CN107262091A - Oxalate diester catalyst for producing and used the catalyst oxalate diester manufacture method - Google Patents
Oxalate diester catalyst for producing and used the catalyst oxalate diester manufacture method Download PDFInfo
- Publication number
- CN107262091A CN107262091A CN201710474766.7A CN201710474766A CN107262091A CN 107262091 A CN107262091 A CN 107262091A CN 201710474766 A CN201710474766 A CN 201710474766A CN 107262091 A CN107262091 A CN 107262091A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- gold
- carrier
- compound
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- B01J23/38—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
-
- 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
- B01J23/38—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
-
- 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
- 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
-
- 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
- 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
-
- 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
- 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
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
Abstract
The present invention provides the catalyst (oxalate diester catalyst for producing) with high catalytic activity in a kind of method for reacting carbon monoxide and nitrous acid ester and manufacturing oxalate diester.The oxalate diester catalyst for producing of the present invention is the catalyst for producing for the oxalate diester for making carbon monoxide be reacted with nitrous acid ester, and platinum group metal or its compound and gold or its compound are supported with the carrier, and the presence ratio of platinum group metal and gold is 100：1~100：100.
Description
Related application
The application is divisional application, the application number of its parent application：2012800124499 (PCT/JP2012/056056),
The applying date：2012.03.09, denomination of invention：Oxalate diester catalyst for producing and used the catalyst oxalate diester system
Make method.
Technical field
The present invention relates to for making carbon monoxide react and manufacture the catalyst (oxalate diester of oxalate diester with nitrous acid ester
Catalyst for producing) and used the catalyst oxalate diester manufacture method.Oxalate diester is for example as oxalic acid, oxalyl
Amine, ethanol acids, dyestuff intermediate and the useful compound of medical material.
Background technology
In the past, as oxalate diester catalyst for producing, for example, the side of various use platinums group metal series catalysts was proposed
Method (referring for example to patent document 1~6).In addition, it is also proposed that cross by the metal in palladium, rhodium, iridium, platinum and gold and iron or copper
The mixed catalyst constituted Deng co-catalyst (referring for example to patent document 7).
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Application 54-81211 publications
Patent document 2：Japanese Unexamined Patent Application 54-100312 publications
Patent document 3：Japanese Unexamined Patent Application 57-42654 publications
Patent document 4：Japanese Unexamined Patent Application 57-122042 publications
Patent document 5：Japanese Unexamined Patent Application 58-126836 publications
Patent document 6：Japanese Unexamined Patent Application 59-80630 publications
Patent document 7：Japanese Unexamined Patent Application 55-22666 publications
The content of the invention
Invent problem to be solved
But, in any one described catalyst, still have from the viewpoint of the catalytic activity industrially used and change
Good leeway, it is desirable to propose the catalyst with higher catalytic activity.
In addition, it is different according to catalyst, can not so as to have sometimes along with the decomposition of the nitrous acid ester as raw material
The problem of effectively utilizing raw material produces the esters as the analyte of nitrous acid ester and makes target product because it is mixed into
The problem of separation becomes miscellaneous.
The problem of the present invention is that there is provided a kind of catalyst (oxalate diester catalyst for producing with high catalytic activity
Agent), the method for oxalate diester is manufactured reacting carbon monoxide and nitrous acid ester, and it can suppress the nitrous as raw material
The decomposition of acid esters, obtains oxalate diester in high yield.
The problem of the present invention also resides in that there is provided the manufacture method for the oxalate diester for having used the catalyst.
The means solved the problems, such as
The present invention problem can be solved using following oxalate diester catalyst for producing, its be make carbon monoxide and
Nitrous acid ester reaction oxalate diester catalyst for producing, be supported with the carrier platinum group metal or its compound and gold or
Its compound, and the presence ratio of platinum group metal and gold is 100：1~100：100.
