CN103415340A - Catalyst for production of oxalic acid diester, and method for producing oxalic acid diester using catalyst - Google Patents
Catalyst for production of oxalic acid diester, and method for producing oxalic acid diester using catalyst Download PDFInfo
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- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
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Abstract
Provided is a catalyst (a catalyst for the production of an oxalic acid diester) which has high catalytic activity in a method for producing an oxalic acid diester by causing carbon monooxide and a nitrous acid ester to react with each other. A catalyst for the production of an oxalic acid diester, which causes carbon monooxide and a nitrous acid ester to react with each other. The catalyst for the production of an oxalic acid diester is obtained by having a carrier support a platinum group metal or a compound thereof and gold or a compound thereof, and the abundance ratio of the platinum group metal to gold is from 100:1 to 100:100.
Description
Technical field
The present invention relates to the manufacture method of manufacturing the catalyst (oxalate diester catalyst for producing) of oxalate diester be used to carbon monoxide is reacted with nitrites and having used the oxalate diester of this catalyst.Oxalate diester is for example as oxalic acid, oxamides, ethanol acids, dyestuff intermediate and the useful compound of medical material.
Background technology
In the past, as the oxalate diester catalyst for producing, the method (for example, with reference to patent documentation 1～6) of various uses platinum group metal series catalysts was for example proposed.In addition, the metal in being selected from palladium, rhodium, iridium, platinum and gold, the mixed catalyst (for example, with reference to patent documentation 7) formed with co-catalysts such as iron or copper were also proposed.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication sho 54-81211 communique
Patent documentation 2: Japanese kokai publication sho 54-100312 communique
Patent documentation 3: Japanese kokai publication sho 57-42654 communique
Patent documentation 4: Japanese kokai publication sho 57-122042 communique
Patent documentation 5: Japanese kokai publication sho 58-126836 communique
Patent documentation 6: Japanese kokai publication sho 59-80630 communique
Patent documentation 7: Japanese kokai publication sho 55-22666 communique
Summary of the invention
Invent problem to be solved
But, in described any one catalyst, from the viewpoint of the catalytic activity of industrial use, consider still to have the leeway of improvement, wish to propose the catalyst with higher catalytic activity.
In addition, according to the catalyst difference, be accompanied by sometimes the decomposition as the nitrites of raw material, thereby have the problem that can't effectively utilize raw material or produce as the ester class of the analyte of nitrites and sneak into because of it problem that separation that makes target product becomes miscellaneous.
Problem of the present invention is, a kind of catalyst (oxalate diester catalyst for producing) with high catalytic activity is provided, in manufacturing the method for oxalate diester, it can suppress the decomposition as the nitrites of raw material carbon monoxide is reacted with nitrites, obtains with high yield oxalate diester.
Problem of the present invention also is, the manufacture method of the oxalate diester that has used this catalyst is provided.
The means of dealing with problems
Problem of the present invention can utilize following oxalate diester catalyst for producing to solve, it is the catalyst for producing that makes the oxalate diester that carbon monoxide reacts with nitrites, in carrier, supported platinum group metal or its compound and gold or its compound, and platinum group metal is 100:1～100:100 with golden existence ratio.
The invention effect
According to the present invention, can be provided for the catalyst that high yield and highly selective obtain oxalate diester.
The specific embodiment
(oxalate diester catalyst for producing)
The catalyst that oxalate diester catalyst for producing of the present invention is expressed as follows, that is,
(1) by platinum group metal or its compound,
(2) gold or its compound
(3) support in carrier,
(4) and platinum group metal with golden existence than being 100:1～100:100.
Here, what is called supports the catalyst in carrier, not only comprise platinum group metal or its compound, gold or its compound are side by side supported to the catalyst in 1 carrier, the catalyst that also comprise by will support the catalyst of platinum group metal or its compound in carrier, supports gold or its compound in carrier physically mixes, and so that platinum group metal with golden existence than the mixed catalyst of preparing for the mode of 100:1～100:100.
