CN108409573A - A method of synthesis dimerization methyl glycollate - Google Patents
A method of synthesis dimerization methyl glycollate Download PDFInfo
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- CN108409573A CN108409573A CN201810463924.3A CN201810463924A CN108409573A CN 108409573 A CN108409573 A CN 108409573A CN 201810463924 A CN201810463924 A CN 201810463924A CN 108409573 A CN108409573 A CN 108409573A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/185—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
- B01J29/24—Iron group metals or copper
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
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Abstract
A method of synthesis dimerization methyl glycollate is related to a kind of method of synthesis industrial chemicals, and the present invention uses the H MOR (Cs+La) of silica alumina ratio Si/Al=12.50.1MIt is co-catalyst with the quality physical mixed such as HMOR Py, in raw material CO and dimethoxym ethane molar ratio 250:1, reaction temperature is 260 DEG C, reaction pressure 5.0MPa, and the mass space velocity of dimethoxym ethane is 1 h‑1When, product dimerization methyl glycollate is selectively stablized 77% or so, 1000 h of steady state operation, catalytic activity and selectivity of product are basically unchanged, for using dimethoxym ethane and carbon monoxide as the highly selective catalysis technique for preparing dimerization methyl glycollate of one step of raw material, the purpose of metal-modified molecular solids sieve catalyst is regulation and control solid acid property, including sour structure, acid strength, acid amount, sour density and activation CO absorption.Dimerization methyl glycollate has wide application in numerous areas such as chemical industry, medicine, dyestuffs, while large industrial chemicals ethylene glycol can be obtained after adding hydrogen.
Description
Technical field
The present invention relates to a kind of methods of synthesis chemical raw material, more particularly to a kind of side of synthesis dimerization methyl glycollate
Method.
Background technology
Dimerization methyl glycollate, structural formula are：HOCH2COOCH2COOCH3, English is commonly used entitled：methyl
Glycolatedimer is abbreviated as DMG, and dimerization methyl glycollate is typical fine chemical product, not only in chemical industry, medicine, dye
The numerous areas such as material have wide application, it is often more important that it can be prepared as the intermediate of organic synthesis and pharmaceutical synthesis
Such as with more application and research value chemical raw material：Hydrolysis glycolic processed, is carbonylated malonic acid (list) methyl esters processed, ammonolysis
Glycine processed, oxidative dehydrogenation glyoxalic acid methylester, to adapt to further production, experiment and the needs of application study.Together
When, dimerization methyl glycollate can prepare large industrial chemicals ethylene glycol and methanol by hydrogenation reaction, and reaction equation is such as
Under：
HOCH2COOCH2COOCH3+ 5H2→ HOCH2CH2OH+3CH3OH……………………….(1)
Ethylene glycol is as large industrial chemicals, mainly for the production of polyester fiber, automotive antifreeze, thawing solution, unsaturated polyester (UP)
Resin, lubricant, plasticizer, nonionic surfactant etc., can be additionally used in addition coating, photomicroscope, brake-fluid and
The industries such as ink, purposes are very extensive.
Currently, dimerization methyl glycollate is mainly passed through with methyl glycollate under liquid acid catalyst system by glycolic
Prepared by esterification, but the reaction side reaction is extremely more, and product is difficult to detach.Glycolic is prepared by formaldehyde carbonylation.Second
Alkyd methyl esters（Methyl glycolate, are abbreviated as MG）, structural formula HOCH2COOCH3, it is simplest a kind of carboxylic ester,
Containing α-H and hydroxyl and ester group Liang Zhong functional groups in molecule, therefore it has both the chemical property of alcohol and ester.Glycolic first at present
The synthetic route of ester is mainly the following：1) glyoxal and methanol are prepared by aldol condensation；2) formaldehyde carbonylation -ester；3)
Dimethoxym ethane and first acid oxidation alkyl glycolate ester；4) methyl formate and acetaldehyde coupling method；5）Chloroactic acid method；6）Formaldehyde and hydrogen
Cyanic acid addition process；7）Dimethoxym ethane and Formaldehyde Radical addition process；8）Hydrogenation of Dimethyl Oxalate partial reduction method；9）Biological oxydasis
Method.
Currently, there are no good methods to realize for the synthesis of extensive dimerization methyl glycollate.
Invention content
The purpose of the present invention is to provide a kind of method of synthesis dimerization methyl glycollate, the present invention proposes a kind of completely new
The synthetic method of dimerization methyl glycollate, core point are the acid with special sour structure, the exploitation of alkali both sexes solid catalyst,
Under modified solid acid, base catalysis, the highly selective method for preparing dimerization methyl glycollate of a step.
