CN107501091B - A kind of method of catalyst preparation methyl glycollate and by-product methoxy menthyl acetate - Google Patents
A kind of method of catalyst preparation methyl glycollate and by-product methoxy menthyl acetate Download PDFInfo
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Abstract
A kind of method of catalyst preparation methyl glycollate and by-product methoxy menthyl acetate, be related to it is a kind of prepare industrial chemicals method, the present invention is using dimethoxym ethane as solvent, trimerization, four poly- or sources that paraformaldehyde and dimethoxym ethane are as formaldehyde, with H2SO4, liquid acids such as HCl or using solid acids such as cation exchange resin, heteropoly acid, immersion-type solid acid, solid super-strong acids as catalyst, a step high conversion, highly selective synthesizing methyl glycolate and by-product methoxy menthyl acetate.In fixed bed reactors, using NKC-9 azochlorosulfonate acid resin catalyst, 300 g of catalyst amount, material rate are as follows: 20 kg dimethoxym ethanes, 4 kg water, 3.9 kg metaformaldehydes, material quality air speed are 30 h‑1, 130 DEG C of reaction temperature, react under 6.0 MPa of reaction pressure, 2000 h non-inactivation of catalyst stabilization, dimethoxym ethane conversion ratio is 89.83%, and product ethanol acid methyl esters Mass Selective is 28.88%, and methoxy menthyl acetate Mass Selective is 67.68%.Synthetic route of the present invention is short, and feed stock conversion is high or product selectivity is high, and synthesis process is without dye environment.
Description
Technical field
The present invention relates to a kind of preparation methods of methyl glycollate, more particularly to a kind of catalyst preparation methyl glycollate
And the method for by-product methoxy menthyl acetate.
Background technique
Methyl glycollate (HOCH2COOCH3), english abbreviation MG is a kind of liquid that is colourless, having euosmia, fusing point 74
DEG C, 150 DEG C of boiling point, density 1.168g/cm3, it is dissolved in water, and pure and mild ether can be dissolved in any proportion.Methyl glycollate has α-
H, hydroxyl and ester functional groups, therefore it has the chemical property of pure and mild ester concurrently, and oxonation, hydrolysis, ammonification can occur
Reaction, oxidation reaction etc..Methyl glycollate itself is the fine solvent of many celluloses, resin and rubber, is soluble in nitro fibre
Tie up element, cellulose acetate, polyvinyl acetate etc..Methyl glycollate is also the important intermediate of organic synthesis and pharmaceutical synthesis,
For example, the different tricuspid ester alkali and the like with anticancer activity can be synthesized using methyl glycollate as intermediate.Glycolic first
Ester is also the raw material for synthesizing the anti-carrier additives of some raising lubricating oil crushing resistances and wearability.
Many important downstream product can be synthesized by raw material of methyl glycollate.For example, methyl glycollate is anti-through carbonylation
Malonic acid monomethyl ester should be synthesized, reaction generates malonic acid dimethyl on acid cation exchange resin at 70 DEG C of malonic acid monomethyl ester
Ester；Methyl glycollate synthesizes DL- glycine through aminating reaction；Methyl glycollate is by adding hydrogen to obtain large chemical products second two
Alcohol；Methyl glycollate hydrolyzes to obtain glycolic, and glycolic is mainly used as the cleaning agent of boiler, printed circuit board, while ethyl alcohol
Sour polycondensation produces polyglycolic acid, and polyglycolic acid is a kind of biodegradable material and the absorbable medical material of human body；Second
Alkyd methyl esters oxidative dehydrogenation generates glyoxalic acid methylester, and glyoxalic acid can be obtained in the latter's hydrolysis.Ethylene glycol, dimethyl malenate, sweet ammonia
Acid, glycolic and glyoxalic acid are all current domestic and international chemical products in short supply or more in short supply.