(1) platinum group metal or its compound
As described platinum group metal, such as enumerating palladium, platinum, iridium, ruthenium, rhodium etc., yet be preferably palladium.In addition, as the compound of platinum group metal, such as enumerating the halide such as palladium bichloride, palladium bromide, palladium iodide, platinum chloride, radium chloride, iridium chloride, ruthenic chloride; The inorganic acid salt such as palladium nitrate, palladium sulfate; The acylates such as oxalic acid palladium, acid chloride, palladium trifluoroacetate; The sulfonate such as TFMS palladium etc., however acylate preferably used, more preferably use acid chloride.
(2) gold or its compound
As described gold or its compound, for example can enumerate gold; The golden halide such as chlorauride (I), chlorauride (III), gold bromide (III); The halogenation auric acid such as tetra chlorauric acid, tetrabromo auric acid; The halogenation aurates such as tetrachloro sodium aurate; Chlorine (trimethyl-phosphine) gold, chlorine (triethyl phosphine) gold, chlorine (triphenylphosphine) gold, chlorine (three (p-trifluoromethyl phenyl) phosphine) gold, (pyridine) gold trichloride, dichloro (diphenylphosphino) gold, chlorine (two (tert-butyl groups) (adjacent xenyl) phosphine) gold, ［ three (triphenylphosphine gold) oxygen ］ tetrafluoro boric acid ester (［ (Ph
3PAu)
3O ］ BF
4), Chlorodimethyl aurosulfo etc., yet preferably use the halogenation auric acid, more preferably use the chlorination auric acid.And they both can be anhydrous, also can contain hydrate.
(3) carrier and supporting
As the carrier in the present invention, be not particularly limited, such as enumerating silica, aluminium oxide (such as Alpha-alumina, beta-alumina, gama-alumina etc.), carborundum, diatomite, active carbon, float stone, zeolite, mesoporous body, clay etc., yet preferably use any one carrier as principal component with Alpha-alumina, gama-alumina, silica, active carbon, carborundum, more preferably use with the carrier of Alpha-alumina as principal component.
Described what is called " aluminium oxide of take is principal component " refers to, the part of carrier also can be by the displacement of the composition beyond aluminium oxide.More than the content of the aluminium oxide of aluminium oxide in the carrier of principal component of take is preferably 90 quality % with respect to the gross mass 100 quality % of carrier, more preferably more than 95 quality %, more preferably more than 98 quality %.And any one carrier as principal component of silica, active carbon, carborundum of take is also identical content.
In addition, described what is called " Alpha-alumina of take is principal component " refers to, beyond Alpha-alumina, also can contain some beta-alumina, gama-alumina, noncrystalline aluminium oxide etc. other the aluminium oxide of form or the composition beyond aluminium oxide.More than the content of the Alpha-alumina in carrier is preferably 90 quality % with respect to the gross mass 100 quality % of carrier, more preferably more than 95 quality %, more preferably more than 98 quality %.
On the other hand, described what is called " gama-alumina of take is principal component " refers to, beyond gama-alumina, also can contain some Alpha-alumina, beta-alumina, noncrystalline aluminium oxide etc. other the aluminium oxide of form or the composition beyond aluminium oxide.More than the content of the gama-alumina in carrier is preferably 90 quality % with respect to the gross mass 100 quality % of carrier, more preferably more than 95 quality %, more preferably more than 98 quality %.
Any one carrier as principal component of Alpha-alumina, gama-alumina, silica, active carbon, carborundum of take for example also can contain the oxide of alkali metal or alkaline-earth metal or the oxide of transition metal.Content for them is not particularly limited, and the content of the oxide of alkali metal or alkaline-earth metal converts and is preferably 0～5 quality %, more preferably 0.01～4 quality % in oxide.In addition, the content of the oxide of transition metal converts and is preferably 0～5 quality %, more preferably 0.01～3 quality % in oxide.
