CN102617345A - Method for continuously producing electronic grade propylene glycol methyl ether acetate - Google Patents
Method for continuously producing electronic grade propylene glycol methyl ether acetate Download PDFInfo
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Abstract
The invention discloses a method for continuously producing electronic grade propylene glycol methyl ether acetate. In the method, an electronic grade propylene glycol methyl ether acetate product can be prepared from propylene glycol methyl ether and acetic acid serving as raw materials by performing esterification, light component removing and ion removing process through a two-stage serial fixed bed esterification process based on a compound solid acid catalyst. In the method, a novel continuous process is adopted, so that industrial production of electronic grade propylene glycol methyl ether acetate is realized, the contents of metal ions such as sodium, potassium, calcium, magnesium, lead, zinc, iron and the like in the product are lower than 10 ppb, and the requirements of electronic grade chemicals are met; in the process, an operating form is simple, azeotropic dehydration and neutralizing water washing processes are eliminated, and the production efficiency is high; and the used compound solid acid catalyst has the advantages of high activity, high mechanical strength, long service life, energy saving, environmental friendliness, high economic benefit and good market prospect.
Description
Technical field
The present invention relates to a kind of preparation method of organic cpds, particularly relate to the method that the electronic grade propylene glycol monomethyl ether acetic ester is produced in a kind of serialization.Belong to fine chemicals new catalytic technical study scope.
Background technology
The molecular formula of 1-Methoxy-2-propyl acetate is CH
3COOCH (CH
3) CH
2OCH
3It is the fine chemicals of one type of excellent property; It is the low toxicity advanced industrial solvent of excellent property; Because it has three the solvency power factor or groups that chemical functional is very strong---ehter bond, hydroxyl and ester group; Polarity and nonpolar material all there are very strong dissolving power, have the title of " omnipotent " solvent, be widely used in industrial circles such as coating, paint, printing ink, printing, dyestuff, leather, sensitive materials, electronic chemical product, senior clean-out system, synthetic brake fluid and additives for jet fuel as solvent or organic raw material.Therefore the toxicity of propylene glycol compounds will progressively replace the latter far below the glycol ether compounds.
The electronic grade propylene glycol monomethyl ether acetic ester has dissolving power very widely, its dissolution characteristics with respect to propylene glycol or ester class more near chlorinated solvents.In being applied to the photosensitive resin of semiconductor machining, electronic-grade PMA can be used to replace EEA, is mainly used in the processing of anode sensitive materials.The electronic grade propylene glycol monomethyl ether acetic ester also is used for liquid crystal display and photoresist material production process TFT-LCD photoresistance thinner, photo resistive removing liquor, stripper, industrial clean-out system, removing photoresistance damping fluid etc. and other special procure the chemical products of specification.Be widely used as the solvent of electronic material production usefulness simultaneously.
Generally adopt the homogeneous phase esterification reaction tech in the industry at present; Promptly adopting liquid acid such as sulfuric acid, hydrochloric acid, phosphoric acid, oxalic acid, Hydrocerol A and tosic acid is catalyzer (Liu Zhun etc.; Chinese patent CN1515537A; On July 28th, 2004), mainly there is long reaction time in this tradition homogeneous phase esterification reaction tech, by product is more, yield is not high, reaction product need add alkali neutralization, equipment corrosion is serious and problem such as product ion concentration severe overweight.In order to address the above problem, Wang Xi is used for the building-up reactions (Wang Xi, Liaoning teachers training school journal: natural science edition, 2000 the 2nd the 1st phases of volume) of 1-Methoxy-2-propyl acetate with heteropolyacid catalyst, and Gu Jingfang then adopts solid super-strong acid SO
4 2-/ TiO
2Catalyzer (Gu Jingfang, East China University of Science, master thesis, 2005) as the catalysis synthesizing propylene glycol monomethyl ether acetate it is reported, more than two kinds of catalyzer all have advantages of high catalytic activity, but heteropolyacid, solid super-strong acid SO
4 2-/ TiO
2Catalyzer is prone to poison, loss of active component, thereby causes work-ing life shorter, so do not see the report of industrial applications so far.Qin Xudong etc. use the catalyzer (Qin Xudong etc. of large hole cation exchanger resin as the industriallization 1-Methoxy-2-propyl acetate; Chinese patent CN101337885A; But whether the 1-Methoxy-2-propyl acetate product that obtains is satisfied electronic-grade require not make reports on January 7th, 2009).It is the electronic grade propylene glycol monomethyl ether acetic ester industrialized preparing process (Zhang Yong etc. of catalyzer with the strong-acid cation-exchange resin that Zhang Yong etc. disclose a kind of; Chinese patent CN101993360A; On August 21st, 2009); But comprise the azeotropic dehydration process of adding the band aqua in the described technology, the introducing of band aqua not only is unfavorable for environment protection, also incites somebody to action the yield of reduction 1-Methoxy-2-propyl acetate to a certain degree.