Invention effect
According to the present invention it is possible to provide the catalyst for obtaining in high yield and with high selectivity oxalate diester.
Embodiment
(oxalate diester catalyst for producing)
The catalyst that the oxalate diester catalyst for producing of the present invention is expressed as follows, i.e.
(1) by platinum group metal or its compound,
(2) gold or its compound
(3) support in carrier,
(4) and platinum group metal with gold presence ratio be 100：1~100：100.
Here, the so-called catalyst supported in carrier, not only including by platinum group metal or its compound, gold or its chemical combination
Thing simultaneously supports the catalyst in 1 carrier, in addition to by the way that platinum group metal or its compound will be supported with the carrier
Catalyst, mix with being supported with gold or the catalyst physical of its compound in the carrier, and so that platinum group metal is deposited with golden
Than for 100：1~100：The mixed catalyst that 100 mode prepares.
(1) platinum group metal or its compound
As the platinum group metal, such as can enumerate palladium, platinum, iridium, ruthenium, rhodium, but preferably palladium.In addition, conduct
The compound of platinum group metal, for example, can enumerate palladium bichloride, palladium bromide, palladium iodide, platinum chloride, radium chloride, iridium chloride, ruthenic chloride
Deng halide；The inorganic acid salts such as palladium nitrate, palladium sulfate；The acylates such as oxalic acid palladium, acid chloride, palladium trifluoroacetate；Fluoroform sulphur
Sulfonate such as sour palladium etc., but acylate is preferably used, more preferably using acid chloride.
(2) gold or its compound
As the gold or its compound, for example, it can enumerate gold；Chlorauride (I), chlorauride (III), gold bromide (III)
Deng golden halide；The halogenation auric acid such as tetra chlorauric acid, four auribromohydric acids；The halogenation aurates such as four chlorination sodium aurates；Chlorine (trimethyl-phosphine)
Gold, chlorine (triethyl phosphine) gold, chlorine (triphenylphosphine) gold, chlorine (three (p-trifluoromethyl phenyl) phosphines) gold, (pyridine) gold trichloride, two
Chlorine (diphenylphosphino) gold, chlorine (two (tert-butyl groups) (adjacent xenyl) phosphine) gold, [three (triphenylphosphine gold) oxygen] tetrafluoro boric acid ester
([(Ph3PAu)3O]BF4), Chlorodimethyl aurosulfo etc., but halogenation auric acid is preferably used, more preferably using chlorination auric acid.And
And, they both can also contain hydrate with anhydrous.
(3) carrier and support
As the carrier in the present invention, it is not particularly limited, for example, can enumerates silica, aluminum oxide (such as α-oxygen
Change aluminium, beta-alumina, gama-alumina etc.), carborundum, diatomite, activated carbon, float stone, zeolite, mesoporous body, clay etc., so
And preferably use using Alpha-alumina, gama-alumina, silica, activated carbon, carborundum any one as principal component load
Body, more preferably uses the carrier using Alpha-alumina as principal component.
Described so-called " using aluminum oxide as principal component " refers to that a part for carrier can also be by the composition beyond aluminum oxide
Displacement.The content of aluminum oxide in using aluminum oxide as the carrier of principal component is preferably relative to the mass % of gross mass 100 of carrier
More than 90 mass %, more preferably more than 95 mass %, more preferably more than 98 mass %.Moreover, with silica, work
Property charcoal, carborundum any one for the carrier of principal component be also identical content.
In addition, described so-called " using Alpha-alumina as principal component " refers to, one can also be contained beyond Alpha-alumina
Composition beyond the aluminum oxide or aluminum oxide of the others form such as part beta-alumina, gama-alumina, noncrystalline aluminum oxide.
The content of Alpha-alumina in carrier is preferably more than 90 mass %, more preferably relative to the mass % of gross mass 100 of carrier
More than 95 mass %, more preferably more than 98 mass %.