Consulting literatures are it is found that methyl glycollate is mainly the following synthetic method:
(1) with glyoxal and methanol one-step synthesis methyl glycollate
HCOCOH+CH3OH → HOCH2COOCH3+H2O....................................(1)
Mitsui East Asia Chemical Co., Ltd. is using glyoxal or its acetal and methanol as raw material, with Al (NO3)3·
9H2O is catalyst, 160 DEG C of reaction temperature, reacts and obtains methyl glycollate after 0.5 h, and glyoxal conversion ratio is up to 98%, ethyl alcohol
The selectivity of sour methyl esters is 97%.But raw material glyoxal is toxic, has strong impulse effect to skin and mucous membrane, and in the market
The price of 40 % glyoxals is at 8000 yuan/ton or so, therefore the method is unfavorable for large-scale industrial production.
(2) dimethoxym ethane and formic acid method
Texaco Oil E.L. Yeakey et al. uses CH3OCH2OCH3(dimethoxym ethane) and HCOOH are raw material,
In the presence of organic peroxide, and alkyl glycolate ester is prepared under non-acidic conditions, but disadvantage of this law is that
Reaction product is difficult to separate.
(3) coupling method
It is raw material that the method, which uses methyl formate and metaformaldehyde (or paraformaldehyde for), using acidic catalyst synthesizing alcohol
Sour methyl esters.
HCOOCH3+HCHO → HOCH2COOCH3....................................(2)
J.S. Lee et al. uses the concentrated sulfuric acid or organic sulfonic acid for catalyst, there is methyl glycollate, ethyl alcohol in reaction product
Acid and methyl formate, have that product is difficult to separate.Kunming University of Science and Technology Li Zhifeng et al. uses peroxophosphoric acid for catalyst,
The yield of methyl glycollate is 59.06 %, but the perishable reactor of strong acid and brings liquid waste processing problem.Mitsubishi chemistry is public
Department uses methyl formate and formaldehyde or trioxane for raw material, and even phosphomolybdic acid, montmorillonite or cation exchange resin etc. are catalyst,
Reaction product has methoxy menthyl acetate, methoxyacetic acid, methyl glycollate, oxalic acid methyl ether etc., though the method solves corrosion
Problem, but need higher reaction pressure.Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences is silver-colored (I)-using carbonyl copper (I) or carbonyl
Sulfuric acid catalyst system, the yield of methyl glycollate are 36.20%.
(4) chloroactic acid method
ClCH2COOH+NaOH → HOCH2COOH +NaCl..................................(3)
2HOCH2COOH → 2HOCH2COOCH3......................................(4)
The method is to mix monoxone with sodium hydroxide solution, heating water bath, is evaporated under reduced pressure.Sodium chloride is filtered out, in oil bath
Upper heating obtains paste liquid, methanol and the concentrated sulfuric acid is added later, flow back to obtain methyl glycollate.Disadvantage of this law is that monoxone system
It is standby difficult, and monoxone severe corrosion to equipment.
(5) formaldehyde and hydrogen cyanide addition process
HCHO + HCN → HOCH2CN → HOCH2COOH → HOCH2COOCH3.......(5)
The method is that addition reaction occurs for formaldehyde and hydrogen cyanide under sulfuric acid catalysis, obtains hydroxyacetonitrile, then hydrolyzes, is esterified
The methyl glycollate that gross production rate is 80 % can be obtained.
(6) Hydrogenation of Dimethyl Oxalate reduction method
(COOCH3) 2 + H2→ HOCH2COOCH3+CH3OH.................................(6)
Italy uses H4Ru(CO)8(PBu3)2Ru(CO)2、(CH3COO)2(PBu3)2、[ ( Ph3P) ( Ph2P)
RuH2]2K2For catalyst, under the conditions of 180 DEG C of reaction temperature, 13. 2MPa of Hydrogen Vapor Pressure, methyl glycollate yield is up to 100
%, but the method is used as catalyst using organic precious metal, and preparation process complexity is expensive and be difficult to recycle；Japan is using load
Type copper and silver catalyst, dimethyl oxalate conversion ratio are 90. 2 %, and methyl glycollate yield is 68 %.