Summary of the invention
Technical problem: the purpose of this invention is to provide the method that the electronic grade propylene glycol monomethyl ether acetic ester is produced in a kind of serialization, overcome long reaction time in traditional homogeneous phase esterification reaction tech, by product is more, yield is not high, reaction product need add the alkali neutralization, need to add band aqua azeotropic dehydration, equipment corrosion is serious and problem such as product ion concentration severe overweight.
The present invention is through adopting the two-stage series connection fixed bed esterification technique based on composite solid-acid catalyst; Through over-churning, take off light constituent, breaking away from three processes of son can electron gain grade propylene glycol monomethyl ether acetic ester product; Realize the suitability for industrialized production of electronic grade propylene glycol monomethyl ether acetic ester; Metal ion neutralization product such as sodium, potassium, calcium, magnesium, lead, zinc, iron etc. reach requirement of electronic grade chemicals all less than 10ppb; The operation format of this technology is simple, no azeotropic dehydration and in and water washing process, production efficiency is high, used composite solid-acid catalyst active high, physical strength is good, the life-span is long, energy-conserving and environment-protective, economic benefit is higher, has good market outlook.
Concrete steps of the present invention are following:
(1) a certain proportion of propylene glycol monomethyl ether and acetic acid pump into device by Ucar 35 fresh feed pump and acetic acid fresh feed pump respectively; Mix through static mixer after being preheating to assigned temperature respectively; First fixed bed that gets into the filling composite solid-acid catalyst carries out esterification, and reaction pressure is that normal pressure, temperature of reaction are 65～85 ℃;
The ratio of said propylene glycol monomethyl ether and acetic acid is the mol ratio 1:1～1:1.5 of propylene glycol monomethyl ether and acetic acid;
Said propylene glycol monomethyl ether is identical with acetic acid preheating assigned temperature, is 65～85 ℃;
Said static mixer is a corrugated plate type, or the simple helix type, or double helical form, or horizontal stripe type static mixer, and static mixer coats thermal insulation layer outward;
Said composite solid-acid catalyst is a kind of loading type PS strong-acid cation-exchange resin, and this catalyzer is obtained on the PS strong-acid cation-exchange resin by active constituent loading;
Said active ingredient is a kind of in nickelous nitrate, aluminum nitrate, nitric acid tin and the zinc nitrate;
Each feed molar proportioning of said PS strong-acid cation-exchange resin is following, monomer styrene: linking agent Vinylstyrene: initiator Sodium Persulfate=85～94:5～15:1～3.
Esterification takes place rapidly in propylene glycol monomethyl ether and acetic acid under the effect of composite solid-acid catalyst; Because reaction reactant concn in early stage is higher and composite solid-acid catalyst is active higher; It is 70 ℃～80 ℃ that the service temperature in this stage maintains lower 65 ℃～85 ℃, preferred temperature, can make the esterification transformation efficiency reach 70%～85%;
Second fixed bed that (2) first fixed bed esterification products get into the filling composite solid-acid catalyst carries out esterification, and reaction pressure is that normal pressure, temperature of reaction are that 85～105 ℃, reaction velocity are 2～20 h
-1Above-mentioned first fixed bed directly links to each other with placed in-line form with second fixed bed, but two Solid Bed service temperatures are different.