On the other hand, described so-called " using gama-alumina as principal component " refers to, can also beyond gama-alumina
Beyond aluminum oxide or aluminum oxide containing other forms such as some Alpha-alumina, beta-alumina, noncrystalline aluminum oxide
Composition.The content of gama-alumina in carrier is preferably more than 90 mass %, more relative to the mass % of gross mass 100 of carrier
Preferably more than 95 mass %, more preferably more than 98 mass %.
Using Alpha-alumina, gama-alumina, silica, activated carbon, carborundum any one as principal component carrier
For example can also the oxide containing alkali metal or alkaline-earth metal or transition metal oxide.For their content without spy
Do not limit, the content of the oxide of alkali metal or alkaline-earth metal is preferably 0~5 mass % in terms of oxide conversion, more preferably
0.01~4 mass %.In addition, the content of the oxide of transition metal is preferably 0~5 mass % in terms of oxide conversion, it is more excellent
Elect 0.01~3 mass % as.
It is not particularly limited for the particle diameter of the support materials such as alumina powder or alpha-alumina powder, its primary particle size
Preferably 0.01~100 μm, more preferably 0.1~20 μm, particularly preferably more preferably 0.5~10 μm, 1~5 μm.Separately
Outside, its aggregate particle size is preferably 0.1~1,000 μm, more preferably 1~500 μm, more preferably 10~200 μm, especially excellent
Elect 30~100 μm as.By being set to the scope, gas phase circulation reaction will become easy.
Specific surface area for the carrier is not particularly limited, preferably 0.03~100m2/ g, more preferably 0.5~
50m2/ g, more preferably 1.0~10m2/g.By being set to the scope, the catalyst component of necessary amounts can be supported, is utilized
The specific surface area of carrier, platinum group metal or its compound and the collective effect of gold or its compound can become easy
The carrier preferably has more than 40N compression strength.The compression strength of carrier is preferably more than 50N, more preferably
For more than 60N.By being set to the scope, the damaged destruction of carrier itself can be prevented.
The bulk density of the carrier is preferably 0.5~1.0kg/L, more preferably 0.6~0.8kg/L, further preferably
For 0.65~0.80kg/L.
The pore volume of the carrier is not particularly limited, preferably 0.1~0.6cm3/ g, more preferably 0.2~
0.5cm3/ g, more preferably 0.3~0.45cm3/g.By being set to the scope, supporting for catalyst component will become to hold
Easily.Moreover, the value of the pore volume as carrier, using the value obtained using mercury injection method.
The size of the pore that the carrier has it is not also specifically limited, but average pore diameter be preferably 0.05~
10 μm, more preferably 0.1~4.0 μm, particularly preferably more preferably 0.15~3.0 μm, 0.15~1.5 μm.By setting
For the scope, the disengaging of absorption and product to the raw material on carrier will become easy.Moreover, being used as average pore diameter
Value, using the value obtained using mercury injection method.
It is not particularly limited for the water absorption rate of the carrier, preferably 10~70%, more preferably 20~60%, enters one
Step is preferably 30~50%.By being set to the scope, catalyst component will become easy to supporting for carrier, and can be by
The intensity of carrier ensures the degree of practicality.
It is so-called to support ratio to the platinum group metal of carrier and gold supports ratio, refer to platinum group metal and metallographic for being supported with
The mass ratio of whole catalytic amounts of the carrier of platinum group metal or its compound, gold or its compound, preferably 0.01~1 matter
Measure %, more preferably 0.1~0.5 mass %.By being set to the scope, it is necessary to the catalyst component of amount will effectively make
With the oxalate diester growing amount of per unit platinum group metal can be kept.If very few, the output of practicality is not up to, such as
Fruit is excessive, then can not fully utilize platinum group metal.Moreover, answering coupled plasma luminescence spectrometer device (ICP) to survey using electricity
Determine platinum group metal and gold support ratio.
