in downstream PET industry is significantly limited, while the cost of catalyst is also higher.
Using aerosil as catalyst carrier, with most of catalyst phases using Ludox as carrier
Than having raw material sources extensive, the features such as small is polluted in catalyst production.But this even particle size distribution of aerosil is received
Rice SiO 2 powder, the characteristics of due to its preparation process so that a large amount of polarity groups, such as hydroxyl are contained in its surface, wherein
Excessive hydroxyl makes it when as catalyst carrier, will produce certain influence to the performance of catalyst.The present invention is for upper
Problem is stated, a kind of relatively simple easy support modification method is proposed, to eliminate the excessive hydroxyl in aerosil surface
Polarity group.
Invention content
The technical problem to be solved by the present invention is to be directed to, aerosil carrier surface group is complicated, nature difference is huge
Big feature makes catalyst prepared by aerosil carrier all have higher second two by being heat-treated modified method
Alcohol selectivity and stability.The catalyst is using Cu as active component, SiO2For carrier, preferred aerosil carrier and through heat
Handle modified aerosil carrier.
The surface of aerosil is since the characteristics of its synthesis technology, contains great amount of hydroxy group isopolarity group, when as urging
When agent carrier, part of hydroxyl can generate strong interaction with active metal, and then influence the performance of catalyst.Due to gas phase two
Silica is mostly used for the additive of rubber, so traditional aerosil carrier surface modification, is mostly focused on elimination
Its polarity group, to change its hydrophily and reduce its grain diameter (CN103059572A.).And the present invention is used as it and urges
The purposes feature of agent carrier reduces the part of hydroxyl on its surface, but not by carrying out heat treatment modification to aerosil
Change its hydrophily, can suitably reduce the action intensity in catalyst between active metal copper and carrier, and then make catalyst
Metal dispersity increases, and the hydrogenation activity of catalyst is improved.
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 places it in the fluidized-bed reactor of quartz material, and reactor is in vertical state in tube furnace, in reactor
Bottom is passed through dry inert gas (nitrogen or argon gas), and it is 800 DEG C~1200 DEG C to keep temperature of reactor, roasts 1~10h,
In roasting process, it is continually fed into dry inert gas, to keep aerosil powder to be in uniform flow state.
The specific practice that the hydroxy radical content of carrier measures is：It weighs sample 2.5g and is put into 500ml (accurately to 0.0002g) and pour
In cup.250ml sodium chloride solutions are added to stir evenly.The pH value that test solution is adjusted with hydrochloric acid is 4, and the soda acid amount that this step consumes is not
It calculates.Then above-mentioned test solution is titrated with the speed of 2~3 drop per second with 0.1~1mol/L standard solution of sodium hydroxide, is dripped
Surely the pH value for arriving solution is equal to 9, and is kept for 5 minutes after not changing being titration end-point.Carrier is calculated according to the alkali number of consumption
Hydroxyl quantity.Calculation formula is：Wherein N is the silicone hydroxyl number of unit quality, and V is consumption
The volume (units/ml) of 0.lmol/L standard solution of sodium hydroxide, m are sample quality (unit g).
The hydroxyl quantity that aerosil titration used in the present invention measures is 3~5 × 1020A/g, at heat
It is 1~3 × 10 to manage the hydroxyl quantity that the modification aerosil of modified acquisition is measured through titration20A/g.
A kind of catalyst of hydrogenation of oxalate for preparing ethylene glycol, it is characterised in that：It is using Ni metal as active component, with modification
Aerosil afterwards is carrier；The mass percentage of each component is in the catalyst：Active metal Cu be 10~
70%, surplus is carrier silicas.
The preparation process of catalyst of the present invention is：Certain density copper salt solution and ammonium hydroxide are mixed first, prepared
At uniform copper ammon solution；Then modified aerosil is added in above-mentioned solution and is sufficiently stirred；Then it heats up again
Remove the ammonia in solution；Most afterwards through washing, roast, mill and tabletting obtain catalyst.