(7) formaldehyde carbonylation -ester is combined to method
HCHO+CO+H2O → HOCH2COOH...........................................(7)
HOCH2COOH +CH3OH → HOCH2COOCH3...................................(8)
Soumay Sano H et al. exists formalin and CO under the catalyst actions such as the concentrated sulfuric acid or boron trifluoride
It is first condensed generation glycolic under 70.9MPa and hot conditions, glycolic and methanol esterification are then generated into methyl glycollate, the method
Used catalyst has strong corrosive and reaction pressure is very high, therefore is unfavorable for large-scale industrial production.Japan
Industrial Co., Ltd, Mitsubishi Chemical and German Hirst company are respectively adopted heteropoly molybdic acid, miscellaneous more wolframic acids and highly acidic cation and hand over
Changing resin etc. is catalyst, and oxonation pressure can be down to 5.9 MPa, and methyl glycollate selectively also greatly improves, but the method
It using strongly acidic catalyst severe corrosion to equipment, and is reaction under high pressure, the high requirements on the equipment.A.T.Bell et al. is used
Methyl formate replaces gaseous CO and formaldehyde carries out carbonylation, but is ratedeterming step since methyl formate decomposes release CO,
Influence catalytic perfomance.
To sum up, all to there is synthetic route too long for the synthetic method of methyl glycollate at present, and feed stock conversion is low or produces
The problems such as product are selectively low, and synthesis process pollutes environment.
Summary of the invention
The purpose of the present invention is to provide the sides of a kind of catalyst preparation methyl glycollate and by-product methoxy menthyl acetate
Method, the present invention is using dimethoxym ethane as solvent, the source of trimerization, four poly- or paraformaldehydes as formaldehyde, to open up a synthesis second
The method of alkyd methyl esters and by-product methoxy menthyl acetate new way, invention synthetic route is short, and feed stock conversion is high or product selects
Selecting property is high, and synthesis process is without dye environment.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of method of catalyst preparation methyl glycollate and by-product methoxy menthyl acetate, the method are with dimethoxym ethane
The source of solvent, aldehyde compound and dimethoxym ethane as formaldehyde, uses solid acid or liquid acid for catalyst, by system
It is middle that a small amount of water, a step high conversion, highly selective synthesizing methyl glycolate and by-product methoxy menthyl acetate is added；Aldehydes
Close that object includes trimerization, four is poly- or one of paraformaldehyde or a variety of；
Including following procedure:
Using dimethoxym ethane as solvent, the source of trimerization, four poly- or paraformaldehydes as formaldehyde, using solid acid as catalyst,
Under the premise of in system with the presence of suitable quantity of water, a step high conversion, highly selective synthesizing methyl glycolate (MG)；In dimethoxym ethane
Source as aldehyde radical of aldehyde radical, trimerization, four poly- or paraformaldehydes, dimethoxym ethane is used as solvent and methoxyl group offer forerunner simultaneously
Body effectively can largely dissolve trimerization, four poly- or paraformaldehydes, under water and catalyst existence condition, trimerization, four it is poly- or
Paraformaldehyde can more exist in the form of free formaldehyde in dimethoxym ethane；With aldehyde radical ratio in system and reaction temperature by
Edge up height, and with water and CO carbonylation occurs for free formaldehyde first, glycolic is generated, as shown in equation (7)；
HCHO+CO+H2O → HOCH2COOH..........................................(7)
Meanwhile water and a large amount of dimethoxym ethanes there are under the premise of, dimethoxym ethane can be reacted with water, generate DMM2, and slowly release
Methanol is released, as shown in equation (8)；
2CH3OCH2OCH3 + H2O → CH3OCH2OCH2OCH3(DMM2)+ 2CH3OH............(8)
The methanol slowly released, be more prone under a large amount of glycolic existence conditions occur esterification, rather than itself
Dehydration；Therefore, easily with the methanol released esterification occurs for the glycolic of generation, such as reaction equation (9), generates MG
And H2O, the reaction can consume glycolic and methanol simultaneously；As reaction (9) carry out, glycolic and methanol are constantly consumed,
Formaldehyde oxonation and methanol can be promoted to discharge reaction to carry out to positive reaction；The water that reaction (9) generates equally is used as reactant
Reaction equation (7,8) are promoted to carry out to positive direction；The reaction system can carry out under low water conditions, and the effect of water is similar to urge
Agent participates in reaction and generates again as product；Avoiding the first step in two-step method in this way must have a large amount of water as reaction
Object participates in reaction；The presence of water can significantly reduce the carbonylation efficiency of catalyst.