Propylene glycol monomethyl ether and acetic acid continue to take place esterification under the effect of composite solid-acid catalyst; Because reaction late phase reaction substrate concentration is relatively low, thus need higher temperature to accelerate speed of reaction, but this esterification is thermopositive reaction; The too high meeting of temperature makes the balance of esterification to reactant one side shifting; Be unfavorable for obtaining high transformation efficiency, comprehensive above-mentioned two factors, the service temperature of selecting second fixed bed is 85 ℃～105 ℃; Be preferably 90 ℃～100 ℃, the conversion rate of esterification that can make the second fixed bed esterification products is greater than 99.5%;
(3) second fixed bed esterification products entering lightness-removing column removes the water of esterification generation, excessive acetic acid and a small amount of unreacted propylene glycol monomethyl ether; The lightness-removing column atmospheric operation; Operating reflux ratio 0.5～2.0; Preferable range is 0.8～1.5, and lightness-removing column top discharge light constituent below 140 ℃ is water, propylene glycol monomethyl ether and acetic acid, and 140～150 ℃ of components in lightness-removing column bottom are thick 1-Methoxy-2-propyl acetate;
(4) thick 1-Methoxy-2-propyl acetate gets into the sub-tower of disengaging and removes ion; Electron gain grade propylene glycol monomethyl ether acetic ester, the operational condition that breaks away from sub-tower is: atmospheric operation, operating reflux ratio 3.0～5.0; Preferable range is 3.5～4.5; Break away from sub-top of tower temperature-stable at 147.0～147.2 ℃, break away from sub-top of tower discharging and be the electronic grade propylene glycol monomethyl ether acetic ester, break away from per 24～48 h discharging of sub-tower bottom debris once.
Above-mentioned four processes are that raw material constantly pumps into device, the serialization production process of the continuous discharger of electronic grade propylene glycol monomethyl ether acetic ester product, and operation is investigated through pilot plant, and the life-span of this composite solid-acid catalyst is more than 3 years.
Beneficial effect: in sum; The method of electronic grade propylene glycol monomethyl ether acetic ester is produced in a kind of serialization of the present invention; Through the new type of continuous metallization processes; Realize the suitability for industrialized production of electronic grade propylene glycol monomethyl ether acetic ester, metals ion in the product such as sodium, potassium, calcium, magnesium, lead, zinc, iron equal size reach requirement of electronic grade chemicals all less than 10ppb; The operation format of this technology is simple, no azeotropic dehydration and in and water washing process, production efficiency is high, used composite solid-acid catalyst active high, physical strength is good, the life-span is long, energy-conserving and environment-protective, economic benefit is higher, has good market outlook.
Description of drawings
Fig. 1 is for adopting the technology main part schematic flow sheet of producing 1-Methoxy-2-propyl acetate based on the two-stage series connection fixed bed esterification technique of composite solid-acid catalyst.
In Fig. 1,1 is the propylene glycol monomethyl ether fresh feed pump, and 2 is the acetic acid fresh feed pump; 3 is the propylene glycol monomethyl ether preheater, and 4 is the acetic acid preheater, and 5 is static mixer; 6 first fixed-bed reactor for the filling composite solid-acid catalyst, 7 second fixed bed reactions for the filling composite solid-acid catalyst, 8 is the lightness-removing column fresh feed pump; 9 is lightness-removing column, and 10 for breaking away from sub-tower fresh feed pump, and 11 for breaking away from sub-tower.
Embodiment
Following embodiment is used for further specifying the present invention and unrestricted the present invention.
Referring to Fig. 1, the process flow diagram of electronic grade propylene glycol monomethyl ether acetic ester is produced in serialization.
Embodiment 1:
(1) propylene glycol monomethyl ether is pumped into device with the flow velocity of 90.12 kg/h through propylene glycol monomethyl ether fresh feed pump 1; And be preheating to 75 ℃ through propylene glycol monomethyl ether preheater 3; Simultaneously acetic acid is pumped into device with the flow velocity of 72.06 kg/h through acetic acid fresh feed pump 2; And be preheating to 75 ℃ through acetic acid preheater 4; Propylene glycol monomethyl ether after the preheating and acetic acid mix through simple helix type static mixer 5, and first fixed bed 6 that gets into the filling composite solid-acid catalyst carries out esterification, and the first fixed bed reaction pressure is that normal pressure, temperature of reaction are that 75 ℃, reaction velocity are 12 h
-1
Composite solid-acid catalyst is a kind of loading type PS strong-acid cation-exchange resin, and this catalyzer is carried on the PS strong-acid cation-exchange resin by nickelous nitrate and obtains; Each feed molar proportioning of PS strong-acid cation-exchange resin is following, monomer styrene: linking agent Vinylstyrene: initiator Sodium Persulfate=88:10:2.
Under the above-mentioned condition, the conversion rate of esterification of the first fixed bed esterification products is 72.70%.
