CN110143876A - A kind of method that can continuously prepare propylene glycol diacetate - Google Patents
A kind of method that can continuously prepare propylene glycol diacetate Download PDFInfo
- Publication number
- CN110143876A CN110143876A CN201910549271.5A CN201910549271A CN110143876A CN 110143876 A CN110143876 A CN 110143876A CN 201910549271 A CN201910549271 A CN 201910549271A CN 110143876 A CN110143876 A CN 110143876A
- Authority
- CN
- China
- Prior art keywords
- propylene glycol
- glycol diacetate
- reaction
- catalytic distillation
- tower
- 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
- 229940116423 propylene glycol diacetate Drugs 0.000 title claims abstract description 68
- UYAAVKFHBMJOJZ-UHFFFAOYSA-N diimidazo[1,3-b:1',3'-e]pyrazine-5,10-dione Chemical compound O=C1C2=CN=CN2C(=O)C2=CN=CN12 UYAAVKFHBMJOJZ-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 174
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 150
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 107
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 90
- 230000003197 catalytic effect Effects 0.000 claims abstract description 68
- 238000004821 distillation Methods 0.000 claims abstract description 67
- 230000032050 esterification Effects 0.000 claims abstract description 14
- 238000005886 esterification reaction Methods 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 52
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 34
- 239000011347 resin Substances 0.000 claims description 32
- 229920005989 resin Polymers 0.000 claims description 32
- 239000000047 product Substances 0.000 claims description 24
- 238000010992 reflux Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 12
- 239000012043 crude product Substances 0.000 claims description 8
- 239000011949 solid catalyst Substances 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 3
- 239000011964 heteropoly acid Substances 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 description 31
- 150000003460 sulfonic acids Chemical class 0.000 description 31
- 150000001768 cations Chemical class 0.000 description 30
- 239000000463 material Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- 230000006837 decompression Effects 0.000 description 16
- 238000002347 injection Methods 0.000 description 15
- 239000007924 injection Substances 0.000 description 15
- 238000004148 unit process Methods 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 206010027627 Miliaria Diseases 0.000 description 4
- 201000004169 miliaria rubra Diseases 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 108010029541 Laccase Proteins 0.000 description 1
- MGWZNPSXDQOMPN-UHFFFAOYSA-N acetic acid;2-acetyloxypropyl acetate Chemical compound CC(O)=O.CC(=O)OC(C)COC(C)=O MGWZNPSXDQOMPN-UHFFFAOYSA-N 0.000 description 1
- 230000003254 anti-foaming effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000007805 chemical reaction reactant Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to field of chemical technology, and in particular to the method that one kind can continuously prepare propylene glycol diacetate, in particular to one kind are prepared and the technique of separating propylene glycol diacetate in the presence of a catalyst using 1,2-PD and acetic acid as raw material.The method of the present invention that propylene glycol diacetate can be continuously prepared, on the basis of existing esterification technique, esterification is completed by adjusting the technological parameter of fixed bed pre-reactor and catalytic distillation tower, and chemical balance is broken by adding water entrainer during catalytic esterification, it can promote reaction is continuous deeply to carry out, the conversion ratio of propylene glycol greatly improved, can finally make the conversion ratio > 99% of propylene glycol.
Description
Technical field
The invention belongs to field of chemical technology, and in particular to one kind can continuously prepare the side of propylene glycol diacetate
Method, in particular to one kind are prepared and two acetic acid of separating propylene glycol in the presence of a catalyst using 1,2-PD and acetic acid as raw material
The technique of ester.
Background technique
Propylene glycol diacetate (PGDA) is a kind of functional form environmentally friendly solvent, the general chemical property with ester.PGDA is easy
It is dissolved in alcohol, ether and other organic solvents, there is splendid levelability, and smell is low, safe and non-toxic, dissolving power is strong, antifoaming ability are good,
It is strong to the dispersibility of pigment, there is anti-floating, prevent the advantages such as laccase prodution, anti-prickly heat, be it is a kind of efficiently, environmental protection,
The organic solvent of prominent function is widely used in pharmacy, chemical industry, ink and organic synthesis field, especially processes and leads in coating
Positive effect is played in domain.
Since PGDA concentrates the excellent properties with tetra- products of CAC, PMA, BCS, CYC, environment-protecting and non-poisonous low gas is had more
The features such as taste, levelling are good, dissolving power is strong, are more easier the compounding of coating production process, reduce material procurement, warehousing management
Fussy degree, and the high-flash performance of PGDA improves the safety of circulation, storage and production process.In addition, due to PGDA
The levelling and the anti-prickly heat of PMA, the anti-dual function secretly steeped for combining CAC, so that PGDA has high richness, high glaze, prevents secretly
Bubble and the good advantage of anti-prickly heat performance.In high boiling solvent system in use, PGDA only substitutes 15% PMA solvent
Greatly improve the levelability of PMA and prevents the defect for secretly steeping anti-prickly heat.When PGDA is in various self-drying paints, it can do completely
Thoroughly, and in paint film it does not remain;When in all finishing coats, have the function of be significantly improved gloss and richness, it is special
Not in white finishing coat, the whiteness of paint film can be promoted, even if can still play the anti-contour painting of paint film in wet weather
Can, prevent finishing coat from whitening with priming paint.As it can be seen that propylene glycol diacetate is as a kind of functionality organic solvent outstanding, in coating
It is played an important role in production.