HOCH2COOH +CH3OH → HOCH2COOCH3 +H2O................................(9)
Solvent DMM itself can also occur oxonation and generate methoxy menthyl acetate (MMAc), as shown in equation (10)；
MMAc itself is a kind of medicine intermediate of high added value, and MMAc dissolubility is splendid, not only can with dissolved organic matter, and
It can also dissolve each other with water arbitrary proportion, can promote and dissolve formaldehyde again during the reaction, while can largely dissolve gas phase
In CO, make catalyst surface in liquid phase have an opportunity to contact more CO, be obviously improved CO and aldehyde radical ratio in liquid phase, promote carbonylation
The progress of reaction；
CH3OCH3OCH3+CO → CH3OCH2COOCH3(MMAc).............................(10)。
A kind of method of catalyst preparation methyl glycollate and by-product methoxy menthyl acetate, the catalyst packet
Include liquid acid (H2SO4, HCl etc.), cation exchange resin (NKC-9, Amberlyst-15, DA330, KAD302, KC107,
D072H etc.), heteropoly acid (phosphotungstic acid, molybdenum wolframic acid, silico-tungstic acid), solid super-strong acid (SO4 2 - / ZrO2, WO3/ZrO2, MoO3/
ZrO2, B2O3/ ZrO2), immersion-type solid acid (SO4 2 - / SiO2) it is one or more.
A kind of method of the catalyst preparation methyl glycollate and by-product methoxy menthyl acetate, the dimethoxym ethane with
The molar ratio of aldehyde radical is 0.5:1-4:1；The additional amount of water is the 3-30% of dimethoxym ethane quality；90-150 DEG C of reaction temperature, reaction pressure
Power 2.0-15.0 MPa, reaction time 1-8 h.
A kind of method of catalyst preparation methyl glycollate and by-product methoxy menthyl acetate, the liquid acid packet
Include H2SO4, HCl it is one or more.
A kind of method of catalyst preparation methyl glycollate and by-product methoxy menthyl acetate, the solid acid packet
Include cation exchange resin, heteropoly acid, solid super-strong acid, immersion-type solid acid it is one or more.
A kind of method of catalyst preparation methyl glycollate and by-product methoxy menthyl acetate, the cation are handed over
Changing resin includes the one or more of NKC-9, Amberlyst-15, DA330, KAD302, KC107, D072H；Heteropoly acid includes
Phosphotungstic acid, molybdenum wolframic acid, silico-tungstic acid it is one or more；Solid super-strong acid includes SO4 2- / ZrO2, WO3/ZrO2, MoO3/ ZrO2,
B2O3/ ZrO2It is one or more；Immersion-type solid acid includes SO4 2 - / SiO2It is one or more.
The advantages and effects of the present invention are:
The method that the present invention opens a completely new methyl glycollate and by-product methoxy menthyl acetate, it is advantageous that
Reaction system can carry out under low water conditions, and water participates in reaction and generates again as product, avoid the first step in two-step method
There must be a large amount of water to participate in reacting as reactant, the methoxy menthyl acetate itself generated during simultaneous reactions is a kind of high
The medicine intermediate of added value can largely dissolve the CO in gas phase, and catalyst surface in liquid phase is made to have an opportunity to contact more CO,
It is obviously improved CO and aldehyde radical ratio in liquid phase, promotes the progress of oxonation.Methyl glycollate (MG), methoxy menthyl acetate
(MMAc) the two boiling point difference is larger, can separate product subsequently through simple distillation.Synthetic route of the present invention
Short, feed stock conversion is high or product selectivity is high, and synthesis process is without dye environment.
Detailed description of the invention
Fig. 1 be when using NKC-9 as catalyst reaction temperature to the influence diagram of feed stock conversion and selectivity of product.
Specific embodiment
The following describes the present invention in detail with reference to examples.
