CN109180425B - Refining process and system for acetic ester recovery liquid containing cyclopentanone and propylene glycol methyl ether - Google Patents
Refining process and system for acetic ester recovery liquid containing cyclopentanone and propylene glycol methyl ether Download PDFInfo
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- CN109180425B CN109180425B CN201811266910.9A CN201811266910A CN109180425B CN 109180425 B CN109180425 B CN 109180425B CN 201811266910 A CN201811266910 A CN 201811266910A CN 109180425 B CN109180425 B CN 109180425B
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- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000007788 liquid Substances 0.000 title claims abstract description 61
- 238000011084 recovery Methods 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 28
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000007670 refining Methods 0.000 title claims abstract description 19
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 235000019439 ethyl acetate Nutrition 0.000 title claims abstract description 8
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 238000009835 boiling Methods 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 239000012223 aqueous fraction Substances 0.000 claims abstract description 13
- HPXGCCXQMCZZHV-UHFFFAOYSA-N cyclopentanone hydrate Chemical compound O.C1(CCCC1)=O HPXGCCXQMCZZHV-UHFFFAOYSA-N 0.000 claims abstract description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000002203 pretreatment Methods 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000005374 membrane filtration Methods 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 13
- 239000012071 phase Substances 0.000 description 12
- TUVYSBJZBYRDHP-UHFFFAOYSA-N acetic acid;methoxymethane Chemical compound COC.CC(O)=O TUVYSBJZBYRDHP-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 229920002120 photoresistant polymer Polymers 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- SYUYWGKVQCNLSX-UHFFFAOYSA-N C(C)(=O)O.C(CC(=O)O)(=O)OC Chemical compound C(C)(=O)O.C(CC(=O)O)(=O)OC SYUYWGKVQCNLSX-UHFFFAOYSA-N 0.000 description 1
- WUWMTFCQIQHXTN-UHFFFAOYSA-N C(C)(=O)O.COC.C(CC(=O)O)(=O)O Chemical compound C(C)(=O)O.COC.C(CC(=O)O)(=O)O WUWMTFCQIQHXTN-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- -1 aliphatic imide Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- GICBTEWABQGGPR-UHFFFAOYSA-N methoxymethane;propanedioic acid Chemical compound COC.OC(=O)CC(O)=O GICBTEWABQGGPR-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000011045 prefiltration Methods 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- 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
-
- 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
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
Abstract
The invention discloses a refining process of acetic ester recovery liquid containing cyclopentanone and propylene glycol methyl ether, which comprises the following steps: dehydrating the recovery liquid, regulating the pH value and filtering to obtain dehydrated recovery liquid; introducing the dehydrated recovery liquid into a first rectifying tower, and separating to obtain a tower top low-boiling point organic solvent fraction and a tower bottom light-removal recovery liquid; introducing the tower bottom light-removal recovery liquid into a second rectifying tower, and separating to obtain a tower top cyclopentanone-water fraction and a tower bottom propylene glycol methyl ether acetate heavy component; introducing the cyclopentanone-water fraction at the top of the tower obtained in the step S3 into a third rectifying tower, and separating to obtain a cyclopentanone product at the top of the tower and a cyclopentanone product at the bottom of the tower; and (3) introducing the heavy components of the propylene glycol methyl ether acetate at the bottom of the tower obtained in the step (S3) into a fourth rectifying tower, and separating to obtain a propylene glycol methyl ether acetate product at the top of the tower and a heavy component raffinate at the bottom of the tower. The continuous rectification method has low energy consumption, safe and reliable production process, less resin residual liquid, high purity of the product of membrane filtration up to 99.91%, and product chromaticity and other indexes reaching electronic grade standard.
Description
Technical Field
The invention relates to the technical field of recovery of dangerous chemicals in the electronic industry, in particular to a refining process and a refining system of recovery liquid in the electronic industry, which contain cyclopentanone and propylene glycol methyl ether acetate.
Background
Cyclopentanone, having a melting point of-58.2 ℃ and a boiling point of 130.6 ℃ and a density of 0.9487g/cm3 (20 ℃), is insoluble in water, is soluble in most organic solvents such as alcohols and ethers, and is readily polymerizable, particularly in the presence of trace amounts of acids. Propylene Glycol Methyl Ether Acetate (PGMEA), colorless hygroscopic liquid, melting point-87 ℃, boiling point 149 ℃, water-solubility (solvent-in-water) 16.0ml/L (25 ℃), explosion limit: 1.5 to 7.0 percent (volume) of the air at 20 ℃.