Second fixed bed 7 that (2) first fixed bed esterification products directly get into the filling composite solid-acid catalyst carries out esterification, and reaction pressure is that normal pressure, temperature of reaction are that 98 ℃, reaction velocity are 12 h
-1, the accumulative total conversion rate of esterification 99.65% of the second fixed bed esterification products;
(3) second fixed bed esterification products remove the water of esterification generation, excessive acetic acid and a small amount of unreacted propylene glycol monomethyl ether through lightness-removing column fresh feed pump 8 entering lightness-removing columns 9; The lightness-removing column atmospheric operation; Operating reflux ratio 1.0; Lightness-removing column top discharge light constituent below 140 ℃ is water, propylene glycol monomethyl ether and acetic acid, and the flow velocity that takes off light constituent is 30.84kg/h, and the lightness-removing column bottom temp is stabilized in 146～149 ℃; Bottom discharge is thick 1-Methoxy-2-propyl acetate, and thick 1-Methoxy-2-propyl acetate discharging speed is 131.35 kg/h;
(4) thick 1-Methoxy-2-propyl acetate removes ion through breaking away from the sub-tower 11 of sub-tower fresh feed pump 10 entering disengagings; The operational condition that breaks away from sub-tower is: atmospheric operation; Operating reflux ratio 4.2 breaks away from sub-top of tower temperature-stable at 147.0～147.2 ℃, breaks away from sub-top of tower discharging and is the electronic grade propylene glycol monomethyl ether acetic ester; Electronic grade propylene glycol monomethyl ether acetic ester discharging speed is 131.10kg/h, breaks away from per 24～48 h discharging of sub-tower bottom debris once.
Detections such as the metals ion sodium in the electronic grade propylene glycol monomethyl ether acetic ester product of embodiment 1 preparation, potassium, calcium, magnesium, lead, zinc, iron gather sees table 1, and detected result shows that metals ion such as sodium in the product, potassium, calcium, magnesium, lead, zinc, iron equal size are all less than 10ppb.
Embodiment 2:
(1) propylene glycol monomethyl ether is pumped into device with the flow velocity of 108.15 kg/h through propylene glycol monomethyl ether fresh feed pump 1; And be preheating to 65 ℃ through propylene glycol monomethyl ether preheater 3; Simultaneously acetic acid is pumped into device with the flow velocity of 90.08kg/h through acetic acid fresh feed pump 2; And be preheating to 65 ℃ through propylene glycol monomethyl ether preheater 4; Propylene glycol monomethyl ether after the preheating and acetic acid mix through double helical form static mixer 5, and first fixed bed 6 that gets into the filling composite solid-acid catalyst carries out esterification, and the first fixed bed reaction pressure is that normal pressure, temperature of reaction are that 77 ℃, reaction velocity are 11.5 h
-1
Composite solid-acid catalyst is a kind of loading type PS strong-acid cation-exchange resin, and this catalyzer is carried on the PS strong-acid cation-exchange resin by aluminum nitrate and obtains; Composite solid-acid catalyst is a kind of loading type PS strong-acid cation-exchange resin, and this catalyzer is carried on the PS strong-acid cation-exchange resin by nickelous nitrate and obtains; Each feed molar proportioning of PS strong-acid cation-exchange resin is following, monomer styrene: linking agent Vinylstyrene: initiator Sodium Persulfate=91:7:2.
Under the above-mentioned condition, the conversion rate of esterification of the first fixed bed esterification products is 78.90%.
Second fixed bed 7 that (2) first fixed bed esterification products directly get into the filling composite solid-acid catalyst carries out esterification, and reaction pressure is that normal pressure, temperature of reaction are that 95 ℃, reaction velocity are 11.5 h
-1, the accumulative total conversion rate of esterification 99.73% of the second fixed bed esterification products;
(3) second fixed bed esterification products remove the water of esterification generation, excessive acetic acid and a small amount of unreacted propylene glycol monomethyl ether through lightness-removing column fresh feed pump 8 entering lightness-removing columns 9; The lightness-removing column atmospheric operation; Operating reflux ratio 1.2; Lightness-removing column top discharge light constituent below 140 ℃ is water, propylene glycol monomethyl ether and acetic acid, and the flow velocity that takes off light constituent is 39.90kg/h, and the lightness-removing column bottom temp is stabilized in 146～149 ℃; Bottom discharge is thick 1-Methoxy-2-propyl acetate, and thick 1-Methoxy-2-propyl acetate discharging speed is 158.33 kg/h;
(4) thick 1-Methoxy-2-propyl acetate removes ion through breaking away from the sub-tower 11 of sub-tower fresh feed pump 10 entering disengagings; The operational condition that breaks away from sub-tower is: atmospheric operation; Operating reflux ratio 4.3 breaks away from sub-top of tower temperature-stable at 147.0-147.2 ℃, breaks away from sub-top of tower discharging and is the electronic grade propylene glycol monomethyl ether acetic ester; Electronic grade propylene glycol monomethyl ether acetic ester discharging speed is 158.10kg/h, breaks away from per 24～48 h discharging of sub-tower bottom debris once.