The present invention is using dimethoxym ethane as solvent, the source of trimerization, four poly- or paraformaldehydes as formaldehyde, with solid acid to urge
Agent, under the premise of in system with the presence of suitable quantity of water, a step high conversion, highly selective synthesizing methyl glycolate (MG).It
The methyl glycollate of preceding document and patent report synthesis have to pass through two steps: be that formaldehyde carbonyl turns to glycolic first, then plus
Entering a large amount of methanol esterifications is methyl glycollate.In the completely new one-step synthesis method route, aldehyde radical, trimerization in dimethoxym ethane, four it is poly- or
Source of person's paraformaldehyde as aldehyde radical, dimethoxym ethane is used as solvent and methoxyl group to provide presoma simultaneously effectively largely to be dissolved
Trimerization, four is poly- or paraformaldehyde (since dimethoxym ethane itself has aldehyde radical, dissolution to aldehyde radical and promotes free effect very
It is good), it is trimerization, four poly- or paraformaldehyde can be in dimethoxym ethane more with first of dissociating under water and catalyst existence condition
Aldehyde form exists.As aldehyde radical ratio and reaction temperature gradually rise in system, with water and CO carbonyl occurs for free formaldehyde first
Glycosylation reaction generates glycolic, as shown in equation (7).
HCHO+CO+H2O → HOCH2COOH.........................................(7)
Meanwhile water and a large amount of dimethoxym ethanes there are under the premise of, dimethoxym ethane can be reacted with water, generate DMM2, and slowly release
Methanol is released, as shown in equation (8).
2CH3OCH2OCH3 + H2O → CH3OCH2OCH2OCH3(DMM2)+ 2CH3OH............(8)
The methanol slowly released, be more prone under a large amount of glycolic existence conditions occur esterification, rather than itself
Dehydration.Therefore, easily with the methanol released esterification occurs for the glycolic of generation, such as reaction equation (9), generates MG
And H2O, the reaction can consume glycolic and methanol simultaneously.As reaction (9) carry out, glycolic and methanol are constantly consumed,
Formaldehyde oxonation and methanol can be promoted to discharge reaction to carry out to positive reaction.The water that reaction (9) generates equally is used as reactant
Reaction equation (7,8) are promoted to carry out to positive direction.The reaction system can carry out under low water conditions, and the effect of water is similar to urge
Agent participates in reaction and generates again as product.Avoiding the first step in two-step method in this way must have a large amount of water as reaction
Object participates in reaction.The presence of water can significantly reduce the carbonylation efficiency of catalyst.
HOCH2COOH +CH3OH → HOCH2COOCH3 +H2O.............................(9)
Solvent DMM itself can also occur oxonation and generate methoxy menthyl acetate (MMAc), as shown in equation (10).
MMAc itself is a kind of medicine intermediate of high added value, and MMAc dissolubility is splendid, not only can with dissolved organic matter, and
It can also dissolve each other with water arbitrary proportion, can promote and dissolve formaldehyde again during the reaction, while can largely dissolve gas phase
In CO, make catalyst surface in liquid phase have an opportunity to contact more CO, be obviously improved CO and aldehyde radical ratio in liquid phase, promote carbonylation
The progress of reaction.
CH3OCH3OCH3+CO → CH3OCH2COOCH3(MMAc).............................(10)
Different types of catalyst of the present invention includes liquid acid (H2SO4, HCl etc.), cation exchange resin (NKC-
9, Amberlyst-15, DA330, KAD302, KC107, D072H etc.), it is heteropoly acid (phosphotungstic acid, molybdenum wolframic acid, silico-tungstic acid etc.), solid
Body super acids (SO4 2 - / ZrO2, WO3/ZrO2, MoO3/ ZrO2, B2O3/ ZrO2), immersion-type solid acid (SO4 2 - / SiO2)
Deng it is one or more.
Embodiment 1
20 kg dimethoxym ethanes (DMM), 3.9 kg metaformaldehydes (DMM and aldehyde radical molar ratio 2:1), 300 g catalysis are weighed respectively
Agent, 4 kg water are fitted into reaction kettle, and catalyst type is respectively liquid acid (H2SO4, HCl), cation exchange resin (NKC-9,
Amberlyst-15, DA330, KAD302, KC107, D072H), heteropoly acid (phosphotungstic acid, molybdenum wolframic acid, silico-tungstic acid), solid super strong
Acid (SO4 2 - / ZrO2, WO3/ZrO2, MoO3/ ZrO2, B2O3/ ZrO2), immersion-type solid acid (SO4 2 - / SiO2), then lead to
Enter 1.0 MPa CO gas, if after not omitting sky gas reactor in printing, repeating aforesaid operations 2 times (air in replacement reaction kettle).