Particle diameter for support material such as alumina powder jointed or alpha-alumina powders is not particularly limited, and its primary particle size is preferably 0.01～100 μ m, 0.1～20 μ m more preferably, and more preferably 0.5～10 μ m, be particularly preferably 1～5 μ m.In addition, its aggregate particle size is preferably 0.1～1,000 μ m, and 1～500 μ m more preferably, more preferably 10～200 μ m, be particularly preferably 30～100 μ m.By being made as this scope, gas phase circulation reaction will become easy.
Specific area for described carrier is not particularly limited, and is preferably 0.03～100m
2/ g, more preferably 0.5～50m
2/ g, more preferably 1.0～10m
2/ g.By being made as this scope, can support the catalyst component of necessary amounts, utilize the specific area of carrier, platinum group metal or its compound become easy with the acting in conjunction meeting of gold or its compound
Described carrier preferably has the above compression strength of 40N.More than the compression strength of carrier is preferably 50N, more preferably more than 60N.By being made as this scope, can prevent that the breakage of carrier self from destroying.
The bulk density of described carrier is preferably 0.5～1.0kg/L, more preferably 0.6～0.8kg/L, more preferably 0.65～0.80kg/L.
The pore volume of described carrier is not particularly limited, and is preferably 0.1～0.6cm
3/ g, more preferably 0.2～0.5cm
3/ g, more preferably 0.3～0.45cm
3/ g.By being made as this scope, supporting of catalyst component will become easy.And, as the value of the pore volume of carrier, adopt the value of utilizing mercury injection method to obtain.
The size of the pore that described carrier has also is not particularly limited, yet average pore diameter is preferably 0.05～10 μ m, 0.1～4.0 μ m more preferably, and more preferably 0.15～3.0 μ m, be particularly preferably 0.15～1.5 μ m.By being made as this scope, will become easy to the absorption of the raw material on carrier and the disengaging of product.And, as the value of average pore diameter, adopt the value of utilizing mercury injection method to obtain.
Water absorption rate for described carrier is not particularly limited, and is preferably 10～70%, and more preferably 20～60%, more preferably 30～50%.By being made as this scope, catalyst component will become easily to supporting of carrier, and the intensity of carrier can be guaranteed for practical degree.
So-called platinum group metal to carrier supports ratio and gold supports ratio, refer to platinum group metal and the metallographic mass ratio for whole catalytic amounts of the carrier that supports platinum group metal or its compound, gold or its compound, be preferably 0.01～1 quality %, more preferably 0.1～0.5 quality %.By being made as this scope, the catalyst component of essential amount will act on effectively, can keep the oxalate diester growing amount of per unit platinum group metal.If very few, can not reach practical output, if too much, can't utilize fully platinum group metal.And, utilize electricity to answer the luminous light-dividing device of coupled plasma (ICP) to measure the ratio that supports of platinum group metal and gold.
(manufacture of oxalate diester catalyst for producing)
Platinum group metal in the manufacture of oxalate diester catalyst for producing of the present invention or its compound, gold or its compound are not particularly limited to the process for fixation of carrier, can use known method.
As in described supported carrier platinum group metal or the method for its compound, gold or its compound, such as adopting method of impregnation, steam seasoning etc.
In the situation that utilize method of impregnation to support platinum group metal or its compound, gold or its compound, such as platinum group metal compounds solution, using and in acidic aqueous solution (aqueous hydrochloric acid solution etc.), to have dissolved the approximately solution of the platinum group metal compounds of 0.01～10 quality %, infiltration temperature is made as approximately to 0～90 ℃ approximately to infiltrate in 1～20 hour.
In platinum group metal or its compound, gold or its compound, used in halid situation, the aqueous alkali of the most handy ammoniacal liquor or sodium hydrate aqueous solution and so on is processed, and removes the halide on catalyst.
The order that supports platinum group metal or its compound, gold or its compound is not particularly limited, and both can side by side support, also can be after supporting platinum family or its compound supported gold or its compound, can also adopt its opposite order.