However the technique of propylene glycol diacetate is produced in the prior art still using conventional esterification technique, but
Continuous production and the selective low process difficulties of esterification are such as unable to there is also identical with general esterification technique, are affected
The production efficiency of propylene glycol diacetate.
Summary of the invention
For this purpose, technical problem to be solved by the present invention lies in provide it is a kind of can continuous production propylene glycol diacetate side
Method, to improve the esterification selectivity and esterifying efficiency of propylene glycol diacetate.
In order to solve the above technical problems, the method that one kind of the present invention can continuously prepare propylene glycol diacetate, packet
Include following steps:
(1) will acetic acid and propylene glycol raw material mix after be passed through in fixed bed pre-reactor, in the presence of a solid catalyst into
Row pre-reaction obtains pre-reaction object;
(2) the pre-reaction object is passed through in catalytic distillation tower, in the presence of a solid catalyst, and is passed through water entrainer progress
Further esterification obtains propylene glycol diacetate crude product;
(3) propylene glycol diacetate crude product obtained separated, purified, obtain required propylene glycol diacetate.
Specifically, the molar ratio of the acetic acid and propylene glycol is 2-4:1 in the step (1).
The purity of the raw material propylene glycol is 70%-100%, and preferred propane diols purity is 85%-100%;Acetic acid
Mass percentage be 70%-100%, preferred acetic acid purity be 85%-100%.In the fixed bed pre-reactor, instead
It answers object and product is liquid phase, propylene glycol conversion ratio is up to 63% or more.
Specifically, controlling the reaction condition of the fixed bed pre-reactor are as follows: reaction temperature 80- in the step (1)
120 DEG C, air speed 1.5-5h-1, reaction pressure is normal pressure -0.3MPa.
Specifically, the water entrainer includes benzene, toluene or hexamethylene in the step (2).
Specifically, in the step (2):
When the water entrainer is benzene, controlling and generating the mass ratio of water in the water entrainer and the catalytic distillation tower is 9:1;
When the water entrainer is toluene, control the water entrainer is with the mass ratio for generating water in the catalytic distillation tower
80.84:19.16;
When the water entrainer is hexamethylene, control the water entrainer is with the mass ratio for generating water in the catalytic distillation tower
91.6:8.4.
Specifically, controlling the reaction condition of the catalytic distillation tower in the step (2) are as follows: control tower top pressure is normal
Pressure, control tower top temperature are 60-100 DEG C, and conversion zone temperature is 80-120 DEG C, and at 200-240 DEG C, tower is returned for bottom temperature control
Stream is than being 0.5-6, preferably 1-4.
Specifically, the water entrainer enters from the bottom of the catalytic distillation tower conversion zone in the step (2), it is made
Propylene glycol diacetate crude product from tower top flow out.
Specifically, the solid catalyst includes resin catalyst, heteropolyacid catalyst in the step (1) and (2)
And/or molecular sieve catalyst.It is preferred that the cation exchange resin catalyst of sulfonic acid series macropore.
Specifically, the separating step is slightly to be produced the propylene glycol diacetate by rectifying column in the step (3)
Acetic acid in object is separated, and the acetic acid isolated is passed through the fixed bed pre-reactor and is recycled.
Specifically, the purification step is rectification under vacuum in the step (3), control operating pressure is -0.085Mpa
~-0.09Mpa.
The method of the present invention that propylene glycol diacetate can be continuously prepared passes through on the basis of existing esterification technique
The technological parameter for adjusting fixed bed pre-reactor and catalytic distillation tower completes esterification, and by adding during catalytic esterification
Add water entrainer to break chemical balance, can promote reaction is continuous deeply to carry out, the conversion ratio of propylene glycol greatly improved, finally may be used
Make the conversion ratio > 99% of propylene glycol.
The method of the present invention that propylene glycol diacetate can be continuously prepared, process conditions are mild, easily operated, effective
Material consumption, energy consumption are reduced, while improving the processing capacity of device, to handle available 98% or more again pure through de- light, de- for product
The propylene glycol diacetate of degree, conversion ratio also improve, and efficiently solve current esterification technique process complexity, divide water tired
Difficult and low conversion ratio disadvantage, is easy to commercial introduction.
Detailed description of the invention
In order to make the content of the present invention more clearly understood, it below according to specific embodiments of the present invention and combines
Attached drawing, the present invention is described in further detail, wherein
Fig. 1 is the structural schematic diagram of propylene glycol diacetate production technology device of the present invention;
Appended drawing reference indicates in figure are as follows: 1- fixed bed pre-reactor, 2- catalytic distillation tower, 3- lightness-removing column, 4- weight-removing column, 5-
Propylene glycol, 6- return to acetic acid, and 7- feeds acetic acid, 8- water entrainer, 9- propylene glycol diacetate, 10- heavy constituent.
Specific embodiment
Shown in process unit structure chart as shown in Figure 1, the side of the present invention that can continuously prepare propylene glycol diacetate
Method can be realized based on existing esterification technique device.
Process unit structure chart as shown in Figure 1, described device include continuous fixed bed pre-reactor 1, catalytic distillation
Tower 2, lightness-removing column 3 and weight-removing column 4.
The fixed bed pre-reactor 1 is used to carry out the pre-reaction of acetic acid and propylene glycol, selectes the charging of molar ratio
Acetic acid 7 and propylene glycol 5 enter after static mixer mixes from the top of the fixed bed pre-reactor 1 in proportion, in solid
Pre-reaction is carried out in the presence of catalyst, obtained pre-reaction object enters described urge after flowing out from the lower part of fixed bed pre-reactor 1
Change and carries out further catalysis reaction in destilling tower.