The gas for being passed through a certain amount of (6.0 MPa) again leaks hunting, and stands 15 min, and pressure gauge registration does not decline, and indicates dress
No gas leakage is set, gas reactor is then emptied, is filled with 6.0 MPa CO gases, heat temperature raising, reaction kettle stirring into kettle again
500 revs/min of speed, 6.0 MPa of reaction pressure, 130 DEG C of reaction temperature, 6 h of reaction time, different catalysts type reaction result
As shown in table 1.
Reaction condition: 20 kg dimethoxym ethanes, 3.9 kg metaformaldehydes, 4 kg water, 300 g catalyst, 130 DEG C of reaction temperature,
Reaction pressure 6.0MPa, 6 h of reaction time.
As can be seen from Table 1, best using azochlorosulfonate acid resin catalyst reaction effect, when using NKC-9 sulfonate resin, anti-
130 DEG C of temperature, 6.0 MPa of reaction pressure, 6 h of reaction time are answered, when catalyst charge is 300 g, DMM conversion ratio is
71.11%, product MMAc Mass Selective is that 14.23%, MG Mass Selective is 60.55%, and preferably NKC-9 sulfonate resin is catalyzed
Agent.
Embodiment 2
Weigh 20 kg dimethoxym ethanes (DMM) respectively, 3.9 kg metaformaldehydes (DMM and aldehyde radical molar ratio 2:1), 4 kg water,
300 g NKC-9 resin catalysts are fitted into reaction kettle, then pass to 1.0 MPa CO gas, if not omitting in printing in sky kettle
After gas, aforesaid operations 2 times (air in replacement reaction kettle) is repeated.The gas for being passed through a certain amount of (6.0 MPa) again is surveyed
Leakage, and 15 min are stood, pressure gauge registration does not decline, and indicates that device does not have gas leakage, gas reactor is then emptied, again to kettle
Inside it is filled with 6.0 MPa CO gases, heat temperature raising, 500 revs/min of reaction kettle mixing speed, 6.0 MPa of reaction pressure, reaction temperature
Respectively 90 DEG C, 100 DEG C, 110 DEG C, 130 DEG C, 150 DEG C, 6 h of reaction time, reaction result are as shown in table 2.
Reaction condition: 20 kg dimethoxym ethanes, 3.9 kg metaformaldehydes, 4 kg water, 300 g NKC-9 catalyst, reaction pressure
6.0MPa, 6 h of reaction time.
As can be seen from Table 2, with the raising of reaction temperature, DMM conversion ratio is gradually increased, when reaction temperature is 130 DEG C
When, DMM conversion ratio is 71.11%, and when reaction temperature is 150 DEG C, DMM conversion ratio is 83.78%.With the liter of reaction temperature
Height, MMAc Mass Selective first increases to be reduced afterwards, and at 110 DEG C of reaction temperature, MMAc Mass Selective is up to 20.48%；
The variation tendency of MG Mass Selective is identical as MMAc, and at 130 DEG C of reaction temperature, MG Mass Selective is up to
60.55%。
Embodiment 3
Weigh 20 kg dimethoxym ethanes (DMM) respectively, 3.9 kg metaformaldehydes (DMM and aldehyde radical molar ratio 2:1), 4 kg water,
300 g NKC-9 resin catalysts are fitted into reaction kettle, then pass to 1.0 MPa CO gas, if not omitting in printing in sky kettle
After gas, aforesaid operations 2 times (air in replacement reaction kettle) is repeated.The gas for being passed through a certain amount of (6.0 MPa) again is surveyed
Leakage, and 15 min are stood, pressure gauge registration does not decline, and indicates that device does not have gas leakage, gas reactor is then emptied, again to kettle
Inside be filled with 6.0 MPa CO gases, heat temperature raising, 500 revs/min of reaction kettle mixing speed, reaction pressure be respectively 2.0 MPa,
3.0 MPa, 4.0 MPa, 5.0 MPa, 6.0MPa, 8.0 MPa, 10.0 MPa, 15.0 MPa, 130 DEG C of reaction temperature, when reaction
Between 6 h, reaction result is as shown in table 3.