(manufacture of oxalate diester catalyst for producing)
Platinum group metal or its compound, gold or its compound in the manufacture of the oxalate diester catalyst for producing of the present invention
It is not particularly limited to the process for fixation of carrier, known method can be used.
As the method in the supported carrier platinum group metal or its compound, gold or its compound, for example, it can use
Method of impregnation, steam seasoning etc..
In the case where supporting platinum group metal or its compound, gold or its compound using method of impregnation, such as platinum family
Metal compound solution uses the platinum family gold that about 0.01~10 mass % has been dissolved in acidic aqueous solution (aqueous hydrochloric acid solution etc.)
Belong to the solution of compound, infiltration temperature is set to about 0~90 DEG C and infiltrated with about 1~20 hour.
In the case of having used halide in platinum group metal or its compound, gold or its compound, most handy ammoniacal liquor or
The aqueous alkali of sodium hydrate aqueous solution etc is handled, and removes the halide on catalyst.
The order for supporting platinum group metal or its compound, gold or its compound is not particularly limited, and both can simultaneously carry on a shoulder pole
Carry, can also after platinum family or its compound is supported supported gold or its compound, its opposite order can also be used.
The catalyst for having supported platinum group metal or its compound, gold or its compound using described loading method preferably exists
Laggard water-filling is separated from platinum group metal compounds solution to wash, and is dried afterwards.
The drying is for example carried out 0.5~20 hour or so at 50~150 DEG C.Pressure now can be under normal pressure or
The appointing under the pressurization of (gauge pressure) left and right under the decompression of (gauge pressure) left and right or from normal pressure to 1.0MPaG from normal pressure to 13kPaG
Meaning is a kind of.In addition, atmosphere when drying is not particularly limited, such as the progress in air or inert gas (nitrogen) atmosphere.
After drying, platinum group metal or its compound and gold or the catalyst of its compound will be equipped with liquid phase or gas phase
Middle use reducing agent is reduced (reduction treatment).
In the case of reducing in the liquid phase, for example by relative to it is described be supported with platinum group metal or its compound,
With gold or its compound carrier for preferably comprise 1~50 mass %, further preferably 2~30 mass % reducing agent also
In the former agent aqueous solution, preferably 0~100 DEG C, more preferably make it at 10~100 DEG C with reducing agent contact and carry out.
As the reducing agent, the reducing agents such as hydrazine, formic acid, sodium formate, formaldehyde are preferably used.
In the case of reducing in the gas phase, by preferably comprising 1~50 volume %, further preferably 2~30 volume %
The inert gas (such as with nitrogen or argon diluent) as low-boiling point alcohols such as the hydrogen or methanol of reducing gas in, make described support
There are platinum group metal or its compound and gold or the catalyst of its compound preferably at 100~600 DEG C, more preferably 200~550
Carried out at DEG C with reducing agent contact.
(4) platinum group metal and the presence ratio of gold
In the present invention, the presence ratio of platinum group metal and gold is 100：1~100：100, but more preferably 100：1~100：
99, more preferably 100：1~100：50, particularly preferably 100：1~100：49, most preferably 25：1~3：1.Moreover,
It is so-called to exist than representing the mol ratio of metallic atom in the present invention.By being set to the scope, it is possible to prevent when gold atom
Catalytic activity step-down, the situation of the lifetime of catalyst when ratio is few, furthermore it is also possible to when suppressing oxalate diester manufacture when
Empty yield and selectivity reduction.
(manufacture for having used the oxalate diester of oxalate diester catalyst for producing)
The manufacture of the oxalate diester of the present invention is in the presence of oxalate diester catalyst for producing, by making carbon monoxide
With with formula (1)
[changing 1]
RONO (1)
(in formula, R can also have the cycloalkanes of substituent, its alkyl for representing carbon number 1~8 or carbon number 3~8
Base.)