The structure of the catalytic distillation tower 2 is by a tower reactor, a stripping section, one or more reaction beds, one
Rectifying section and an overhead reflux condenser composition;A certain number of catalytic distillation baskets are uniform-distribution in reaction bed, are catalyzed
Distillation basket is provided with solid catalyst same as fixed bed pre-reactor.It is pre- after the fixed bed pre-reactor 1 reaction
Reactant from 1 lower part of fixed bed pre-reactor flow out after enter the catalytic distillation tower 2 conversion zone top, water entrainer 8 then from
The lower part of 2 conversion zone of catalytic distillation tower enters, and propylene glycol diacetate crude product a part reflux a part of tower top is made
For product outflow.Such a feeding manner can be such that reactant comes into full contact with, and the water that reaction generates is taken out of, improve reaction
Efficiency, so that propylene glycol conversion ratio in catalytic distillation tower optimizes purification & isolation process, improve third up to 99.5% or more
The conversion ratio of glycol, reduces costs.
The lightness-removing column 3 is common rectifying tower, mainly plays a part of to separate acetic acid, the return acetic acid 6 isolated is again defeated
Enter the fixed bed pre-reactor 1 to be recycled.
The weight-removing column 4 is common vacuum rectification tower, mainly plays a part of to purify propylene glycol diacetate, after separating acetic acid
Propylene glycol diacetate crude product through the weight-removing column 4 rectification under vacuum handle, obtained products propylene glycol diacetate 9 from
Tower top outflow is collected, and isolated heavy constituent 10 is then flowed out from tower bottom and recycled.The weight-removing column 4 operating pressure control for-
0.085Mpa~-0.09Mpa, decompression operation can prevent material decomposition and coking.
In the following embodiments of the present invention, the purity of the propylene glycol raw material is 85%-100%, and the quality percentage of acetic acid contains
Amount is 85%-100%.
Embodiment 1
According to process unit process shown in attached drawing 1, the acetic acid of mass fraction 98% and anhydrous propylene glycol are pressed through plunger pump
Fixed bed of the injection equipped with sulfonic acid series large hole cation exchanger resin (charge weight 40ml) is pre- anti-after molar ratio 3:1 metering mixing
It answers in device, controls the reaction condition of the fixed bed pre-reactor are as follows: reaction temperature is 80 DEG C, reaction pressure 0.1MPa, sky
Fast 3h-1, carry out pre-reaction.
It is entered back into catalytic distillation tower by the mixture of pre-reaction, in sulfonic acid series large hole cation exchanger resin (dress
Enter amount 100ml) in the presence of, and being passed through benzene from tower bottom is that water entrainer carries out catalysis reaction;Control the reaction of the catalytic distillation tower
Condition are as follows: control tower top pressure is normal pressure, and control tower top temperature is 70 DEG C, and conversion zone temperature is 91 DEG C, and bottom temperature control exists
212 DEG C, the reflux ratio of tower is 2;The amount of water entrainer is related with total water yield, and the mass ratio that benzene and water are controlled in the present embodiment is 9:
1。
Kettle material after catalytic distillation tower catalysis reaction separates acetic acid through the lightness-removing column and weight-removing column decompression is steamed
It evaporates, the propylene glycol diacetate product after being refined.
Embodiment 2
According to process unit process shown in attached drawing 1, the acetic acid of mass fraction 98% and anhydrous propylene glycol are pressed through plunger pump
Fixed bed of the injection equipped with sulfonic acid series large hole cation exchanger resin (charge weight 40ml) is pre- anti-after molar ratio 3:1 metering mixing
It answers in device, controls the reaction condition of the fixed bed pre-reactor are as follows: reaction temperature is 95 DEG C, reaction pressure 0.1MPa, sky
Fast 3h-1, carry out pre-reaction.
It is entered back into catalytic distillation tower by the mixture of pre-reaction, in sulfonic acid series large hole cation exchanger resin (dress
Enter amount 100ml) in the presence of, and being passed through benzene from tower bottom is that water entrainer carries out catalysis reaction;Control the reaction of the catalytic distillation tower
Condition are as follows: control tower top pressure is normal pressure, and control tower top temperature is 70 DEG C, and conversion zone temperature is 91 DEG C, and bottom temperature control exists
212 DEG C, the reflux ratio of tower is 2;The amount of water entrainer is related with total water yield, and the mass ratio that benzene and water are controlled in the present embodiment is 9:
1。
Kettle material after catalytic distillation tower catalysis reaction separates acetic acid through the lightness-removing column and weight-removing column decompression is steamed
It evaporates, the propylene glycol diacetate product after being refined.
Embodiment 3
According to process unit process shown in attached drawing 1, the acetic acid of mass fraction 98% and anhydrous propylene glycol are pressed through plunger pump
Fixed bed of the injection equipped with sulfonic acid series large hole cation exchanger resin (charge weight 40ml) is pre- anti-after molar ratio 3:1 metering mixing
It answers in device, controls the reaction condition of the fixed bed pre-reactor are as follows: reaction temperature is 110 DEG C, reaction pressure 0.2MPa, sky
Fast 2h-1, carry out pre-reaction.