The reactivity worth evaluation of programme of catalyst of the present invention is：By 1.0g. Catalyst packings in continuous fixed bed reaction
In device, it is filled with 10mm quartz sands up and down.Catalyst reduction uses pure hydrogen to be warming up to 230 under normal pressure with the rate of 1~2 DEG C/min
DEG C reduction, hydrogen flow rate 100mL/min, keep 4h after be down to reaction temperature.Then H2Oxalic acid diformazan is conveyed with constant-flux pump
Ester or its methanol solution are reacted after vaporizer is sufficiently mixed into reactor.Product is analyzed with gas-chromatography, color
Spectrum column is 30m FFAP type polarity capillary columns, and hydrogen flame detector (FID) detects reaction raw materials and product.
Catalyst Conversion and selective computational methods are as follows：
M refers to reaction product, such as ethylene glycol in above formula
(EG), methyl glycollate (MG), 2- methyl ethyl ethers (2-MEO), 1,2- propylene glycol (1,2-POD), 1,2- butanediols (1,2-
BOD) etc..
The present invention can make the catalyst prepared as carrier by it by being simply heat-treated to aerosil
Oxalate hydrogenation activity be greatly improved, while the stability of catalyst is also preferable.
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 heat-treating methods to carrying
Body is modified.The carrier of catalyst 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：
The aerosil sample that two parts of quality are 50g is weighed respectively, is placed it in fluidized-bed reactor, is being reacted
Device bottom is passed through dry nitrogen so that aerosil to be modified is in flow regime, then heats to 1000 DEG C, point
Not Bei Shao 3h and 6h, and be labeled as SiO2- A and SiO2-B。
Embodiment 2
Weigh 36.3g Cu (NO3)2·3H2O is dissolved in 500mL deionized waters.Measure above-mentioned Cu (NO3)2Solution
157mL is poured into 250mL beakers, and Cu (NO are then added in ammonium hydroxide (25wt%) while stirring3)2In solution, it is molten to be configured to cuprammonium
Liquid, the final pH of solution is between 9-10.Then by modified SiO2- A is added in copper ammon solution, and in 35 DEG C of water-baths
Aging 4 hours.90 DEG C are then heated to, and maintains 2.5 hours at such a temperature to steam the ammonia in solution.Finally incite somebody to action
To sediment be filtered, after washing to filtrate pH is 7 or so, gained worry cake is placed in 120 DEG C of baking ovens it is 12 hours dry,
It is roasted 4 hours through 450 DEG C again after taking-up.Obtained material is crushed and is screened by 20-40 mesh mesh screens, catalyst A is labeled as：
20wt%Cu/SiO2。
Embodiment 3
Preparation process is with embodiment 2, but used carrier is changed to SiO2-B.Catalyst B is prepared：20wt%Cu/
SiO2。
Comparative example 1
Preparation process is with embodiment 1, but calcination temperature is 700 DEG C, roasts 6h, the carrier indicium of acquisition is SiO2-C。
Comparative example 2
Preparation process is with embodiment 2, but used carrier is changed to SiO2-C.Catalyst C is prepared：20wt%Cu/
SiO2。
Comparative example 3
Preparation process is with embodiment 2, but used carrier is changed to non-modified aerosil (SiO2-D).It prepares
Obtain catalyst D：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 1000 DEG C of heat treatment, hence it is evident that real better than the unmodified comparison of carrier
Apply the catalyst D of example 3.Wherein use SiO2- A has the optimal second up to 95.2% as the catalyst of the embodiment 2 of carrier
Glycol selectivity, and close to 100% dimethyl oxalate conversion ratio.Simultaneously it can be seen that with the catalyst of support heat-tr eatment 6h,
The catalyst compared to vehicle treated 3h such as its glycol selectivity is not obviously improved, when this illustrates to extend the processing of carrier
Between, the performance of its catalyst prepared cannot be made to obtain constantly improve.In table 1 comparative example 2 statistics indicate that, when carrier
When heat treatment temperature is relatively low, the modified effect of carrier is not obvious.
Embodiment 5：
By embodiment 1 and comparative example 1 and non-modified aerosil, its surface is measured using titration
Hydroxyl quantity.Acquired results are listed in table 2.
The adsorbed hydroxyl content of 2. different carriers of table
As seen from Table 2, the adsorbed hydroxyl content of the carrier after 1000 DEG C of heat treatment has different degrees of decline.