The purpose of the present invention is what is be achieved through the following technical solutions：
A method of synthesis dimerization methyl glycollate, the method includes the composite solids with unique acid activity position and basic active
The preparation method of body catalyst, the purpose of metal-modified molecular solids sieve catalyst are regulation and control solid acid property, including sour structure,
Acid strength, acid amount, sour density and activation CO absorption；Solid acid catalyst is selected from MOR mordenite molecular sieves, wherein molecule
Sieve content is 10-95 wt%；Atomic ratio Si/Al=10-30 of silicon and aluminium in MOR modenites；Synthesis reactor is that fixed bed is anti-
Answer device, fluidized-bed reactor or tank reactor.
A kind of method of the synthesis dimerization methyl glycollate, the MOR mordenite molecular sieves include calcium, barium, strontium,
One or more of magnesium, lanthanum, cerium, zirconium, zinc, gold, silver, gallium, lanthanum, copper, caesium, ferrous metal；Introducing method includes fabricated in situ, gold
Belong to ion exchange or dipping supports；And tenor accounts for the 0.01-10.0 wt% of total catalyst weight in terms of metal simple-substance.
A kind of method of synthesis dimerization methyl glycollate, the tenor preferably account for total catalyst weight
0.05-5.0 wt%。
A kind of method of synthesis dimerization methyl glycollate contains binder in the MOR mordenite molecular sieves,
The binder is any one or more in aluminium oxide, silica, magnesia, and binder content is that catalyst is total
The 0-70 wt % of weight.
Advantages of the present invention is with effect：
1）It is reaction raw materials by cheap dimethoxym ethane and carbon monoxide according to method provided herein, a step is highly selective
Ground synthesizes dimerization methyl glycollate.
2）According to method provided herein, product be methyl glycollate, dimerization methyl glycollate, methanol, dimethyl ether,
Methyl formate, boiling point difference is larger under condition of normal pressure, easily detaches, therefore can be with low energy consumption, low cost two polyglycolic acids of production
Methyl esters and methyl glycollate.
Description of the drawings
Fig. 1 is influence of the differential responses temperature to raw material DMM conversion ratios and selectivity of product.
Specific implementation mode
The following describes the present invention in detail with reference to examples.
The present invention is used for the urging as the highly selective preparation dimerization methyl glycollate of one step of raw material using dimethoxym ethane and carbon monoxide
Change technology, the purpose of metal-modified molecular solids sieve catalyst are regulation and control solid acid property, including sour structure, acid strength, acid amount,
Sour density and activation CO absorption：Solid acid catalyst is selected from MOR mordenite molecular sieves, and wherein molecular sieve content is 10-
95 wt%；Atomic ratio Si/Al=10-30 of silicon and aluminium in MOR modenites.MOR mordenite molecular sieves include calcium, barium, strontium,
One or more of metals such as magnesium, lanthanum, cerium, zirconium, zinc, gold, silver, gallium, lanthanum, copper, caesium, iron；Introducing method may include original position
Synthesis, metal ion exchanged or dipping support；And tenor accounts for the 0.01-10.0 of total catalyst weight in terms of metal simple-substance
wt%.Tenor preferably accounts for the 0.05-5.0 wt% of total catalyst weight.Binder in MOR mordenite molecular sieves can be with
It is the mixing of any one or more in aluminium oxide, silica, zirconium oxide, kaolin, and binder content is catalyst
The 0-70 wt % of total weight.
Influence of Fig. 1 differential responses temperature to raw material DMM conversion ratios and selectivity of product
Reaction condition：The molar ratio of CO and DMM is 250:1,1 h-1 of air speed, 2000 mL/min of CO flow velocitys, reaction pressure 5.0
MPa,（The mass mixings such as H-MOR- (Cs+La) 0.1M and HMOR-Py of silica alumina ratio Si/Al=12.5）Make catalyst, catalyst
10 g of quality.
The preparation method of several typical catalysts is as follows：
H-MOR system with molecular sieve for preparing is standby：With sodium aluminate (NaAlO2) it is that silicon source prepares mordenite molecular sieve, the silica alumina ratio (Si/ of colloidal sol
Al) it is 10-50.The sodium aluminate of metering is dissolved in water first, stirs into clear solution, sodium hydroxide is added and continues to stir.