Utilize catalyst that described loading method supported platinum group metal or its compound, gold or its compound preferably after platinum group metal compounds solution, separating, washing, carry out afterwards drying.
Described drying is for example carried out about 0.5～20 hour at 50～150 ℃.Pressure now can be under normal pressure or from normal pressure to the 13kPaG(gauge pressure) under the decompression of left and right or from normal pressure to the 1.0MPaG(gauge pressure) left and right add any one that depress.In addition, the atmosphere when dry is not particularly limited, such as in air or inert gas (nitrogen etc.) atmosphere, carrying out.
After drying, in liquid phase or gas phase, use reducing agent to be reduced (reduction processing) by being equipped with platinum group metal or its compound and gold or the catalyst of its compound.
In the situation that reduce in liquid phase, for example by with respect to the described carrier that supports platinum group metal or its compound and gold or its compound, preferably containing 1～50 quality %, more preferably contain in the reducing agent aqueous solution of reducing agent of 2～30 quality %, preferably 0～100 ℃, more preferably under 10～100 ℃, make it with reducing agent, contact to carry out.
As described reducing agent, preferably use the reducing agents such as hydrazine, formic acid, sodium formate, formaldehyde.
In the situation that reduce in gas phase, in the inert gas (for example, with nitrogen or argon diluent) preferably containing the low-boiling point alcohols such as 1～50 volume %, the hydrogen as reducing gas that more preferably contains 2～30 volume % or methyl alcohol, make the described catalyst that supports platinum group metal or its compound and gold or its compound preferably 100～600 ℃, more preferably under 200～550 ℃, contact with reducing agent to carry out.
(4) platinum group metal and golden existence ratio
In the present invention, platinum group metal with golden existence than being 100:1～100:100, yet 100:1～100:99 more preferably, more preferably 100:1～100:50, be particularly preferably 100:1～100:49, most preferably is 25:1～3:1.And in the present invention, there is ratio in what is called, mean the mol ratio of metallic atom.By being made as this scope, just can prevent the situation of the lifetime of catalytic activity step-down, catalyst when the ratio of gold atom is lacked, in addition, space-time yield and elective reduction in the time of can also suppressing the oxalate diester manufacture.
(having used the manufacture of the oxalate diester of oxalate diester catalyst for producing)
The manufacture of oxalate diester of the present invention is under the existence of oxalate diester catalyst for producing, by make carbon monoxide with general formula (1)
[changing 1]
RONO (1)
(in formula, R also can have substituting group, and it means the alkyl of carbon number 1～8 or the cycloalkyl of carbon number 3～8.）
The nitrites reaction meaned (below be called reaction of the present invention.) carry out, and the oxalate diester of gained is with general formula (2)
(in formula, R and above-mentioned equivalent in meaning.）
The compound meaned, reaction of the present invention means with following formula.
[changing 3]
(in formula, R and above-mentioned equivalent in meaning.）
The nitrites used in reaction of the present invention means with general formula (1), and in this general formula (1), R also can have substituting group, the cycloalkyl of the carbon numbers 3～8 such as the alkyl of carbon numbers 1～8 such as expression methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group or cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, ring octyl group.And these bases also comprise various isomers.
Described nitrites, as shown in following formula (3), can react to manufacture by making nitric oxide, alcohol and oxygen.
[changing 4]
2NO+2ROH+1/20
2→2RONO+H
2O (3)
In addition, the decomposition reaction of nitrites for example, in the situation that R is alkyl, means with following formula.
[changing 5]
(R and above-mentioned equivalent in meaning, R ' means the alkyl with respect to few 1 carbon number of R here.) in described formula (4), for example in the situation that R is methyl (methyl nitrite), owing to there is no R ', so analyte is formic acid esters.
In the manufacture method of oxalate diester of the present invention, described nitrites is reacted in gas phase with carbon monoxide.