Reaction condition: 20 kg dimethoxym ethanes, 3.9 kg metaformaldehydes, 4 kg water, 300 g NKC-9 catalyst, reaction temperature
130 DEG C, 6 h of reaction time.
As can be seen from Table 3, with the raising of reaction pressure, CO concentration is gradually increased in liquid phase, in system aldehyde radical total amount
Under conditions of certain, CO and aldehyde radical ratio are gradually risen, therefore DMM conversion ratio gradually increases, when reaction pressure is 15.0 MPa
When, DMM tends to convert completely.With the raising of reaction pressure, MMAc Mass Selective is first increased and is reduced afterwards, is in reaction pressure
When 5.0 MPa, MMAc Mass Selective is up to 27.78%.The Mass Selective of MG is with the raising of reaction pressure and gradually
It increases, this is because reaction pressure increases, CO and aldehyde radical ratio are increased in liquid phase, it is more advantageous to the generation of aldehyde radical oxonation,
When reaction pressure is 15.0 MPa, the Mass Selective of MG is up to 80.55%.
Embodiment 4
Weigh 20 kg dimethoxym ethanes (DMM) respectively, 3.9 kg metaformaldehydes (DMM and aldehyde radical molar ratio 2:1), 4 kg water,
300 g NKC-9 resin catalysts are fitted into reaction kettle, then pass to 1.0 MPa CO gas, if not omitting in printing in sky kettle
After gas, aforesaid operations 2 times (air in replacement reaction kettle) is repeated.The gas for being passed through a certain amount of (6.0 MPa) again is surveyed
Leakage, and 15 min are stood, pressure gauge registration does not decline, and indicates that device does not have gas leakage, gas reactor is then emptied, again to kettle
6.0 MPa CO gases are inside filled with, heat temperature raising, 500 revs/min of reaction kettle mixing speed, reaction pressure is 6.0 MPa, reaction temperature
130 DEG C of degree, the reaction time is respectively 1 h, 2 h, 4 h, 6 h, 8 h, and reaction result is as shown in table 4.
Reaction condition: 20 kg dimethoxym ethanes, 3.9 kg metaformaldehydes, 4 kg water, 300 g NKC-9 catalyst, reaction temperature
130 DEG C, reaction pressure 6.0MPa.
As can be seen from Table 4, with the increase in reaction time, DMM conversion ratio is gradually increased, when 8 h of reaction time, DMM
Conversion ratio is 80.28%.The Mass Selective of MMAc and MG is gradually increased with the increase in reaction time, in 8 h of reaction time
When, MMAc Mass Selective is that 20.81%, MG Mass Selective is 63.34%.
Embodiment 5
20 kg dimethoxym ethanes (DMM), 3.9 kg metaformaldehydes (DMM and aldehyde radical molar ratio 2:1), 300 g are weighed respectively
NKC-9 resin catalyst is fitted into reaction kettle, and the additional amount of water is respectively 3%, 5%, 10%, 20%, the 30% of dimethoxym ethane quality, so
After be passed through 1.0 MPa CO gas, if it is (empty in replacement reaction kettle to repeat aforesaid operations 2 times after not omitting sky gas reactor in printing
Gas).The gas for being passed through a certain amount of (6.0 MPa) again leaks hunting, and stands 15 min, and pressure gauge registration does not decline, table
Showing device does not have gas leakage, then empties gas reactor, is filled with 6.0 MPa CO gases, heat temperature raising, reaction kettle into kettle again
500 revs/min of mixing speed, 6.0 MPa of reaction pressure, 130 DEG C of reaction temperature, 6 h of reaction time, reaction result such as 5 institute of table
Show.
Reaction condition: 20 kg dimethoxym ethanes, 3.9 kg metaformaldehydes, 300 g NKC-9 resin catalysts, reaction temperature 130
DEG C, reaction pressure 6.0MPa, 6 h of reaction time.