It is entered back into catalytic distillation tower by the mixture of pre-reaction, in sulfonic acid series large hole cation exchanger resin (dress
Enter amount 100ml) in the presence of, and being passed through benzene from tower bottom is that water entrainer carries out catalysis reaction;Control the reaction of the catalytic distillation tower
Condition are as follows: control tower top pressure is normal pressure, and control tower top temperature is 70 DEG C, and conversion zone temperature is 91 DEG C, and bottom temperature control exists
212 DEG C, the reflux ratio of tower is 2;The amount of water entrainer is related with total water yield, and the mass ratio that benzene and water are controlled in the present embodiment is 9:
1。
Kettle material after catalytic distillation tower catalysis reaction separates acetic acid through the lightness-removing column and weight-removing column decompression is steamed
It evaporates, the propylene glycol diacetate product after being refined.
Embodiment 4
According to process unit process shown in attached drawing 1, the acetic acid of mass fraction 98% and anhydrous propylene glycol are pressed through plunger pump
Fixed bed of the injection equipped with sulfonic acid series large hole cation exchanger resin (charge weight 40ml) is pre- anti-after molar ratio 3:1 metering mixing
It answers in device, controls the reaction condition of the fixed bed pre-reactor are as follows: reaction temperature is 80 DEG C, reaction pressure 0.2MPa, sky
Fast 4h-1, carry out pre-reaction.
It is entered back into catalytic distillation tower by the mixture of pre-reaction, in sulfonic acid series large hole cation exchanger resin (dress
Enter amount 100ml) in the presence of, and being passed through benzene from tower bottom is that water entrainer carries out catalysis reaction;Control the reaction of the catalytic distillation tower
Condition are as follows: control tower top pressure is normal pressure, and control tower top temperature is 70 DEG C, and conversion zone temperature is 91 DEG C, and bottom temperature control exists
212 DEG C, the reflux ratio of tower is 2;The amount of water entrainer is related with total water yield, and the mass ratio that benzene and water are controlled in the present embodiment is 9:
1。
Kettle material after catalytic distillation tower catalysis reaction separates acetic acid through the lightness-removing column and weight-removing column decompression is steamed
It evaporates, the propylene glycol diacetate product after being refined.
Embodiment 5
According to process unit process shown in attached drawing 1, the acetic acid of mass fraction 98% and anhydrous propylene glycol are pressed through plunger pump
Fixed bed of the injection equipped with sulfonic acid series large hole cation exchanger resin (charge weight 40ml) is pre- anti-after molar ratio 3:1 metering mixing
It answers in device, controls the reaction condition of the fixed bed pre-reactor are as follows: reaction temperature is 85 DEG C, reaction pressure 0.3MPa, sky
Fast 1.5h-1, carry out pre-reaction.
It is entered back into catalytic distillation tower by the mixture of pre-reaction, in sulfonic acid series large hole cation exchanger resin (dress
Enter amount 100ml) in the presence of, and being passed through benzene from tower bottom is that water entrainer carries out catalysis reaction;Control the reaction of the catalytic distillation tower
Condition are as follows: control tower top pressure is normal pressure, and control tower top temperature is 70 DEG C, and conversion zone temperature is 91 DEG C, and bottom temperature control exists
212 DEG C, the reflux ratio of tower is 2;The amount of water entrainer is related with total water yield, and the mass ratio that benzene and water are controlled in the present embodiment is 9:
1。
Kettle material after catalytic distillation tower catalysis reaction separates acetic acid through the lightness-removing column and weight-removing column decompression is steamed
It evaporates, the propylene glycol diacetate product after being refined.
Embodiment 6
According to process unit process shown in attached drawing 1, the acetic acid of mass fraction 98% and anhydrous propylene glycol are pressed through plunger pump
Fixed bed of the injection equipped with sulfonic acid series large hole cation exchanger resin (charge weight 40ml) is pre- anti-after molar ratio 3:1 metering mixing
It answers in device, controls the reaction condition of the fixed bed pre-reactor are as follows: reaction temperature is 100 DEG C, reaction pressure 0.3MPa, sky
Fast 2.5h-1, carry out pre-reaction.
It is entered back into catalytic distillation tower by the mixture of pre-reaction, in sulfonic acid series large hole cation exchanger resin (dress
Enter amount 100ml) in the presence of, and being passed through benzene from tower bottom is that water entrainer carries out catalysis reaction;Control the reaction of the catalytic distillation tower
Condition are as follows: control tower top pressure is normal pressure, and control tower top temperature is 70 DEG C, and conversion zone temperature is 91 DEG C, and bottom temperature control exists
212 DEG C, the reflux ratio of tower is 2;The amount of water entrainer is related with total water yield, and the mass ratio that benzene and water are controlled in the present embodiment is 9:
1。
Kettle material after catalytic distillation tower catalysis reaction separates acetic acid through the lightness-removing column and weight-removing column decompression is steamed
It evaporates, the propylene glycol diacetate product after being refined.
Embodiment 7
According to process unit process shown in attached drawing 1, the acetic acid of mass fraction 98% and anhydrous propylene glycol are pressed through plunger pump
Fixed bed of the injection equipped with sulfonic acid series large hole cation exchanger resin (charge weight 40ml) is pre- anti-after molar ratio 3:1 metering mixing
It answers in device, controls the reaction condition of the fixed bed pre-reactor are as follows: reaction temperature is 90 DEG C, reaction pressure is normal pressure, air speed
4h-1, carry out pre-reaction.