But when treatment temperature is relatively low, the adsorbed hydroxyl content of carrier does not change, this is also by comparative example 2 in table 1
Data with 3 are proved.
Embodiment 6：
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 3.
The dispersion degree of the metallic copper of catalyst prepared by 3. different carriers of table
Table 3 statistics indicate that, when carrier by 1000 DEG C heat treatment after, prepare catalyst metal dispersity, phase
Than in the made catalyst of untreated carrier, being greatly improved, and when heat treatment temperature is less than 800 DEG C, then carry
The property change of body is not obvious.This and the evaluating catalyst data of table 1 and the carrier surface hydroxyl data of table 2, are presented
Rule is very identical.
Embodiment 7：
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 4.
Influence of 4. temperature of table to ethylene glycol catalyst prepared by dimethyl oxalate plus hydrogen reactivity worth
The experimental result of table 4 shows that the selectivity of the conversion ratio of dimethyl oxalate and each product is influenced by reaction temperature
It is larger.At 190 DEG C, the conversion ratio of dimethyl oxalate has reached~100%, and glycol selectivity has reached 95.2%, but with
The selectivity for temperature increase ethylene glycol continuously decreases, and the selectivity of ethyl alcohol gradually rises.It will thus be seen that by changing temperature
Distribution of the dimethyl oxalate to hydrogenation reaction product can be changed, high temperature is conducive to Hydrogenation of Dimethyl Oxalate and generates ethyl alcohol.
Embodiment 8：
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
℃,3MPa、0.5h-1LHSVDMOUnder the conditions of, reaction result is listed in table 4.
Preparing ethylene glycol by using dimethyl oxalate plus hydrogen reactivity worth on 4. copper-based catalysts 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 (7)
1. a kind of method of modifying of the catalyst carrier of hydrogenation of oxalate for preparing ethylene glycol, it is characterised in that：The catalyst is with SiO2
For carrier, carrier is modified 1~10 hour through 800~1200 DEG C of heat treatments.
2. the method for modifying of catalyst carrier according to claim 1, it is characterised in that：Its carrier S iO2It is preferred that gas phase dioxy
SiClx；The hydroxyl quantity that the modification aerosil of modified acquisition is measured through titration is 1~3 × 1020A/g, preferably
1.5~2.5 × 1020A/g.
3. the method for modifying of catalyst carrier according to claim 1 or claim 2, it is characterised in that：In 800~1200 DEG C of high temperature
Under the conditions of, to the fluidized-bed bottom of quartz material be passed through dry inert gas (one kind in nitrogen or argon gas or two kinds with
On), to make aerosil to be modified in reactor be in flow regime, calcination time continues 1~10 hour；It is modified
The hydroxyl quantity that the modification aerosil obtained afterwards is measured through titration is 1~3 × 1020A/g, preferably 1.5~2.5 ×
1020A/g.
4. a kind of catalyst of hydrogenation of oxalate for preparing ethylene glycol, it is characterised 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；
The preparation process of the catalyst is first to mix the copper salt solution that molar concentration is 0.01~1mol/L with ammonium hydroxide,
It is configured to the copper ammon solution of pH=9~10；Then any modified aerosils of claim 1-3 are added
In copper ammon solution；Then heating removes the ammonia in solution；Catalyst is made in last washed, 300~600 DEG C of roastings, grinding.
5. application of the catalyst in hydrogenation of oxalate for preparing ethylene glycol described in a kind of claim 4.
6. application according to claim 5, 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.
7. according to the application of claim 5 or 6, it is characterised in that：Hydrogenation of oxalate for preparing ethylene glycol reaction, 150~
It carries out at a temperature of 260 DEG C or preferably 160~200 DEG C, is carried out at 0.5~6MPa or preferably 2~3Mpa pressure, 10~
It is carried out under 200 or preferably 50~120 hydrogen ester molar ratio.
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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 |
| CN102151568A (en) * | 2011-01-30 | 2011-08-17 | 山东华鲁恒升集团德化设计研究有限公司 | Catalyst for preparing ethylene glycol by dimethyl oxalate hydrogenation, and preparation and use thereof |
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