Detections such as the metals ion sodium in the electronic grade propylene glycol monomethyl ether acetic ester product of embodiment 2 preparation, potassium, calcium, magnesium, lead, zinc, iron gather sees table 1, and detected result shows that metals ion such as sodium in the product, potassium, calcium, magnesium, lead, zinc, iron equal size are all less than 10ppb.
Embodiment 3:
(1) propylene glycol monomethyl ether is pumped into device with the flow velocity of 153.21kg/h through propylene glycol monomethyl ether fresh feed pump 1; And be preheating to 85 ℃ through propylene glycol monomethyl ether preheater 3; Simultaneously acetic acid is pumped into device with the flow velocity of 117.70 kg/h through acetic acid fresh feed pump 2; And be preheating to 85 ℃ through propylene glycol monomethyl ether preheater 4; Propylene glycol monomethyl ether after the preheating and acetic acid mix through horizontal stripe type static mixer 5, and first fixed bed 6 that gets into the filling composite solid-acid catalyst carries out esterification, and the first fixed bed reaction pressure is that normal pressure, temperature of reaction are that 79 ℃, reaction velocity are 12 .5h
-1
Composite solid-acid catalyst is a kind of loading type PS strong-acid cation-exchange resin, and this catalyzer is carried on the PS strong-acid cation-exchange resin by nitric acid tin and obtains; Composite solid-acid catalyst is a kind of loading type PS strong-acid cation-exchange resin, and this catalyzer is carried on the PS strong-acid cation-exchange resin by nickelous nitrate and obtains; Each feed molar proportioning of PS strong-acid cation-exchange resin is following, monomer styrene: linking agent Vinylstyrene: initiator Sodium Persulfate=92:6:2.
Under the above-mentioned condition, the conversion rate of esterification of the first fixed bed esterification products is 71.06%.
Second fixed bed 7 that (2) first fixed bed esterification products directly get into the filling composite solid-acid catalyst carries out esterification, and reaction pressure is that normal pressure, temperature of reaction are that 96 ℃, reaction velocity are 12.5 h
-1, the accumulative total conversion rate of esterification 99.64% of the second fixed bed esterification products;
(3) second fixed bed esterification products remove the water of esterification generation, excessive acetic acid and a small amount of unreacted propylene glycol monomethyl ether through lightness-removing column fresh feed pump 8 entering lightness-removing columns 9; The lightness-removing column atmospheric operation; Operating reflux ratio 1.3; Lightness-removing column top discharge light constituent below 140 ℃ is water, propylene glycol monomethyl ether and acetic acid, and the flow velocity that takes off light constituent is 59.51kg/h, and the lightness-removing column bottom temp is stabilized in 146～149 ℃; Bottom discharge is thick 1-Methoxy-2-propyl acetate, and thick 1-Methoxy-2-propyl acetate discharging speed is 184.36 kg/h;
(4) thick 1-Methoxy-2-propyl acetate removes ion through breaking away from the sub-tower 11 of sub-tower fresh feed pump 10 entering disengagings; The operational condition that breaks away from sub-tower is: atmospheric operation; Operating reflux ratio 4.15 breaks away from sub-top of tower temperature-stable at 147.0～147.2 ℃, breaks away from sub-top of tower discharging and is the electronic grade propylene glycol monomethyl ether acetic ester; Electronic grade propylene glycol monomethyl ether acetic ester discharging speed is 184.05kg/h, breaks away from per 24～48 h discharging of sub-tower bottom debris once.
Detections such as the metals ion sodium in the electronic grade propylene glycol monomethyl ether acetic ester product of embodiment 3 preparation, potassium, calcium, magnesium, lead, zinc, iron gather sees table 1, and detected result shows that metals ion such as sodium in the product, potassium, calcium, magnesium, lead, zinc, iron equal size are all less than 10ppb.