Nitrous acid ester reaction (the hereinafter referred to as reaction of the invention of expression.) carry out, and the oxalate diester of gained be with
Formula (2)
(in formula, R with it is above-mentioned equivalent in meaning.)
The compound of expression, reaction of the invention is represented with following formula.
[changing 3]
(in formula, R with it is above-mentioned equivalent in meaning.)
The nitrous acid ester used in the reaction of the present invention is represented with formula (1), and in the formula (1), R can also have
Substituent, such as represent methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, the alkyl of carbon number 1~8 octyl group or
The cycloalkyl of the carbon numbers such as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl 3~8.Moreover, these bases
Including various isomers.
, can be by manufacturing nitric oxide, alcohol and oxygen reaction shown in the nitrous acid ester such as following formula (3).
[changing 4]
2 NO+2 ROH+1/2O2→2 RONO+H2O (3)
In addition, the decomposition reaction of nitrous acid ester is represented for example in the case where R is alkyl with following formula.
[changing 5]
(R and above-mentioned equivalent in meaning, alkyl of the R ' expressions here relative to few 1 carbon number of R.) in the formula (4), example
Such as in the case where R is methyl (methyl nitrite), due to no R ', therefore analyte is formic acid esters.
In the manufacture method of the oxalate diester of the present invention, preferably make the nitrous acid ester anti-in the gas phase with carbon monoxide
Should.
The reaction of the present invention can be utilized for example if gas phase reaction, then fills in the reaction tube for possess heater
After the oxalate diester catalyst for producing of the present invention, supply carbon monoxide, nitrous acid ester and inert gas and be allowed to the side such as reaction
Method is carried out.Reaction temperature now is preferably 50~200 DEG C, more preferably 80~150 DEG C.In addition, reaction pressure is preferably
Normal pressure is to 1MPaG (gauge pressure), and more preferably normal pressure is to 0.5MPaG (gauge pressure).By being set to the temperature range and pressure model
Enclose, it is possible to maintaining space-time yield (the Space Time Yield of necessary amounts：STY in the state of), the production of accessory substance is suppressed
It is raw.
The nitrous acid ester supplied is included sometimes turns into its nitric oxide or alcohol for manufacturing raw material, and in the reaction of the present invention
Even if in comprising they there will not be especially hinder reaction situation.In addition, carbon monoxide is either pure, still use indifferent gas
What body was diluted can use.
The concentration of the nitrous acid ester imported in the unstrpped gas in reactor is preferably 1~50 capacity %, more preferably 3~
30 capacity %, the concentration of carbon monoxide is preferably 10~90 capacity %.
Oxalate diester can be obtained using the reaction of the present invention, but distilation etc. can be carried out as needed, is removed
Carbonic diester as accessory substance etc..Furthermore it is possible to unreacted alkyl nitrite, carbon monoxide are reclaimed and recycled,
The nitric oxide of pair generation can be re-used for the manufacture of alkyl nitrite.
Embodiment
Below, embodiment is enumerated the present invention is specifically described, but the scope of the present invention is not limited to them.
Moreover, the analysis of reaction product is carried out using gas chromatography (fid detector, internal standard method), ICP (Inductively are utilized
Coupled Plasma) come analyze gained solid (catalyst) in metallic atom amount.
Embodiment 1 (manufacture of oxalate diester catalyst for producing)
After acid chloride 0.106g is added in acetone 12ml, irradiate ultrasonic wave and acid chloride is completely dissolved in acetone
In.Then, 1~2mm of diameter spherical Alpha-alumina (the mass % of Alpha-alumina content 99.5) 10g is impregnated into the solution,
Acetone is distilled off after 1 hour in stirring.
Then, the solid impregnating of gained is being dissolved with chlorination auric acid trihydrate 0.180g solution with water 7ml,
(about 80 DEG C) are dried overnight in drier after stirring 1 hour.After drying, a diameter of 30mm for the internal diameter for possessing electric furnace is transferred to
Quartz glass tube in, with 60ml/min circulate hydrogen while, at about 200 DEG C reduce 6 hours, obtain in Alpha-alumina
On be supported with palladium and gold globular solids catalyst.