Reaction of the present invention is for example if gas-phase reaction, can utilize in possessing the reaction tube of heater, fill oxalate diester catalyst for producing of the present invention after, supply with carbon monoxide, nitrites and inert gas and make it the method such as reaction and carry out.Reaction temperature now is preferably 50～200 ℃, more preferably 80～150 ℃.In addition, reaction pressure is preferably normal pressure to the 1MPaG(gauge pressure), more preferably normal pressure is to the 0.5MPaG(gauge pressure).By being made as this temperature range and pressure limit, just can, under the state that maintains the space-time yield of necessary amounts (Space Time Yield:STY), suppress the generation of accessory substance.
The nitrites of supplying with comprises sometimes becomes nitric oxide or the alcohol that it manufactures raw material, even and in reaction of the present invention, comprise the situation that they do not have special obstruction reaction yet.In addition, carbon monoxide be no matter pure or with inert gas dilution can use.
The concentration that imports the nitrites in the unstrpped gas in reactor is preferably 1～50 capacity %, 3～30 capacity % more preferably, and the concentration of carbon monoxide is preferably 10～90 capacity %.
Utilize reaction of the present invention can obtain oxalate diester, yet can carry out as required distilation etc., remove carbonic diester as accessory substance etc.In addition, unreacted alkyl nitrite, carbon monoxide can be reclaimed and recycle, the secondary nitric oxide generated can be again for the manufacture of alkyl nitrite.
Embodiment
Below, enumerate embodiment the present invention is specifically described, yet scope of the present invention is not limited to them.And the analysis of product is to utilize gas chromatography (fid detector, internal standard method) to carry out, and utilizes ICP(Inductively Coupled Plasma) analyze the metallic atom amount in the solid (catalyst) of gained.
The manufacture of embodiment 1(oxalate diester catalyst for producing)
After adding acid chloride 0.106g in acetone 12ml, irradiate ultrasonic wave and acid chloride fully is dissolved in acetone.Then, spherical Alpha-alumina (the Alpha-alumina content 99.5 quality %) 10g to dipping diameter 1～2mm in this solution, stirs after 1 hour and distills and remove acetone.
Then, the solid impregnating of gained is dissolved with in the solution of chlorination auric acid trihydrate 0.180g at water 7ml, stirs after 1 hour (approximately 80 ℃) dry night in drier.After drying, the diameter of transferring to the internal diameter that possesses electric furnace is in the quartz glass tube of 30mm, in 60ml/min circulation hydrogen, in approximately reduction 6 hours under 200 ℃, obtains supporting palladium and golden globular solids catalyst on Alpha-alumina.
And, shown in the catalyst of gained composed as follows.
Palladium supports ratio; 0.50 quality %
Gold supports ratio; 0.93 quality %
There is the mol ratio of ratio=1(metallic atom in gold/palladium)
The manufacture of embodiment 2～8, comparative example 1～2(oxalate diester catalyst for producing)
In embodiment 1, change the acid chloride use and the ratio of chlorination auric acid trihydrate, produce that palladium supports ratio, gold supports ratio and gold/palladium exists than (mol ratio of metallic atom) different catalyst.In addition, as a comparison, do not produce gold with also not using together chlorination auric acid trihydrate to support ratio be the material of 0 quality %, do not produce palladium with using acid chloride and support the material that ratio is 0 quality %.
In table 1, express the composition of the catalyst of manufacturing.
[table 1]
Synthesizing of embodiment 9～16 and comparative example 3～4(dimethyl oxalate)
[changing 6]
In the glass of internal diameter 10mm, long 20cm reaction tube processed, fill in described embodiment 1～8 and comparative example 1～2 the catalyst 1ml(0.8g of preparation), more thereon with the bead of the highly-filled diameter 2mm of 5mm.