Embodiment 4:
(1) propylene glycol monomethyl ether is pumped into device with the flow velocity of 135.18 kg/h through propylene glycol monomethyl ether fresh feed pump 1; And be preheating to 70 ℃ through propylene glycol monomethyl ether preheater 3; Simultaneously acetic acid is pumped into device with the flow velocity of 120.11kg/h through acetic acid fresh feed pump 2; And be preheating to 70 ℃ through propylene glycol monomethyl ether preheater 4; Propylene glycol monomethyl ether after the preheating and acetic acid mix through corrugated plate type static mixer 5, and first fixed bed 6 that gets into the filling composite solid-acid catalyst carries out esterification, and the first fixed bed reaction pressure is that normal pressure, temperature of reaction are that 70 ℃, reaction velocity are 12 h
-1
Composite solid-acid catalyst is a kind of loading type PS strong-acid cation-exchange resin, and this catalyzer is carried on the PS strong-acid cation-exchange resin by zinc nitrate and obtains; Composite solid-acid catalyst is a kind of loading type PS strong-acid cation-exchange resin, and this catalyzer is carried on the PS strong-acid cation-exchange resin by nickelous nitrate and obtains; Each feed molar proportioning of PS strong-acid cation-exchange resin is following, monomer styrene: linking agent Vinylstyrene: initiator Sodium Persulfate=85:12:3.
Under the above-mentioned condition, the conversion rate of esterification of the first fixed bed esterification products is 75.76%.
Second fixed bed 7 that (2) first fixed bed esterification products directly get into the filling composite solid-acid catalyst carries out esterification, and reaction pressure is that normal pressure, temperature of reaction are that 94 ℃, reaction velocity are 12 h
-1, the accumulative total conversion rate of esterification 99.69% of the second fixed bed esterification products;
(3) second fixed bed esterification products remove the water of esterification generation, excessive acetic acid and a small amount of unreacted propylene glycol monomethyl ether through lightness-removing column fresh feed pump 8 entering lightness-removing columns 9; The lightness-removing column atmospheric operation; Operating reflux ratio 1.25; Lightness-removing column top discharge light constituent below 140 ℃ is water, propylene glycol monomethyl ether and acetic acid, and the flow velocity that takes off light constituent is 57.60kg/h, and the lightness-removing column bottom temp is stabilized in 146～149 ℃; Bottom discharge is thick 1-Methoxy-2-propyl acetate, and thick 1-Methoxy-2-propyl acetate discharging speed is 197.69 kg/h;
(4) thick 1-Methoxy-2-propyl acetate removes ion through breaking away from the sub-tower 11 of sub-tower fresh feed pump 10 entering disengagings; The operational condition that breaks away from sub-tower is: atmospheric operation; Operating reflux ratio 4.2 breaks away from sub-top of tower temperature-stable at 147.0～147.2 ℃, breaks away from sub-top of tower discharging and is the electronic grade propylene glycol monomethyl ether acetic ester; Electronic grade propylene glycol monomethyl ether acetic ester discharging speed is 197.25kg/h, breaks away from per 24～48 h discharging of sub-tower bottom debris once.
Detections such as the metals ion sodium in the electronic grade propylene glycol monomethyl ether acetic ester product of embodiment 4 preparation, potassium, calcium, magnesium, lead, zinc, iron gather sees table 1, and detected result shows that metals ion such as sodium in the product, potassium, calcium, magnesium, lead, zinc, iron equal size are all less than 10ppb.
Embodiment 5:
(1) propylene glycol monomethyl ether is pumped into device with the flow velocity of 139.69 kg/h through propylene glycol monomethyl ether fresh feed pump 1; And be preheating to 80 ℃ through propylene glycol monomethyl ether preheater 3; Simultaneously acetic acid is pumped into device with the flow velocity of 132.12 kg/h through acetic acid fresh feed pump 2; And be preheating to 80 ℃ through propylene glycol monomethyl ether preheater 4; Propylene glycol monomethyl ether after the preheating and acetic acid mix through double helical form static mixer 5, and first fixed bed 6 that gets into the filling composite solid-acid catalyst carries out esterification, and the first fixed bed reaction pressure is that normal pressure, temperature of reaction are that 83 ℃, reaction velocity are 11.2 h
-1
Composite solid-acid catalyst is a kind of loading type PS strong-acid cation-exchange resin, and this catalyzer is carried on the PS strong-acid cation-exchange resin by nickelous nitrate and obtains; Composite solid-acid catalyst is a kind of loading type PS strong-acid cation-exchange resin, and this catalyzer is carried on the PS strong-acid cation-exchange resin by nickelous nitrate and obtains; Each feed molar proportioning of PS strong-acid cation-exchange resin is following, monomer styrene: linking agent Vinylstyrene: initiator Sodium Persulfate=86:13:1.