It is entered back into catalytic distillation tower by the mixture of pre-reaction, in sulfonic acid series large hole cation exchanger resin (dress
Enter amount 100ml) in the presence of, and being passed through benzene from tower bottom is that water entrainer carries out catalysis reaction;Control the reaction of the catalytic distillation tower
Condition are as follows: control tower top pressure is normal pressure, and control tower top temperature is 70 DEG C, and conversion zone temperature is 91 DEG C, and bottom temperature control exists
212 DEG C, the reflux ratio of tower is 2;The amount of water entrainer is related with total water yield, and the mass ratio that benzene and water are controlled in the present embodiment is 9:
1。
Kettle material after catalytic distillation tower catalysis reaction separates acetic acid through the lightness-removing column and weight-removing column decompression is steamed
It evaporates, the propylene glycol diacetate product after being refined.
Embodiment 8
According to process unit process shown in attached drawing 1, through plunger pump by the acetic acid of mass fraction 90% and mass fraction 90%
The propylene glycol mixing of 4:1 metering in molar ratio after injection equipped with sulfonic acid series large hole cation exchanger resin (charge weight 40ml)
In fixed bed pre-reactor, the reaction condition of the fixed bed pre-reactor is controlled are as follows: reaction temperature is 80 DEG C, reaction pressure is
0.1MPa, air speed 2h-1, carry out pre-reaction.
It is entered back into catalytic distillation tower by the mixture of pre-reaction, in sulfonic acid series large hole cation exchanger resin (dress
Enter amount 100ml) in the presence of, and being passed through toluene from tower bottom is that water entrainer carries out catalysis reaction;Control the anti-of the catalytic distillation tower
Answer condition are as follows: control tower top pressure is normal pressure, and control tower top temperature is 84 DEG C, and conversion zone temperature is 110 DEG C, bottom temperature control
At 231 DEG C, the reflux ratio of tower is 2;The amount of water entrainer is related with total water yield, and the mass ratio of toluene and water is controlled in the present embodiment
For 80.84:19.16.
Kettle material after catalytic distillation tower catalysis reaction separates acetic acid through the lightness-removing column and weight-removing column decompression is steamed
It evaporates, the propylene glycol diacetate product after being refined.
Embodiment 9
According to process unit process shown in attached drawing 1, through plunger pump by the acetic acid of mass fraction 90% and mass fraction 90%
The propylene glycol mixing of 4:1 metering in molar ratio after injection equipped with sulfonic acid series large hole cation exchanger resin (charge weight 40ml)
In fixed bed pre-reactor, the reaction condition of the fixed bed pre-reactor is controlled are as follows: reaction temperature is 100 DEG C, reaction pressure
For 0.3MPa, air speed 1.5h-1, carry out pre-reaction.
It is entered back into catalytic distillation tower by the mixture of pre-reaction, in sulfonic acid series large hole cation exchanger resin (dress
Enter amount 100ml) in the presence of, and being passed through toluene from tower bottom is that water entrainer carries out catalysis reaction;Control the anti-of the catalytic distillation tower
Answer condition are as follows: control tower top pressure is normal pressure, and control tower top temperature is 84 DEG C, and conversion zone temperature is 110 DEG C, bottom temperature control
At 231 DEG C, the reflux ratio of tower is 3;The amount of water entrainer is related with total water yield, and the mass ratio of toluene and water is controlled in the present embodiment
For 80.84:19.16.
Kettle material after catalytic distillation tower catalysis reaction separates acetic acid through the lightness-removing column and weight-removing column decompression is steamed
It evaporates, the propylene glycol diacetate product after being refined.
Embodiment 10
According to process unit process shown in attached drawing 1, through plunger pump by the acetic acid of mass fraction 90% and mass fraction 90%
The propylene glycol mixing of 4:1 metering in molar ratio after injection equipped with sulfonic acid series large hole cation exchanger resin (charge weight 40ml)
In fixed bed pre-reactor, the reaction condition of the fixed bed pre-reactor is controlled are as follows: reaction temperature is 95 DEG C, reaction pressure is
0.2MPa, air speed 2h-1, carry out pre-reaction.
It is entered back into catalytic distillation tower by the mixture of pre-reaction, in sulfonic acid series large hole cation exchanger resin (dress
Enter amount 100ml) in the presence of, and being passed through toluene from tower bottom is that water entrainer carries out catalysis reaction;Control the anti-of the catalytic distillation tower
Answer condition are as follows: control tower top pressure is normal pressure, and control tower top temperature is 84 DEG C, and conversion zone temperature is 110 DEG C, bottom temperature control
At 231 DEG C, the reflux ratio of tower is 2;The amount of water entrainer is related with total water yield, and the mass ratio of toluene and water is controlled in the present embodiment
For 80.84:19.16.
Kettle material after catalytic distillation tower catalysis reaction separates acetic acid through the lightness-removing column and weight-removing column decompression is steamed
It evaporates, the propylene glycol diacetate product after being refined.
Embodiment 11
According to process unit process shown in attached drawing 1, through plunger pump by the acetic acid of mass fraction 90% and mass fraction 90%
The propylene glycol mixing of 4:1 metering in molar ratio after injection equipped with sulfonic acid series large hole cation exchanger resin (charge weight 40ml)
In fixed bed pre-reactor, the reaction condition of the fixed bed pre-reactor is controlled are as follows: reaction temperature is 110 DEG C, reaction pressure
For 0.1MPa, air speed 3.5h-1, carry out pre-reaction.
It is entered back into catalytic distillation tower by the mixture of pre-reaction, in sulfonic acid series large hole cation exchanger resin (dress
Enter amount 100ml) in the presence of, and being passed through toluene from tower bottom is that water entrainer carries out catalysis reaction;Control the anti-of the catalytic distillation tower
Answer condition are as follows: control tower top pressure is normal pressure, and control tower top temperature is 84 DEG C, and conversion zone temperature is 110 DEG C, bottom temperature control
At 231 DEG C, the reflux ratio of tower is 2;The amount of water entrainer is related with total water yield, and the mass ratio of toluene and water is controlled in the present embodiment
For 80.84:19.16.