This reaction tube is vertically fixing, in being located at the chuck section at reaction tube place, flow through the silicone oil be heated, so that the temperature in catalyst layer reaches the mode of 120 ℃ heat after, from reaction tube top, with catalyst feed speed (S.T.P) 20.0L/h, supply with the admixture of gas formed by carbon monoxide 20.0 capacity %, methyl nitrite 13.0 capacity %, methyl alcohol 7.0 capacity %, nitric oxide 1.0 capacity % and nitrogen 59.0 capacity %.
Will from reaction tube by the compound that obtains by with the chilled methyl alcohol of frozen water, trapping, carry out the analysis of product.The results are shown in table 2.The analysis result of the product that the analysis result of the product that embodiment 9～16 obtains corresponding to the catalyst that uses embodiment 1～8, comparative example 3～4 obtain corresponding to the catalyst of usage comparison example 1～2.And, so-called DMO space-time yield (STY), mean per unit catalyst capacity, the dimethyl oxalate of unit interval (DMO) growing amount (mole), the selection rate of dimethyl oxalate (DMO) and dimethyl carbonate (DMC) is to take carbon monoxide to be benchmark.
Will from above-mentioned admixture of gas, only stop supplying with carbon monoxide by methyl nitrite capacity 14%, methyl alcohol capacity 7%, the ratio that supports of the embodiment 17(acid chloride shown in the admixture of gas use table 3 that nitric oxide capacity 4% and nitrogen capacity 75% form is 0.5 quality %, the ratio that supports of chlorination auric acid trihydrate is 0.1 quality %) catalyst and the ratio that supports of comparative example 5(acid chloride be 0.5 quality %, the ratio that supports of chlorination auric acid trihydrate is 0 quality %) catalyst, with catalyst feed speed (S.T.P) 12.7L/h, supply with, by the Temperature Setting in catalyst layer, it is 130 ℃.After the methyl nitrite analyte of trapping gained, carried out the analysis of catabolite.The results are shown in table 3.So-called MN(methyl nitrite) resolution ratio, mean the ratio (%) that waits the methyl nitrite that the methyl nitrite that there is no recovery supplies with respect to per unit catalyst capacity, the time of supporting because decomposing.
[table 2]
[table 3]
As can be known according to above result, as shown in table 2, if use oxalate diester catalyst for producing of the present invention, can obtain dimethyl oxalate with high DMO space-time yield (that is, catalytic activity of the present invention is high) and with high yield.In addition we know, as shown in table 3, if use oxalate diester catalyst for producing of the present invention, can suppress the decomposition as the methyl nitrite of raw material.According to analysis, the major part of catabolite is methyl formate.
Utilizability on industry
The present invention relates to the manufacture method of manufacturing the catalyst (oxalate diester catalyst for producing) of oxalate diester be used to carbon monoxide is reacted with nitrites and having used the oxalate diester of this catalyst.Oxalate diester is for example as oxalic acid, oxamides, ethanol acids, dyestuff intermediate and the useful compound of medical material.
Claims (5)
1. oxalate diester catalyst for producing, it is the catalyst for producing that makes the oxalate diester that carbon monoxide reacts with nitrites,
In carrier, supported platinum group metal or its compound and gold or its compound, and platinum group metal is 100:1～100:100 with golden existence ratio.
2. oxalate diester catalyst for producing according to claim 1, wherein,
Carrier is to take the carrier of aluminium oxide as principal component.
3. oxalate diester catalyst for producing according to claim 2, wherein,
Carrier is to take the carrier of Alpha-alumina as principal component.
4. according to the described oxalate diester catalyst for producing of any one in claim 2 or 3, wherein,
Platinum group metal is palladium.
5. the manufacture method of an oxalate diester,
It is under the existence of the described oxalate diester catalyst for producing of any one in claim 1 to 4, and carbon monoxide is reacted with nitrites.