Under the above-mentioned condition, the conversion rate of esterification of the first fixed bed esterification products is 81.20%.
Second fixed bed 7 that (2) first fixed bed esterification products directly get into the filling composite solid-acid catalyst carries out esterification, and reaction pressure is that normal pressure, temperature of reaction are that 100 ℃, reaction velocity are 11.2 h
-1, the accumulative total conversion rate of esterification 99.76% of the second fixed bed esterification products;
(3) second fixed bed esterification products remove the water of esterification generation, excessive acetic acid and a small amount of unreacted propylene glycol monomethyl ether through lightness-removing column fresh feed pump 8 entering lightness-removing columns 9; The lightness-removing column atmospheric operation; Operating reflux ratio 1.0; Lightness-removing column top discharge light constituent below 140 ℃ is water, propylene glycol monomethyl ether and acetic acid, and the flow velocity that takes off light constituent is 67.43kg/h, and the lightness-removing column bottom temp is stabilized in 146～149 ℃; Bottom discharge is thick 1-Methoxy-2-propyl acetate, and thick 1-Methoxy-2-propyl acetate discharging speed is 207.38kg/h;
(4) thick 1-Methoxy-2-propyl acetate removes ion through breaking away from the sub-tower 11 of sub-tower fresh feed pump 10 entering disengagings; The operational condition that breaks away from sub-tower is: atmospheric operation; Operating reflux ratio 4.2 breaks away from sub-top of tower temperature-stable at 147.0～147.2 ℃, breaks away from sub-top of tower discharging and is the electronic grade propylene glycol monomethyl ether acetic ester; Electronic grade propylene glycol monomethyl ether acetic ester discharging speed is 206.90kg/h, breaks away from per 24～48 h discharging of sub-tower bottom debris once.
Detections such as the metals ion sodium in the electronic grade propylene glycol monomethyl ether acetic ester product of embodiment 5 preparation, potassium, calcium, magnesium, lead, zinc, iron gather sees table 1, and detected result shows that metals ion such as sodium in the product, potassium, calcium, magnesium, lead, zinc, iron equal size are all less than 10ppb.
Metals ion sodium in the electronic grade propylene glycol monomethyl ether acetic ester product of above-mentioned each embodiment preparation, potassium, calcium, magnesium, lead, zinc, iron ion detect and gather, and see table 1: unit: ppb
| ? | Sodium ion | Potassium ion | Calcium ion | Mg ion | Lead ion | Zine ion | Iron ion |
| Embodiment 1 | 5.31 | 1.35 | 4.47 | 2.88 | 1.36 | 1.48 | 4.86 |
| Embodiment 2 | 7.19 | 2.28 | 3.46 | 1.15 | 1.19 | 1.63 | 5.23 |
| Embodiment 3 | 1.25 | 3.00 | 1.43 | 0.36 | 1.20 | 4.24 | 5.00 |
| Embodiment 4 | 3.74 | 1.43 | 2.08 | 1.66 | 0.31 | 1.71 | 7.53 |
| Embodiment 5 | 1.73 | 1.32 | 2.13 | 2.66 | 0.49 | 1.71 | 5.36 |
Above-described embodiment, just several kinds of the specific embodiment of the invention, common variation and replacement that those skilled in the art carries out in technical scheme scope of the present invention are included in protection scope of the present invention.