As can be seen from Table 5, with the increase of dampening additional amount, DMM conversion ratio and MMAc Mass Selective gradually under
Drop, when the additional amount of water is the 3% of dimethoxym ethane quality, DMM conversion ratio is that 99.58%, MMAc Mass Selective is 50.48%；When
When the additional amount of water is the 30% of dimethoxym ethane quality, DMM conversion ratio is that 60.57%, MMAc Mass Selective is 10.28%.With dampening
The increase of additional amount, the Mass Selective of MG first increases to be reduced afterwards, when the additional amount of water is the 20% of dimethoxym ethane quality, MG's
Mass Selective is up to 60.55%.Since formaldehyde carbonylation needs the water in consumption system, when the additional amount of water is less
(3%, 5%, 10%), in system formaldehyde largely free can not carbonylation generate glycolic, while the additional amount of water less leads to DMM
Discharge methanol rate it is slack-off, these are all unfavorable for the generation of MG, therefore when the additional amount of water is less, MG Mass Selective compared with
It is low.When the additional amount of water is more (30%), MG Mass Selective decline the reason of be that water is formed in conjunction with catalyst acid center
H3O+, cause part acid site to be covered with water, the decline of catalyst carbonylation activity.It is preferred that the additional amount of water is dimethoxym ethane quality
20%。
Embodiment 6
In fixed bed reactors, it is packed into 300 g of solid acid catalyst, material rate are as follows: 20 kg dimethoxym ethanes (DMM), 4
Above-mentioned raw materials are pumped into reactor by kg water, 3.9 kg metaformaldehydes using constant flow pump, and air speed is 30 h-1, reaction temperature 130
DEG C, it is reacted under 6.0 MPa of reaction pressure, sampling carries out chromatography point after 200 h, 500 h, 1000h, 2000 h are stablized in reaction respectively
Analysis calculates, and feed stock conversion, selectivity of product are as shown in table 6.
Reaction condition: 20 kg dimethoxym ethanes, 3.9 kg metaformaldehydes, 4 kg water, 300 g NKC-9 catalyst, reaction temperature
130 DEG C, reaction pressure 6.0MPa, 30 h of air speed-1。
As can be seen from Table 6,2000 h feed stock conversions of reaction experience, selectivity of product are basically unchanged, and catalyst is basic
Do not inactivate.
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, a little variation or modification are made using the technology contents of the disclosure above and is equal to
Case study on implementation is imitated, is belonged in technical proposal scope.
Claims (1)
1. a kind of method of catalyst preparation methyl glycollate and by-product methoxy menthyl acetate, which is characterized in that the method
Are as follows: 20 kg dimethoxym ethanes, 3.9 kg metaformaldehydes, dimethoxym ethane and aldehyde radical molar ratio 2:1,4 kg water, 300 g NKC- are weighed respectively
9 resin catalysts are fitted into reaction kettle, then pass to 1.0 MPa CO gas, if after not omitting sky gas reactor in printing, repeating
Aforesaid operations 2 times, the gas for being passed through 6.0 MPa again leaks hunting, and stands 15 min, and pressure gauge registration does not decline, table
Showing device does not have gas leakage, then empties gas reactor, is filled with 6.0 MPa CO gases, heat temperature raising, reaction kettle into kettle again
500 revs/min of mixing speed, 15.0 MPa of reaction pressure, 130 DEG C of reaction temperature, 6 h of reaction time converts to get to dimethoxym ethane
Rate is 99.99%, and the selectivity of methoxy menthyl acetate is 9.00%, and the selectivity of methyl glycollate is 80.55%.
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| CN109550506A (en) * | 2018-12-07 | 2019-04-02 | 徐州伯利恒生物科技有限公司 | A kind of low-corrosiveness catalyst |
| CN112705265B (en) * | 2019-10-25 | 2023-04-07 | 中国石油化工股份有限公司 | Supported solid acid catalyst for synthesizing methyl glycolate and preparation method and application thereof |
| CN112705264A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Catalyst for producing methyl methoxyacetate through carbonylation of formaldehyde and preparation method and application thereof |
| CN114436845B (en) * | 2020-10-20 | 2024-01-30 | 中国石油化工股份有限公司 | Method for synthesizing methyl methoxyacetate by carbonylation of formaldehyde |
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