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| CN201710474766.7A CN107262091A (en) | 2011-03-11 | 2012-03-09 | Oxalate diester catalyst for producing and used the catalyst oxalate diester manufacture method |
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| JP2011-054614 | 2011-03-11 | ||
| JP2011054614 | 2011-03-11 | ||
| PCT/JP2012/056056 WO2012124616A1 (en) | 2011-03-11 | 2012-03-09 | Catalyst for production of oxalic acid diester, and method for producing oxalic acid diester using catalyst |
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| CN201710474766.7A Pending CN107262091A (en) | 2011-03-11 | 2012-03-09 | Oxalate diester catalyst for producing and used the catalyst oxalate diester manufacture method |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5888322B2 (en) |
| CN (2) | CN107262091A (en) |
| WO (1) | WO2012124616A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116056788A (en) * | 2020-07-29 | 2023-05-02 | 积水化学工业株式会社 | Catalyst for organic carbonate synthesis, method for producing the same, electrode for synthesis, battery for synthesis, method for producing organic carbonate, and system for synthesizing the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2025950A (en) * | 1978-06-23 | 1980-01-30 | Montedison Spa | The Preparation of Esters of Oxalic Acid |
| CN1235561A (en) * | 1996-10-31 | 1999-11-17 | 米兰纽姆石化公司 | Improved process for production of supported palladium-gold catalysts |
| CN101596455A (en) * | 2008-06-04 | 2009-12-09 | 中国石油天然气股份有限公司 | Catalyst for synthesizing oxalate and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57123142A (en) * | 1981-01-26 | 1982-07-31 | Ube Ind Ltd | Production of oxalic diester |
| JP3829465B2 (en) * | 1998-03-27 | 2006-10-04 | 宇部興産株式会社 | Process for producing dialkyl carbonate |
| JP2006212571A (en) * | 2005-02-04 | 2006-08-17 | Nippon Shokubai Co Ltd | Method for suppressing deterioration of au catalyst |
| JP2007326837A (en) * | 2006-06-09 | 2007-12-20 | Mitsubishi Chemicals Corp | Method for producing diaryl carbonate |
| CN101279257B (en) * | 2008-03-27 | 2012-05-30 | 上海焦化有限公司 | Catalyst for synthesizing oxalic ester and preparation method and application thereof |
| CN101791555B (en) * | 2010-03-19 | 2011-08-24 | 丹阳市丹化金煤化工有限公司 | Catalyst for gas-phase dimethyloxalate synthesis by CO and preparation method thereof |
-
2012
- 2012-03-09 CN CN201710474766.7A patent/CN107262091A/en active Pending
- 2012-03-09 WO PCT/JP2012/056056 patent/WO2012124616A1/en active Application Filing
- 2012-03-09 CN CN2012800124499A patent/CN103415340A/en active Pending
- 2012-03-09 JP JP2013504700A patent/JP5888322B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2025950A (en) * | 1978-06-23 | 1980-01-30 | Montedison Spa | The Preparation of Esters of Oxalic Acid |
| CN1235561A (en) * | 1996-10-31 | 1999-11-17 | 米兰纽姆石化公司 | Improved process for production of supported palladium-gold catalysts |
| CN101596455A (en) * | 2008-06-04 | 2009-12-09 | 中国石油天然气股份有限公司 | Catalyst for synthesizing oxalate and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116056788A (en) * | 2020-07-29 | 2023-05-02 | 积水化学工业株式会社 | Catalyst for organic carbonate synthesis, method for producing the same, electrode for synthesis, battery for synthesis, method for producing organic carbonate, and system for synthesizing the same |
| US12054833B2 (en) | 2020-07-29 | 2024-08-06 | Sekisui Chemical Co., Ltd. | Catalyst for synthesizing organic carbonate and method of producing thereof, electrode for synthesizing organic carbonate, cell for synthesizing organic carbonate, method of producing organic carbonate, and synthesis system |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5888322B2 (en) | 2016-03-22 |
| WO2012124616A1 (en) | 2012-09-20 |
| JPWO2012124616A1 (en) | 2014-07-24 |
| CN107262091A (en) | 2017-10-20 |
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