Wafers are the basic material for manufacturing semiconductor chips. Photolithography is one of the common processes in wafer production. Photoresists are composed primarily of photosensitive high molecular polymers that are very sensitive to light and energy, and organic solvents (diluents): the former is the main body of the photoresist, and the main components are aliphatic imide polymer, polyamide and the like; the latter is a medium of photoresist, and the main components are cyclopentanone, propylene glycol methyl ether acetate, propylene glycol monomethyl ether and the like. In order to firmly adhere the photoresist on the surface of the substrate, the photoresist is uniformly coated with the photoresist and then dried. In the drying process, the organic waste gas volatilized by the organic solvent in the photoresist is condensed and recovered to obtain a mixed solution containing cyclopentanone as a main component, wherein the mixed solution is alkaline and has ammonia taste, and the mixed solution also contains 20-30% of propylene glycol monomethyl ether, a small amount of low-boiling-point organic solvents such as water, acetone and the like, organic amines, solid impurities, high-boiling-point resin substances and light components with the boiling point of 60-70 ℃. Because the products are inflammable and explosive products, the products are dangerous chemicals after being recovered, the national directory is dangerous solid waste at present, and dangerous waste specialized companies are required to be disposed and reused.
The refining process has the technical difficulties that: the components of the recovery liquid are complex, the boiling point of propylene glycol methyl ether acetate is higher, each component has the characteristics of azeotropy and low relative volatility, and the components are easy to polymerize or decompose and explode in the separation process. No technical proposal for refining waste liquid containing cyclopentanone and propylene glycol methyl ether acetate is found in the prior art.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a refining process of acetic ester recovery liquid containing cyclopentanone and propylene glycol methyl ether, which has the advantages of low probability of component polymerization or decomposition in the rectification process, less waste liquid and waste residue, and higher product purity and recovery rate.
In order to achieve the technical effects, the technical scheme of the invention is as follows: a refining process of acetic ester recovery liquid containing cyclopentanone and propylene glycol methyl ether is characterized by comprising the following steps:
s1: dehydrating the recovery liquid, regulating the pH value to 6-14, and filtering to obtain a dehydrated recovery liquid;
s2: introducing the dehydration recovery liquid into a first rectifying tower, and separating to obtain a tower top light component low-boiling point organic solvent fraction and a tower bottom light recovery liquid;
s3: introducing the tower bottom light-removal recovery liquid into a second rectifying tower, and separating to obtain a tower top cyclopentanone-water fraction and a tower bottom propylene glycol methyl ether acetate heavy component;
s4: introducing the cyclopentanone-water fraction at the top of the tower obtained in the step S3 into a third rectifying tower, and separating to obtain a cyclopentanone product at the top of the tower and a cyclopentanone product at the bottom of the tower;
s5: and (3) introducing the heavy components of the propylene glycol methyl ether acetate at the bottom of the tower obtained in the step (S3) into a fourth rectifying tower, and separating to obtain a propylene glycol methyl ether acetate product at the top of the tower and a heavy component raffinate at the bottom of the tower.
The cyclopentanone product and the propylene glycol methyl ether acetate product are filtered by a membrane to further obtain electronic-grade cyclopentanone and propylene glycol methyl ether acetate. The light component low boiling point organic solvent fraction obtained from the top of the first rectifying tower and the water fraction obtained from the top of the third rectifying tower are condensed by a condenser and then are led into a storage tank.
The dehydrating agent is usually selected from the group consisting of inorganic salts having water absorbing properties or capable of reacting with water to form crystalline hydrates, silica gel, for example, one or a combination of two or more selected from sodium carbonate, sodium hydroxide, calcium chloride and silica gel.
S2, the boiling point of the low-boiling point organic solvent is lower than that of cyclopentanone, the main component is acetone, and a small amount of low-boiling point organic base such as propylamine, ethylenediamine and propylenediamine is contained, when the pH value of the recovery liquid is alkaline, that is, the pH value of the recovery liquid is higher than 7, the recovery liquid is directly filtered and introduced into the first rectifying tower without adding acid to adjust the pH value.
Further, S1 also includes a decoloring treatment in which a decoloring agent is added to the recovery liquid at the same time. The decoloring agent is one or two selected from diatomite, activated clay and activated carbon. The solid impurity content in the material subjected to S1 filtration treatment is extremely low.