Kettle material after catalytic distillation tower catalysis reaction separates acetic acid through the lightness-removing column and weight-removing column decompression is steamed
It evaporates, the propylene glycol diacetate product after being refined.
Embodiment 12
According to process unit process shown in attached drawing 1, through plunger pump by the acetic acid of mass fraction 85% and mass fraction 85%
The propylene glycol mixing of 3:1 metering in molar ratio after injection equipped with sulfonic acid series large hole cation exchanger resin (charge weight 40ml)
In fixed bed pre-reactor, the reaction condition of the fixed bed pre-reactor is controlled are as follows: reaction temperature is 100 DEG C, reaction pressure
For 0.3MPa, air speed 2h-1, carry out pre-reaction.
It is entered back into catalytic distillation tower by the mixture of pre-reaction, in sulfonic acid series large hole cation exchanger resin (dress
Enter amount 100ml) in the presence of, and being passed through hexamethylene from tower bottom is that water entrainer carries out catalysis reaction;Control the catalytic distillation tower
Reaction condition are as follows: control tower top pressure is normal pressure, and control tower top temperature is 69 DEG C, and conversion zone temperature is 89 DEG C, bottom temperature control
For system at 218 DEG C, the reflux ratio of tower is 3;The amount of water entrainer is related with total water yield, and the matter of hexamethylene and water is controlled in the present embodiment
Amount is than being 91.6:8.4.
Kettle material after catalytic distillation tower catalysis reaction separates acetic acid through the lightness-removing column and weight-removing column decompression is steamed
It evaporates, the propylene glycol diacetate product after being refined.
Embodiment 13
According to process unit process shown in attached drawing 1, through plunger pump by the acetic acid of mass fraction 85% and mass fraction 85%
The propylene glycol mixing of 3:1 metering in molar ratio after injection equipped with sulfonic acid series large hole cation exchanger resin (charge weight 40ml)
In fixed bed pre-reactor, the reaction condition of the fixed bed pre-reactor is controlled are as follows: reaction temperature is 90 DEG C, reaction pressure is
0.3MPa, air speed 1.5h-1, carry out pre-reaction.
It is entered back into catalytic distillation tower by the mixture of pre-reaction, in sulfonic acid series large hole cation exchanger resin (dress
Enter amount 100ml) in the presence of, and being passed through hexamethylene from tower bottom is that water entrainer carries out catalysis reaction;Control the catalytic distillation tower
Reaction condition are as follows: control tower top pressure is normal pressure, and control tower top temperature is 69 DEG C, and conversion zone temperature is 89 DEG C, bottom temperature control
For system at 218 DEG C, the reflux ratio of tower is 3;The amount of water entrainer is related with total water yield, and the matter of hexamethylene and water is controlled in the present embodiment
Amount is than being 91.6:8.4.
Kettle material after catalytic distillation tower catalysis reaction separates acetic acid through the lightness-removing column and weight-removing column decompression is steamed
It evaporates, the propylene glycol diacetate product after being refined.
Embodiment 14
According to process unit process shown in attached drawing 1, through plunger pump by the acetic acid of mass fraction 85% and mass fraction 85%
The propylene glycol mixing of 3:1 metering in molar ratio after injection equipped with sulfonic acid series large hole cation exchanger resin (charge weight 40ml)
In fixed bed pre-reactor, the reaction condition of the fixed bed pre-reactor is controlled are as follows: reaction temperature is 110 DEG C, reaction pressure
For 0.1MPa, air speed 3h-1, carry out pre-reaction.
It is entered back into catalytic distillation tower by the mixture of pre-reaction, in sulfonic acid series large hole cation exchanger resin (dress
Enter amount 100ml) in the presence of, and being passed through hexamethylene from tower bottom is that water entrainer carries out catalysis reaction;Control the catalytic distillation tower
Reaction condition are as follows: control tower top pressure is normal pressure, and control tower top temperature is 69 DEG C, and conversion zone temperature is 89 DEG C, bottom temperature control
For system at 218 DEG C, the reflux ratio of tower is 3;The amount of water entrainer is related with total water yield, and the matter of hexamethylene and water is controlled in the present embodiment
Amount is than being 91.6:8.4.
Kettle material after catalytic distillation tower catalysis reaction separates acetic acid through the lightness-removing column and weight-removing column decompression is steamed
It evaporates, the propylene glycol diacetate product after being refined.
Embodiment 15
According to process unit process shown in attached drawing 1, through plunger pump by the acetic acid of mass fraction 85% and mass fraction 85%
The propylene glycol mixing of 3:1 metering in molar ratio after injection equipped with sulfonic acid series large hole cation exchanger resin (charge weight 40ml)
In fixed bed pre-reactor, the reaction condition of the fixed bed pre-reactor is controlled are as follows: reaction temperature is 95 DEG C, reaction pressure is
0.1MPa, air speed 3.5h-1, carry out pre-reaction.
It is entered back into catalytic distillation tower by the mixture of pre-reaction, in sulfonic acid series large hole cation exchanger resin (dress
Enter amount 100ml) in the presence of, and being passed through hexamethylene from tower bottom is that water entrainer carries out catalysis reaction;Control the catalytic distillation tower
Reaction condition are as follows: control tower top pressure is normal pressure, and control tower top temperature is 69 DEG C, and conversion zone temperature is 89 DEG C, bottom temperature control
For system at 218 DEG C, the reflux ratio of tower is 3;The amount of water entrainer is related with total water yield, and the matter of hexamethylene and water is controlled in the present embodiment
Amount is than being 91.6:8.4.