Moreover, the composition of the catalyst of gained is as follows.
Palladium supports ratio；0.50 mass %
Gold supports ratio；0.93 mass %
Gold/palladium is present than=1 (mol ratio of metallic atom)
Embodiment 2~8, comparative example 1~2 (manufacture of oxalate diester catalyst for producing)
In embodiment 1, the ratio of acid chloride and chlorination auric acid trihydrate, produces palladium and supports used in changing
Ratio, gold support ratio and gold/palladium has the catalyst more different than (mol ratio of metallic atom).In addition, as a comparison, also one
And ground produces gold without using chlorination auric acid trihydrate and supports material that ratio is 0 mass %, without using acid chloride
Produce palladium and support the material that ratio is 0 mass %.
The composition of manufactured catalyst is represented in table 1.
[table 1]
Embodiment 9~16 and comparative example 3~4 (synthesis of dimethyl oxalate)
[changing 6]
In internal diameter 10mm, long 20cm glass system reaction tube, fill in the embodiment 1~8 and comparative example 1~2 and make
Standby catalyst 1ml (0.8g), then thereon with the highly-filled diameter 2mm of 5mm bead.
The reaction tube is fitted vertically, the silicone oil being heated is flowed through in the chuck portion at reaction tube, so that
After temperature in catalyst layer reaches that 120 DEG C of mode is heated, from reaction tube top, with catalyst feed rate (S.T.P)
20.0L/h is supplied by the capacity % of carbon monoxide 20.0, the capacity % of methyl nitrite 13.0, the capacity % of methanol 7.0, nitric oxide
The admixture of gas that the 1.0 capacity % and capacity % of nitrogen 59.0 are constituted.
Trapped in the methanol that will be cooled from reaction tube compound obtained by by using frozen water, carry out point of product
Analysis.It the results are shown in table 2.Embodiment 9~16 corresponds to point of the product obtained using the catalyst of embodiment 1~8
Result is analysed, comparative example 3~4 corresponds to the analysis result of the product obtained using the catalyst of comparative example 1~2.Moreover, so-called
DMO space-time yields (STY), represent that per unit catalyst capacity, the growing amount of the dimethyl oxalate of unit interval (DMO) (rub
You), the selection rate of dimethyl oxalate (DMO) and dimethyl carbonate (DMC) is on the basis of carbon monoxide.
Being held by methyl nitrite capacity 14%, methanol for supply carbon monoxide will only be stopped from above-mentioned admixture of gas
The admixture of gas that amount 7%, nitric oxide capacity 4% and nitrogen capacity 75% are constituted uses (the acid chloride of embodiment 17 shown in table 3
The ratio that supports be that 0.5 mass %, the ratio that supports of chlorination auric acid trihydrate are 0.1 mass %) catalyst and compare
The catalysis of example 5 (ratio that supports of acid chloride is that 0.5 mass %, the ratio that supports of chlorination auric acid trihydrate are 0 mass %)
Agent, is supplied with catalyst feed rate (S.T.P) 12.7L/h, the temperature in catalyst layer is set as into 130 DEG C.Trapping gained
Methyl nitrite analyte after carried out the analysis of catabolite.It the results are shown in table 3.So-called MN (nitrous acid first
Ester) resolution ratio, represent because decompose etc. without recovery methyl nitrite relative to per unit catalyst capacity, support time institute
The ratio (%) of the methyl nitrite of supply.
[table 2]
[table 3]
It can be seen from result more than, as shown in table 2, if using the oxalate diester catalyst for producing of the present invention,
Can be with high DMO space-time yields (that is, catalytic activity of the invention is high) and to obtain dimethyl oxalate in high yield.In addition may be used
Know, as shown in table 3, if using the oxalate diester catalyst for producing of the present invention, the nitrous acid as raw material can be suppressed
The decomposition of methyl esters.According to analysis, the major part of catabolite is methyl formate.