Then the Ludox of metering is added into above-mentioned solution under stirring, continues to stir the homogeneous gel that will be obtained after 30min
Have in the stainless steel cauldron of tetrafluoro liner in being transferred to, the crystallization 20h under 180 DEG C of constant temperature oven, rotary state.Sample after crystallization
Product are washed through filtering, deionized water to neutrality.Sodium form mordenite molecular sieve is obtained after being dried overnight at 120 DEG C.Thereto plus
Enter certain density NH4NO3Solution, 80 DEG C of 10 h of exchange, filtration washing.After continuous exchange 3 times, 120 DEG C are dried overnight, and obtain
To NH4-MOR molecular sieves, 500 DEG C of 4 h of roasting obtain h-mordenite molecular sieve.Molecular sieve is pushed in 40MPa pressure
Piece is crushed to 20-40 mesh, obtains catalyst.
It is prepared by H-MOR- metal modified molecular screens：To NH4The nitric acid of 0.1M different metals is separately added into-MOR molecular sieves
Salting liquid（Metal includes：Na, Ga, Fe, La, Ca, Zr, Cu, K, Cs etc.）, 80 DEG C of 2 h of exchange, after filtration washing, 120 DEG C dry
Dry overnight, 500 DEG C of 4 h of roasting obtain H-MOR- metals0.1M（0.1 M represents the concentration of metal nitrate）Molecular sieve.
40MPa pressure lower sheetings, are crushed to 20-40 mesh, obtain catalyst.
H-MOR- (Cs+La) catalyst preparation：By infusion process by 0.1M La (NO3)3Solution is distinguished in ultrasound environments
Repeatedly it is impregnated in H-MOR-Cs0.1MOn molecular sieve.The catalyst precursor obtained after dipping is dried overnight for 120 DEG C in an oven.
4h is roasted at 500 DEG C, molecular sieve is crushed to 20-40 mesh in 40MPa pressure lower sheetings after having roasted, obtains H-MOR- (Cs+
La)0.1MCatalyst.
HMOR-Py system with molecular sieve for preparing is standby：HMOR or metal-modified molecular sieve are positioned in tube furnace, N2Flow velocity is 30
ML/min is heated to 300 DEG C with the heating rate of 10 DEG C/min, maintains 2h at such a temperature.Then 280 DEG C are cooled to, then is used
Pyridine and N2Mixing（30mL / min）12h is purged, N is then used2（30mL/ min）4h is purged, after being saturated Adsorption of Pyridine
HMOR molecular sieves are denoted as HMOR-Py.In 40MPa pressure lower sheetings, it is crushed to 20-40 mesh, obtains catalyst.
Embodiment 1
10 g variety classes catalyst are filled into fixed bed reactors respectively（If two kinds of catalyst mixing additions, are pressed
According to mass ratio 1:1 is uniformly mixed）, carry out pre-treatment.Catalyst pre-treatment condition is：N2Flow velocity 100mL/min, since 25 DEG C
500 DEG C are risen to through 150min, and 180min is kept under the conditions of 500 DEG C.Using dimethoxym ethane as raw material, by high pressure constant flow pump to be catalyzed
1 h of agent mass space velocity-1It is pumped into reactor, the molar ratio of CO flow velocitys 2000 mL/min, wherein CO and DMM are respectively 250:1, instead
Answer 260 DEG C of temperature, 5.0 MPa of reaction gross pressure.
Dimethoxym ethane conversion ratio indicates that DME indicates that dimethyl ether, MeOH indicate that methanol, MF indicate methyl formate, MMAc with DMM
Indicate that methoxy menthyl acetate, MG indicate that methyl glycollate, DMG indicate that dimerization methyl glycollate selectivity, selectivity of product are pressed
It is calculated according to Mass Selective.We can obtain from table 1, under the same reaction conditions, with silica alumina ratio Si/Al=12.5
H-MOR-(Cs+La)0.1MWith HMOR-Py according to mixing quality 1:When 1 addition, product dimerization methyl glycollate selectively reaches most
A height of 76%, raw material DMM conversion ratios are close to 100%.
Table 1 uses variety classes catalyst raw material dimethoxym ethane conversion ratio and selectivity of product result
Embodiment 2
By 10 g silica alumina ratios Si/Al=12.5（H-MOR-(Cs+La)0.1M+HMOR-Py）It is anti-that catalyst is filled into fixed bed
It answers in device, carries out pre-treatment.Catalyst pre-treatment condition is：N2Flow velocity 100mL/min rises to since 25 DEG C through 150min
500 DEG C, and keep 180min under the conditions of 500 DEG C.Using dimethoxym ethane as raw material, by high pressure constant flow pump with catalyst quality air speed
1h-1It is pumped into reactor, the molar ratio of CO flow velocitys 2000 mL/min, wherein CO and DMM are respectively 100:1、125:1、150:1、
175:1、200:1、250:1,260 DEG C of reaction temperature, 5.0 MPa of reaction gross pressure.