Kettle material after catalytic distillation tower catalysis reaction separates acetic acid through the lightness-removing column and weight-removing column decompression is steamed
It evaporates, the propylene glycol diacetate product after being refined.
It measures in above-described embodiment 1-15 respectively, the conversion ratio of propylene glycol, entire anti-in the fixed bed pre-reactor
The purity of the total conversion of propylene glycol and obtained propylene glycol diacetate product during answering records result in the following table 1 institute
Show.
Reaction result in each embodiment of table 1
Number | Propylene glycol conversion ratio/% | Propylene glycol total conversion/% | Product purity/% |
Embodiment 1 | 63.27 | 99.63 | 98.58 |
Embodiment 2 | 67.15 | 99.63 | 97.56 |
Embodiment 3 | 67.25 | 100 | 99.17 |
Embodiment 4 | 71.14 | 99.56 | 98.55 |
Embodiment 5 | 69.13 | 100 | 99.56 |
Embodiment 6 | 67.61 | 99.76 | 98.85 |
Embodiment 7 | 63.65 | 99.53 | 98.26 |
Embodiment 8 | 63.19 | 99.63 | 98.55 |
Embodiment 9 | 66.27 | 100 | 99.67 |
Embodiment 10 | 65.11 | 99.53 | 98.31 |
Embodiment 11 | 67.61 | 99.73 | 98.55 |
Embodiment 12 | 66.27 | 99.63 | 98.26 |
Embodiment 13 | 65.18 | 100 | 99.39 |
Embodiment 14 | 64.17 | 99.93 | 98.27 |
Embodiment 15 | 66.76 | 99.05 | 98.16 |
The method that can be seen that preparation propylene glycol diacetate of the present invention from upper table data, not only may be implemented third
The continuous production of glycol diacetate, and the transformation efficiency of propylene glycol is higher, and the purity of propylene glycol diacetate product
Reach 98% or more.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. the method that one kind can continuously prepare propylene glycol diacetate, which comprises the steps of:
(1) it is passed through in fixed bed pre-reactor, carries out in the presence of a solid catalyst pre- after mixing acetic acid and propylene glycol raw material
Reaction, obtains pre-reaction object;
(2) the pre-reaction object is passed through in catalytic distillation tower, in the presence of a solid catalyst, and is passed through water entrainer and carries out into one
The esterification of step obtains propylene glycol diacetate crude product;
(3) propylene glycol diacetate crude product obtained separated, purified, obtain required propylene glycol diacetate.
2. the method according to claim 1 that can continuously prepare propylene glycol diacetate, which is characterized in that the step
(1) in, the molar ratio of the acetic acid and propylene glycol is 2-4:1.
3. the method according to claim 1 or 2 that can continuously prepare propylene glycol diacetate, which is characterized in that the step
Suddenly in (1), the reaction condition of the fixed bed pre-reactor is controlled are as follows: reaction temperature is 80-120 DEG C, air speed 1.5-5h-1, instead
Answering pressure is normal pressure -0.3MPa.
4. the method according to claim 1-3 that can continuously prepare propylene glycol diacetate, which is characterized in that institute
It states in step (2), the water entrainer includes benzene, toluene or hexamethylene.
5. the method according to claim 4 that can continuously prepare propylene glycol diacetate, which is characterized in that the step
(2) in:
When the water entrainer is benzene, controlling and generating the mass ratio of water in the water entrainer and the catalytic distillation tower is 9:1;
When the water entrainer is toluene, controlling and generating the mass ratio of water in the water entrainer and the catalytic distillation tower is 80.84:
19.16;
When the water entrainer is hexamethylene, control the water entrainer is with the mass ratio for generating water in the catalytic distillation tower
91.6:8.4.
6. the method according to claim 1-5 that can continuously prepare propylene glycol diacetate, which is characterized in that institute
It states in step (2), controls the reaction condition of the catalytic distillation tower are as follows: control tower top pressure is normal pressure, and control tower top temperature is
60-100 DEG C, conversion zone temperature is 80-120 DEG C, and at 200-240 DEG C, the reflux ratio of tower is 0.5-6 for bottom temperature control.
7. the method according to claim 1-6 that can continuously prepare propylene glycol diacetate, which is characterized in that institute
It states in step (2), the water entrainer enters from the bottom of the catalytic distillation tower conversion zone, and propylene glycol diacetate obtained is thick
Product is flowed out from tower top.
8. the method according to claim 1-7 that can continuously prepare propylene glycol diacetate, which is characterized in that institute
It states in step (1) and (2), the solid catalyst includes resin catalyst, heteropolyacid catalyst and/or molecular sieve catalyst.
9. the method according to claim 1-8 that can continuously prepare propylene glycol diacetate, which is characterized in that institute
It states in step (3), the separating step is to be divided the acetic acid in the propylene glycol diacetate crude product by rectifying column
From, and the acetic acid isolated is passed through the fixed bed pre-reactor and is recycled.