Industrial applicability
The present invention relates to for making carbon monoxide react and manufacture the catalyst (oxalate diester of oxalate diester with nitrous acid ester
Catalyst for producing) and used the catalyst oxalate diester manufacture method.Oxalate diester is for example as oxalic acid, oxalyl
Amine, ethanol acids, dyestuff intermediate and the useful compound of medical material.
Claims (9)
1. a kind of dimethyl oxalate catalyst for producing, it is the dimethyl oxalate for making carbon monoxide be reacted with methyl nitrite
Catalyst for producing,
Palladium or its compound and gold or its compound, and gold and palladium are supported with using aluminum oxide as the carrier of principal component
In the presence of than Au/Pd be 0.04~0.1.
2. dimethyl oxalate catalyst for producing according to claim 1, wherein,
It does not contain Cu (OCH3)Cl。
3. dimethyl oxalate catalyst for producing according to claim 1, wherein,
Carrier is the carrier using Alpha-alumina as principal component.
4. dimethyl oxalate catalyst for producing according to claim 1, wherein, using aluminum oxide as the carrier of principal component in
Aluminum oxide content relative to carrier the mass % of gross mass 100 be more than 90 mass %.
5. dimethyl oxalate catalyst for producing according to claim 3, wherein, using Alpha-alumina as the load of principal component
The content of Alpha-alumina in body is more than 90 mass % relative to the mass % of gross mass 100 of carrier.
6. dimethyl oxalate catalyst for producing according to claim 1, wherein, gold or its compound are halogenation auric acid.
7. dimethyl oxalate catalyst for producing according to claim 1, wherein, gold or its compound are chlorination auric acid.
8. dimethyl oxalate catalyst for producing according to claim 1, wherein, palladium supports ratio relative to complete with gold
Portion's catalytic amount is 0.01~1 mass %.
9. a kind of manufacture method of dimethyl oxalate,
It is in the presence of dimethyl oxalate catalyst for producing according to any one of claims 1 to 8, to make carbon monoxide
Reacted with methyl nitrite under conditions of 80 DEG C~130 DEG C of reaction temperature.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-054614 | 2011-03-11 | ||
| JP2011054614 | 2011-03-11 | ||
| CN2012800124499A CN103415340A (en) | 2011-03-11 | 2012-03-09 | Catalyst for production of oxalic acid diester, and method for producing oxalic acid diester using catalyst |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012800124499A Division CN103415340A (en) | 2011-03-11 | 2012-03-09 | Catalyst for production of oxalic acid diester, and method for producing oxalic acid diester using catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107262091A true CN107262091A (en) | 2017-10-20 |
Family
ID=46830688
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012800124499A Pending CN103415340A (en) | 2011-03-11 | 2012-03-09 | Catalyst for production of oxalic acid diester, and method for producing oxalic acid diester using catalyst |
| CN201710474766.7A Pending CN107262091A (en) | 2011-03-11 | 2012-03-09 | Oxalate diester catalyst for producing and used the catalyst oxalate diester manufacture method |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012800124499A Pending CN103415340A (en) | 2011-03-11 | 2012-03-09 | Catalyst for production of oxalic acid diester, and method for producing oxalic acid diester using catalyst |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5888322B2 (en) |
| CN (2) | CN103415340A (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 |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1097268B (en) * | 1978-06-23 | 1985-08-31 | Montedison Spa | PROCESS FOR THE PREPARATION OF ESTERS OF OXALIC ACID |
| JPS57123142A (en) * | 1981-01-26 | 1982-07-31 | Ube Ind Ltd | Production of oxalic diester |