Claims (6)
1. the method for electronic grade propylene glycol monomethyl ether acetic ester is produced in a serialization; With propylene glycol monomethyl ether and acetic acid is raw material; It is characterized in that: adopt two-stage series connection fixed bed esterification technique based on composite solid-acid catalyst; Esterification reaction product can obtain the electronic grade propylene glycol monomethyl ether acetic ester through the follow-up processing of taking off light constituent, breaking away from two processes of son;
Said composite solid-acid catalyst is a loading type PS strong-acid cation-exchange resin, and it is made in the PS strong-acid cation-exchange resin by active constituent loading;
Said active ingredient is a kind of in nickelous nitrate, aluminum nitrate, nitric acid tin and the zinc nitrate;
Each feed molar proportioning of said PS strong-acid cation-exchange resin is following, monomer styrene: linking agent Vinylstyrene: initiator Sodium Persulfate=85～94:5～15:1～3.
2. the method for electronic grade propylene glycol monomethyl ether acetic ester is produced in a kind of serialization according to claim 1; It is characterized in that: said two-stage series connection fixed bed esterification technique is that first fixed bed is directly linked to each other with placed in-line form with second fixed bed; Two Solid Bed service temperatures are different, respectively are 65～85 ℃ and 85～105 ℃.
3. the method for electronic grade propylene glycol monomethyl ether acetic ester is produced in a kind of serialization according to claim 2, and it is characterized in that: the said first fixed bed operation temperature is 70 ℃～80 ℃.
4. the method for electronic grade propylene glycol monomethyl ether acetic ester is produced in a kind of serialization according to claim 2, and it is characterized in that: the said second fixed bed operation temperature is 90 ℃～100 ℃.
5. the method for electronic grade propylene glycol monomethyl ether acetic ester is produced in a kind of serialization according to claim 2, it is characterized in that:
This method may further comprise the steps:
(1) a certain proportion of propylene glycol monomethyl ether and acetic acid pump into device by propylene glycol monomethyl ether fresh feed pump and acetic acid fresh feed pump respectively; Mix through static mixer after being preheating to assigned temperature respectively; First fixed bed that gets into the filling composite solid-acid catalyst carries out esterification, and reaction pressure is that normal pressure, temperature of reaction are 65～85 ℃;
The ratio of said propylene glycol monomethyl ether and acetic acid is the mol ratio 1:1～1:1.5 of propylene glycol monomethyl ether and acetic acid;
The preheating assigned temperature of said propylene glycol monomethyl ether and acetic acid is identical, is 65～85 ℃;
Second fixed bed that (2) first fixed bed esterification products get into the filling composite solid-acid catalyst carries out esterification, and reaction pressure is that normal pressure, temperature of reaction are 85～105 ℃;
(3) second fixed bed esterification products entering lightness-removing column removes the water of esterification generation, excessive acetic acid and a small amount of unreacted propylene glycol monomethyl ether; The lightness-removing column atmospheric operation; Operating reflux ratio 0.5～2.0,140～150 ℃ of components in lightness-removing column bottom are thick 1-Methoxy-2-propyl acetate;
(4) thick 1-Methoxy-2-propyl acetate gets into the sub-tower of disengaging and removes ion; Electron gain grade propylene glycol monomethyl ether acetic ester; The operational condition that breaks away from sub-tower is: atmospheric operation, and operating reflux ratio 3.0～5.0 breaks away from sub-top of tower temperature-stable at 147.0～147.2 ℃; Break away from sub-top of tower discharging and be the electronic grade propylene glycol monomethyl ether acetic ester, break away from per 24～48 h discharging of sub-tower bottom debris once.
6. the method for electronic grade propylene glycol monomethyl ether acetic ester is produced in a kind of serialization according to claim 5; It is characterized in that: static mixer is a corrugated plate type described in the step (1), or the simple helix type, or double helical form; Or horizontal stripe type static mixer, static mixer coats thermal insulation layer outward.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103769215A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Modified cation exchange resin catalyst and its preparation method and application |
| CN107098810A (en) * | 2017-05-16 | 2017-08-29 | 天津大学 | A kind of process for separation and purification for preparing electronic grade propylene glycol methyl ether acetate |
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| CN101337885A (en) * | 2008-08-08 | 2009-01-07 | 德纳（南京）化工有限公司 | Method for preparing 1-Methoxy-2-propyl acetate by continuous esterification reaction |
| CN101722027A (en) * | 2009-11-26 | 2010-06-09 | 沈阳工业大学 | Esterification catalyst for synthesizing ethylene/propylene glycol ether carboxylate, and preparation method thereof |
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| CN101337885A (en) * | 2008-08-08 | 2009-01-07 | 德纳（南京）化工有限公司 | Method for preparing 1-Methoxy-2-propyl acetate by continuous esterification reaction |
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