According to table 2 it is found that in 260 DEG C of identical reaction temperature, reaction pressure（5.0 MPa）Under the conditions of, as reaction is former
Material CO and DMM molar ratios gradually increase（It is increased to 250/1 from 100/1）, dimerization methyl glycollate Mass Selective gradually increases
（It is promoted to 76% from 39%）, when CO and DMM molar ratios are 250:When 1, the selectivity of dimerization methyl glycollate reaches maximum value and is
76%.Meanwhile the selectivity of methyl glycollate also reaches and is up to 10%.If continuing growing CO and DMM ratios, it is anticipated that two
Polyglycolic acid methyl esters can selectively further increase.
2 difference CO/DMM molar ratios of table influence feed stock conversion and selectivity of product
Embodiment 3
By 10g silica alumina ratios Si/Al=12.5（H-MOR-(Cs+La)0.1M+HMOR-Py）Catalyst is filled into fixed bed reaction
In device, pre-treatment is carried out.Catalyst pre-treatment condition is：N2Flow velocity 100mL/min rises to 500 since 25 DEG C through 150min
DEG C, and keep 180min under the conditions of 500 DEG C.Using dimethoxym ethane as raw material, by high pressure constant flow pump with 1 h of catalyst quality air speed-1
It is pumped into reactor, the molar ratio of CO flow velocitys 2000 mL/min, wherein CO and DMM are 250:1, reaction temperature is respectively 200,
220,240,260,280,300 DEG C, 5.0 MPa of reaction gross pressure.
Influence of the 3 differential responses temperature of table to feed stock conversion and selectivity of product
According to table 3 it is found that when temperature is 200 DEG C, dimerization methyl glycollate is only selectively 40%, with reaction temperature
Gradually rise, dimerization methyl glycollate selectively gradually increases, and when 260 DEG C of temperature, it is 76% selectively to reach maximum value,
Reaction temperature continues to increase later, and dimerization methyl glycollate selectively continuously decreases.By-product dimethyl ether and methanol selectivity with
The raising of temperature first reduces and increases afterwards.
Embodiment 4
By 10 g silica alumina ratios Si/Al=12.5（H-MOR-(Cs+La)0.1M+HMOR-Py）It is anti-that catalyst is filled into fixed bed
It answers in device, carries out pre-treatment.Catalyst pre-treatment condition is：N2Flow velocity 100mL/min rises to since 25 DEG C through 150min
500 DEG C, and keep 180min under the conditions of 500 DEG C.Using dimethoxym ethane as raw material, by high pressure constant flow pump with catalyst quality air speed
1h-1It is pumped into reactor, CO flow velocitys 2000 mL/min's, wherein CO and DMM mole is 250:1,260 DEG C of reaction temperature, reaction
Gross pressure is respectively 2.5,3.0,3.5,4.0,4.5,5.0 MPa.
Influence of the 4 differential responses pressure of table to feed stock conversion and selectivity of product
According to table 4 it is found that in identical reaction temperature（260 ℃）, identical CO and DMM molar ratios（250/1）, with
Reaction pressure gradually rises（2.5-5.0 MPa）, the selectivity of product dimerization methyl glycollate is consequently increased（It is promoted from 34%
To 76%）.When reaction pressure is 3.5 MPa, the selectivity of dimerization methyl glycollate reaches 52%, and reaction pressure continues to increase to
When 5.0MPa, product dimerization methyl glycollate selectively reaches as high as 76%.Product dimethyl ether, methanol and methyl formate selection
Property is also to be continuously decreased with the raising of reaction pressure.
Embodiment 5
By 10 g silica alumina ratios Si/Al=12.5（H-MOR-(Cs+La)0.1M+HMOR-Py）It is anti-that catalyst is filled into fixed bed
It answers in device, carries out pre-treatment.Catalyst pre-treatment condition is：N2Flow velocity 100mL/min rises to since 25 DEG C through 150min
500 DEG C, and keep 180min under the conditions of 500 DEG C.Using dimethoxym ethane as raw material, by high pressure constant flow pump respectively with catalyst quality sky
Speed 0.25,0.75,1.0,1.25,1.50,2.0h-1It is pumped into reactor, 2000 mL/min of CO flow velocitys, mole of wherein CO and DMM
Than being respectively 250:1,260 DEG C of reaction temperature, reaction gross pressure is 3.0 MPa.