In order to facilitate the discharge of the heavy component raffinate in the step S5, reduce the viscosity of the heavy component raffinate, and ensure that a certain amount of propylene glycol methyl ether acetate remains in the heavy component raffinate, in order to improve the recovery rate of acetate components, the preferable technical scheme is that the method further comprises the step S6: and (3) introducing the heavy component raffinate at the bottom of the tower obtained in the step (S5) into an evaporator for evaporation, separating to obtain a gas phase material and a resin raffinate, and introducing the gas phase material into a fourth rectifying tower. Further, the evaporator is a wiped film evaporator.
The preferable technical proposal is that the dehydration recovery liquid is preheated and then is led into a first rectifying tower, the operation pressure of the first rectifying tower is 10 to 101KPa, the temperature of the top of the tower is 10 to 60 ℃ and the temperature of the bottom of the tower is 58 to 142 ℃ when the light component low boiling point organic solvent fraction at the top of the tower is extracted. The main composition of the overhead component at the extraction temperature is acetone. In the normal pressure rectification process, the temperature of the top of the tower is 54.5-58.5 ℃ and the temperature of the bottom of the tower is 135-142 ℃ when the light component low boiling point organic solvent fraction at the top of the tower is extracted. The boiling point of the component decreases under reduced pressure distillation.
The preferable technical proposal is that the operating pressure of the second rectifying tower is 10-101 KPa, the temperature of the top of the tower is 60-131 ℃ and the temperature of the bottom of the tower is 85-150 ℃ when the cyclopentanone-water fraction at the top of the tower is extracted. The rectification process of the second rectification tower is normal pressure rectification or reduced pressure rectification. In the normal pressure rectification process, the temperature of the top of the tower is 105-125 ℃ and the temperature of the bottom of the tower is 135-149 ℃ when the cyclopentanone-water fraction at the top of the tower is extracted.
The preferable technical proposal is that the operating pressure of the third rectifying tower is 10-101 KPa, the temperature of the top of the tower is 50-121 ℃ and the temperature of the bottom of the tower is 70-132 ℃ when the water fraction at the top of the tower is extracted. The rectification process of the third rectification tower is normal pressure rectification or reduced pressure rectification. In the normal pressure rectification process, the temperature of the tower top is 90-110 ℃ and the temperature of the tower bottom is 130-132 ℃ when the water fraction at the tower top is extracted.
The preferable technical proposal is that the operating pressure of the fourth rectifying tower is 5-101 KPa, the temperature of the tower top is 70-150 ℃ and the temperature of the tower bottom is 85-160 ℃ when the propylene glycol methyl ether acetate product at the tower top is extracted. The rectification process of the fourth rectification tower is normal pressure rectification or reduced pressure rectification. In the normal pressure rectification process, the temperature of the tower top is 144-147 ℃ and the temperature of the tower bottom is 155-158 ℃ when propylene glycol methyl ether acetate products at the tower top are extracted.
The preferable technical proposal is that the gas phase outlet temperature of the evaporator is 85-160 ℃ and the operating pressure is 5-101 KPa. In the normal pressure rectification process, the gas phase outlet temperature of the evaporator is 155-160 ℃.
The second object of the invention is to provide a refining system of acetic ester recovery liquid containing cyclopentanone and propylene glycol methyl ether, which is characterized by comprising a pretreatment kettle, a first rectifying tower, a second rectifying tower, a third rectifying tower and a fourth rectifying tower;
a discharge hole of the pretreatment kettle is communicated with a first rectifying tower, and a bottom liquid phase outlet of the first rectifying tower is communicated with a feed hole of a second rectifying tower;
the top gas phase discharge port of the second rectifying tower is communicated with the feed port of the third rectifying tower, and the bottom discharge port of the third rectifying tower is communicated with the cyclopentanone receiving tank;
the bottom liquid phase outlet of the second rectifying tower is communicated with the feed inlet of the fourth rectifying tower, and the top discharge outlet of the fourth rectifying tower is communicated with the propylene glycol methyl ether acetate receiving tank through a condenser.
In order to reduce the content of acetate in the raffinate of the fourth rectifying still and improve the recovery rate of acetate, the preferable technical scheme is that the method further comprises an evaporator, wherein a feed inlet of the evaporator is communicated with a heavy component discharge port at the bottom of the fourth rectifying tower, and a gas phase outlet of the evaporator is communicated with a feed inlet of the fourth rectifying tower.