10. -9 described in any item methods that can continuously prepare propylene glycol diacetate according to claim 1, which is characterized in that
In the step (3), the purification step is rectification under vacuum, and control operating pressure is -0.085Mpa~-0.09Mpa.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910549271.5A CN110143876A (en) | 2019-06-24 | 2019-06-24 | A kind of method that can continuously prepare propylene glycol diacetate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910549271.5A CN110143876A (en) | 2019-06-24 | 2019-06-24 | A kind of method that can continuously prepare propylene glycol diacetate |
Publications (1)
Publication Number | Publication Date |
---|---|
CN110143876A true CN110143876A (en) | 2019-08-20 |
Family
ID=67596338
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910549271.5A Pending CN110143876A (en) | 2019-06-24 | 2019-06-24 | A kind of method that can continuously prepare propylene glycol diacetate |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110143876A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112691658A (en) * | 2019-10-22 | 2021-04-23 | 中国石油化工股份有限公司 | Solid acid catalyst for propylene glycol monomethyl ether acetate and preparation method and application thereof |
CN113336683A (en) * | 2021-06-28 | 2021-09-03 | 山东益丰生化环保股份有限公司 | Method for preparing 3-methyl mercaptopropionate by using reactive distillation technology |
CN114456060A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Ethylene glycol diacetate or propylene glycol diacetate production system and method |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101514157A (en) * | 2008-02-18 | 2009-08-26 | 大赛璐化学工业株式会社 | Process for preparation of esters solvent |
US20130109882A1 (en) * | 2011-10-27 | 2013-05-02 | Cpc Corporation, Taiwan | Method of Synthesizing Polyol Acetate by Using Catalyst of Ionic Liquid Heteropoly Acid |
CN104557524A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Production method of ethyl acetate |
CN106478417A (en) * | 2016-09-28 | 2017-03-08 | 南京工业大学 | A kind of method that continuous reaction rectification prepares propylene glycol methyl ether acetate |
-
2019
- 2019-06-24 CN CN201910549271.5A patent/CN110143876A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101514157A (en) * | 2008-02-18 | 2009-08-26 | 大赛璐化学工业株式会社 | Process for preparation of esters solvent |
US20130109882A1 (en) * | 2011-10-27 | 2013-05-02 | Cpc Corporation, Taiwan | Method of Synthesizing Polyol Acetate by Using Catalyst of Ionic Liquid Heteropoly Acid |
CN104557524A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Production method of ethyl acetate |
CN106478417A (en) * | 2016-09-28 | 2017-03-08 | 南京工业大学 | A kind of method that continuous reaction rectification prepares propylene glycol methyl ether acetate |
Non-Patent Citations (1)
Title |
---|
ROLF H. PRAGER等: "《Preparation of carboxylate esters of polyhydric alcohols by using a sulfonated charcoal catalyst》", 《AUSTRALIAN JOURNAL OF CHEMISTRY》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112691658A (en) * | 2019-10-22 | 2021-04-23 | 中国石油化工股份有限公司 | Solid acid catalyst for propylene glycol monomethyl ether acetate and preparation method and application thereof |
CN114456060A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Ethylene glycol diacetate or propylene glycol diacetate production system and method |
CN113336683A (en) * | 2021-06-28 | 2021-09-03 | 山东益丰生化环保股份有限公司 | Method for preparing 3-methyl mercaptopropionate by using reactive distillation technology |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110143876A (en) | A kind of method that can continuously prepare propylene glycol diacetate | |
CN101475472B (en) | Method for preparing oxalate by coupling reaction of CO in gaseous phase | |
CN206232628U (en) | A kind of production system of cyclohexanone | |
CN102260149B (en) | Preparation process of 2-ethyl hexenal and 2-ethyl hexanol | |
CN106478514B (en) | A method of synthesis gamma, delta unsaturated ketone class compound | |
CN105111079A (en) | Method and device for separating acetic acid sec-butyl ester and sec-butyl alcohol | |
CN101381283B (en) | Method for continuously preparing 3-methyl-2-butenol | |
JP7305848B2 (en) | Method and apparatus for producing high-purity 1,6-hexanediol | |
CN101723834A (en) | Method for continuously producing carbonate mixed ester | |
CN108821971A (en) | A kind of cyclopentyl acetate synthesis technology | |
CN108997085A (en) | The recovery method and recovery system of by-product in a kind of dimethyl oxalate synthesis technology | |
CN104370740B (en) | Compounding acetic isoborneol ester production method | |
WO2023071938A1 (en) | Maleic anhydride hydrogenation method and succinic acid production method comprising same | |
CN101684064A (en) | Environment-friendly process for producing dihydromyrcenol by using dihydromyrcene hydration reaction | |
CN103242158A (en) | Technological method for synthesizing ethyl acetate | |
CN102701917A (en) | Method for synthesizing MTBE (methyl tert-butyl ether) by reaction of mixed C4 with low isobutene content and methanol | |
CN105461515A (en) | Method for preparing cyclopentanol from cyclopentene | |
CN102452934B (en) | Preparation method of sec-butyl acetate | |
CN110981721A (en) | Method for continuously producing n-propyl acetate | |
CN106518641A (en) | Preparation method and device of polyoxymethylene dimethyl ether reaction raw material | |
CN113443960B (en) | Preparation method of 1, 4-butanediol | |
CN107876037A (en) | Solid base catalyst, its preparation method, application and the method that dihydric alcohol diacetate is prepared using its catalysis | |
CN110483282A (en) | A kind of device and method producing high concentration glycol acetate | |
CN110508018B (en) | Device and method for producing polymethoxy dimethyl ether | |
CN106831413B (en) | The method for producing ethyl acetate |
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 | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190820 |
|
RJ01 | Rejection of invention patent application after publication |