According to table 5 it is found that in reaction temperature（260 ℃）, reaction pressure（3.0 MPa）Under the same conditions, with catalysis
The reduction of agent mass space velocity（It is reduced to 0.25h from 2.00-1）, the selectivity of product dimerization methyl glycollate dramatically increases.When urging
Agent mass space velocity is 0.25 h-1When, the selectivity of dimerization methyl glycollate is up to 88%, the selectivity of methyl glycollate
It is 7%.
Influence of the 5 different quality air speed of table to feed stock conversion and selectivity of product
Embodiment 6
Catalyst stability is evaluated
By processed silica alumina ratio Si/Al=12.5 2000 g（H-MOR-(Cs+La)0.1MWith HMOR-Py according to mass ratio
1:1 physical mixed）It is 10cm that catalyst, which is packed into internal diameter, highly in the stainless steel fixed bed reactors of 200cm, reactor is vacant
Volume fractiion is filled with quartz sand.Reaction temperature in reactor is 260 DEG C, reaction pressure 5.0MPa, reaction system stable state behaviour
When making, CO in reactor:Dimethoxym ethane=250:1, the mass space velocity of raw material dimethoxym ethane is 1 h-1, the choosing of product dimerization methyl glycollate
Selecting property is stablized 77% or so, and 1000 h of steady state operation, catalytic activity and selectivity of product are basically unchanged.
The above is only several embodiments of the application, not does any type of limitation to the application, although this Shen
Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off
In the range of technical scheme, makes a little variation using the technology contents of the disclosure above or modification is equal to
Case study on implementation is imitated, is belonged in technical proposal scope.
Claims (4)
1. it is a kind of synthesis dimerization methyl glycollate method, which is characterized in that the method includes have unique acid activity position and
The purpose of the preparation method of the complex solid catalyst of basic active, metal-modified molecular solids sieve catalyst is regulation and control solid acid
Matter, including sour structure, acid strength, acid amount, sour density and activation CO absorption；Solid acid catalyst is selected from MOR modenites
Molecular sieve, wherein molecular sieve content are 10-95 wt%；Atomic ratio Si/Al=10-30 of silicon and aluminium in MOR modenites；Synthesis
Reactor is fixed bed reactors, fluidized-bed reactor or tank reactor.
2. a kind of method of synthesis dimerization methyl glycollate according to claim 1, which is characterized in that the MOR mercerisings
Zeolite molecular sieve includes one or more of calcium, barium, strontium, magnesium, lanthanum, cerium, zirconium, zinc, gold, silver, gallium, lanthanum, copper, caesium, ferrous metal；
Introducing method includes that fabricated in situ, metal ion exchanged or dipping support；And tenor accounts for catalyst in terms of metal simple-substance
The 0.01-10.0 wt% of total weight.
3. a kind of method of synthesis dimerization methyl glycollate according to claim 2, which is characterized in that the tenor
It is preferred that accounting for the 0.05-5.0 wt% of total catalyst weight.
4. a kind of method of synthesis dimerization methyl glycollate according to claim 1, which is characterized in that the MOR mercerisings
Containing binder in zeolite molecular sieve, the binder is any one or more in aluminium oxide, silica, magnesia,
And the 0-70 wt % that binder content is total catalyst weight.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112645816A (en) * | 2019-10-10 | 2021-04-13 | 中国石油化工股份有限公司 | Catalytic synthesis method of methyl methoxyacetate |
| CN113019441A (en) * | 2021-03-17 | 2021-06-25 | 中国矿业大学 | Preparation method and application of MOR molecular sieve doped with metallic iron in situ |
-
2018
- 2018-05-15 CN CN201810463924.3A patent/CN108409573A/en not_active Withdrawn
Non-Patent Citations (1)
| Title |
|---|
| 王岩等: "丝光沸石分子筛内不同酸性位对气相甲缩醛羰化转化影响的研究", 《第19届全国分子筛学术大会论文集》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112645816A (en) * | 2019-10-10 | 2021-04-13 | 中国石油化工股份有限公司 | Catalytic synthesis method of methyl methoxyacetate |
| CN112645816B (en) * | 2019-10-10 | 2023-04-07 | 中国石油化工股份有限公司 | Catalytic synthesis method of methyl methoxyacetate |
| CN113019441A (en) * | 2021-03-17 | 2021-06-25 | 中国矿业大学 | Preparation method and application of MOR molecular sieve doped with metallic iron in situ |
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Application publication date: 20180817 |