The preferable technical scheme is that a liquid filter is communicated between a discharge port of the pretreatment kettle and a feed port of the first rectifying tower. Further, a liquid filter and a heater are sequentially communicated between the discharge port of the pretreatment kettle and the feed port of the first rectifying tower. The heater is used for preheating the materials added into the first rectifying tower, and the preheating temperature is 45-53 ℃.
The invention has the advantages and beneficial effects that:
the refining process of the recovery liquid containing cyclopentanone and propylene glycol methyl ether acetate is reasonable in steps, the pH value is adjusted, the corrosion of rectification on a refining system is reduced, the polymerization probability of cyclopentanone is reduced to the maximum extent, and the pre-filtration can reduce the corrosion and blockage phenomena of a separation device;
the continuous rectification method is low in energy consumption, safe and reliable in production process, less in resin residual liquid production amount, and the purity of the product subjected to membrane filtration reaches more than 99.91%, and the chromaticity and other indexes of the product can reach electronic grade standards, so that the product can be recycled.
Drawings
FIG. 1 is a schematic diagram of a refining process example 1 of a recovery liquid containing cyclopentanone and propylene glycol methyl ether acetate according to the present invention;
FIG. 2 is a schematic diagram of the refining process of example 2 of the recovery liquid of cyclopentanone and propylene glycol methyl ether acetate according to the present invention.
In the figure: 1. a pretreatment kettle; 2. a first rectifying column; 3. a second rectifying column; 4. a third rectifying column; 5. a fourth rectifying column; 6. propylene glycol methyl ether acetate receiving tank; 7. an evaporator; 8. a liquid filter; 9. a preheater; 10. cyclopentanone receiving pot.
Detailed Description
The following describes the embodiments of the present invention further with reference to the drawings and examples. The following examples are only for more clearly illustrating the technical aspects of the present invention, and are not intended to limit the scope of the present invention.
Example 1
As shown in fig. 1, the refining system of the cyclopentanone-containing and propylene glycol methyl ether acetate recovery liquid of example 1 includes a pretreatment tank 1, a first rectifying tower 2, a second rectifying tower 3, a third rectifying tower 4, and a fourth rectifying tower 5;
the discharge port of the pretreatment kettle 1 is communicated with the first rectifying tower 2, and the bottom liquid phase outlet of the first rectifying tower 2 is communicated with the feed port of the second rectifying tower 3;
the top gas phase discharge port of the second rectifying tower 3 is communicated with the feed port of the third rectifying tower 4, and the bottom discharge port of the third rectifying tower 4 is communicated with a cyclopentanone receiving tank 10;
the bottom liquid phase outlet of the second rectifying tower 3 is communicated with the feed inlet of the fourth rectifying tower 5, and the top discharge outlet of the fourth rectifying tower 5 is communicated with the propylene glycol methyl ether acetate receiving tank 6 through a condenser.
A liquid filter 8 is communicated between the discharge port of the pretreatment kettle 1 and the feed port of the first rectifying tower 2.
Example 2
As shown in fig. 2, embodiment 2 further comprises an evaporator 7, wherein the feed inlet of the evaporator 7 is communicated with the heavy component discharge outlet at the bottom of the fourth rectifying tower 5, and the gas phase outlet of the evaporator 7 is communicated with the feed inlet of the fourth rectifying tower 5.
A liquid filter 8 and a preheater 9 are communicated between the discharge port of the pretreatment kettle 1 and the feed port of the first rectifying tower 2.