| US6022823A (en) * | 1995-11-07 | 2000-02-08 | Millennium Petrochemicals, Inc. | Process for the production of supported palladium-gold catalysts |
| 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 |
| CN101596455B (en) * | 2008-06-04 | 2011-09-07 | 中国石油天然气股份有限公司 | Catalyst for synthesizing oxalic ester and preparation method 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 WO PCT/JP2012/056056 patent/WO2012124616A1/en active Application Filing
- 2012-03-09 CN CN2012800124499A patent/CN103415340A/en active Pending
- 2012-03-09 CN CN201710474766.7A patent/CN107262091A/en active Pending
- 2012-03-09 JP JP2013504700A patent/JP5888322B2/en not_active Expired - Fee Related
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 |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012124616A1 (en) | 2012-09-20 |
| CN103415340A (en) | 2013-11-27 |
| JP5888322B2 (en) | 2016-03-22 |
| JPWO2012124616A1 (en) | 2014-07-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Roh et al. | Trifluoroethylation of Alkynes: Synthesis of Allylic‐CF3 Compounds by Visible‐Light Photocatalysis | |
| Oliver Meseguer et al. | Very Small (3-6 Atoms) Gold Cluster Catalyzed Carbon-Carbon and Carbon-Heteroatom Bond-Forming Reactions in Solution | |
| KR102285717B1 (en) | Apparatus and method of preparing formic acid by hydrogenation of carbon dioxide | |
| Naeimi et al. | Highly efficient copper-imprinted functionalized mesoporous organosilica nanocomposites as a recyclable catalyst for click synthesis of 1, 2, 3-triazole derivatives under ultrasound irradiation: Multivariate study by factorial design of experiments | |
| Hosseini-Sarvari et al. | Nano copper (I) oxide/zinc oxide catalyzed N-arylation of nitrogen-containing heterocycles with aryl halides and arylboronic acids in air | |
| CN106414419A (en) | Chelate-controlled diastereoselective hydrogenation with heterogeneous catalyst | |
| JP7291142B2 (en) | Method for producing 1-acyloxy-2-methyl-2-propene | |
| CN106083724B (en) | A kind of preparation method of Dexmedetomidine | |
| CN107262091A (en) | Oxalate diester catalyst for producing and used the catalyst oxalate diester manufacture method | |
| EP0056993A1 (en) | Process for preparing oxalic acid diesters | |
| JPS6357409B2 (en) | ||
| JP6818094B2 (en) | Catalyst and method for producing it, method for producing N-alkylimidazole compound | |
| KR101199999B1 (en) | Supported Copper Catalysts for Synthesis of Dimethyl Carbonate by Oxidative Carbonylation of Methanol | |
| JPH0446618B2 (en) | ||
| CN105777494A (en) | Preparation method of glycol | |
| CN106824231A (en) | A kind of noble metal catalyst for acetylene hydrochlorination synthesis vinyl chloride thereof and preparation method thereof | |
| CN106179333A (en) | A kind of method of palladium magnesia-alumina hydrotalcite catalyzed Sonogashira cross-coupling reaction | |
| CN107344904A (en) | A kind of method of palladium chtalyst oxyalkylene generation MIBK | |
| KR20120016904A (en) | Method for preparing palladium and heteropolyacid catalysts supported on mesoporous silica, and method for producing the same | |
| CN105396584B (en) | CO couplings catalyst for synthesizing oxalic ester, preparation method and its usage | |
| JP6761791B2 (en) | (4Z, 7Z) -4,7-Decadien-1-yl = Acetate Production Method | |
| KR102110743B1 (en) | Method for producing saturated aldehyde from 1,2-alkanediol | |
| US10843998B2 (en) | Method for producing bis-acyloxylated exomethylene compound | |
| CN107226774A (en) | The manufacture method of the ethylene glycol of solid catalyst and the use solid catalyst | |
| KR101616195B1 (en) | Direct synthesis of hydrogen peroxide using Pd/silica-alumina catalysts having core/shell structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20171020 |