Based on example 2, the refining process of cyclopentanone and propylene glycol methyl ether acetate recovery liquid examples 3-5 are as follows:
the pH of the starting material for example 3 was 5.5 and the composition of the light black liquid was as follows:
| component (A) | Content (weight percent) |
| Low boiling point organic solvents such as acetone | 10 |
| Water and its preparation method | 1.2 |
| Cyclopentanone (CNG) | 50 |
| Propylene glycol methyl ether acetate | 35 |
| Resin and metal impurities | 3.8 |
In the embodiment 3, the first, the second, the third and the fourth are all normal pressure rectification;
the raw materials with the PH value of 5.5 enter a pre-treatment kettle, magnesium hydroxide is added, the mixture is stirred and neutralized until the PH value is 7.0 to 8.0, and the mixture enters the middle part of a first rectifying tower;
acetone is extracted from the top of the first rectifying tower, the temperature of the top of the tower is 56.5+/-2 ℃, the temperature of the bottom of the tower is 135-138 ℃, and the light component removing recovery liquid extracted from the bottom of the tower enters the middle part of the second rectifying tower;
feeding cyclopentanone-water fraction extracted from the top of the second rectifying tower into the middle part of the third rectifying tower, wherein the temperature of the top of the second rectifying tower is 110-125 ℃, the temperature of the bottom of the second rectifying tower is 135-140 ℃, and propylene glycol methyl ether acetate heavy components extracted from the bottom of the second rectifying tower are introduced into the middle part of the fourth rectifying tower;
the top of the third rectifying tower produces water with the temperature of 100-110 ℃ and the bottom temperature of 130-132 ℃ and the bottom produces cyclopentanone;
propylene glycol methyl ether acetate product is extracted from the top of the fourth rectifying tower, the extraction temperature is 146-147 ℃, the bottom temperature is 155-160 ℃, and the bottom heavy component is introduced into a scraper evaporator;
the gas phase material of the scraper evaporator enters the tower kettle of the fourth rectifying tower, the gas phase temperature is 155-160 ℃, the bottom of the evaporator discharges black viscous resin residual liquid, the resin residual liquid is properly cooled and barreled to be treated by professional solid waste factories, and the resin residual liquid contains 20-25% of dimethyl ether malonate.
The purity of cyclopentanone and malonic methyl ether acetate was detected by gas chromatography, and the product recovery = (mass of target component in product/mass of target component in raw material) ×100%. Examples 4 and 5 are the same as example 3.
The rectifying product obtained in the embodiment 3 is subjected to membrane filtration, the purity of the obtained cyclopentanone product is 99.91%, the purity of the malonic methyl ether acetate product is 99.93%, the recovery rate of the cyclopentanone is 96%, the recovery rate of the malonic methyl ether acetate is 88.6%, the chromaticity and other indexes of the product can reach electronic grade standards, the acetone amount is less, the water content is 0.5-1%, and the product is sold as fraction; the scraper evaporator is a black viscous liquid with a large amount of resin residual liquid (metal impurities are contained in the resin residual liquid).
Example 4
The pH of the raw material of example 4 was 7.1, a milky white liquid, the composition of which is shown in the following table:
| component (A) | Content (weight percent) |
| Low boiling point organic solvents such as acetone | 3 |
| Water and its preparation method | 0.7 |
| Cyclopentanone (CNG) | 55 |
| Propylene glycol methyl ether acetate | 40 |
| Resin and metal impurities | 1.3 |
Example 4 differs from examples 1 and 2 in that the first, second, third and fourth rectifying towers and the scraper evaporator are all vacuum rectification, the pressure is controlled between 0.09 and 0.095MPa,
the PH value of the raw material is 7.1, the liquid with milky appearance enters a pre-treatment kettle, activated carbon is added, stirred and filtered, and then enters the middle part of a first rectifying tower;
acetone is extracted from the top of the first rectifying tower, the temperature of the top of the tower is 10-12 ℃, the temperature of the bottom of the tower is 58-60 ℃, and the light component removing recovery liquid extracted from the bottom of the tower enters the middle part of the second rectifying tower;
cyclopentanone-water fraction extracted from the top of the second rectifying tower enters the middle part of the third rectifying tower, the temperature of the top of the second rectifying tower is 60-75 ℃, and the temperature of the bottom of the second rectifying tower is 85-88 ℃;
the top of the third rectifying tower produces water with the temperature of 50-60 ℃ and the bottom temperature of 82-86 ℃ and the bottom produces cyclopentanone; propylene glycol methyl ether acetate heavy components extracted from the bottom of the second rectifying tower are introduced into the middle part of the fourth rectifying tower;
propylene glycol methyl ether acetate products are extracted from the top of the fourth rectifying tower, the temperature is 96-97 ℃, the temperature of the bottom of the tower is 105-110 ℃, and the heavy components at the bottom of the tower enter a scraper evaporator;
the gas phase material of the scraper evaporator enters the tower kettle of the fourth rectifying tower, the gas phase temperature is 105-110 ℃, the bottom of the evaporator is used for removing resin residual liquid, and the resin residual liquid contains 8-12% of dimethyl ether malonate acetate.
The rectification product obtained in example 3 is subjected to membrane filtration to obtain cyclopentanone product with purity of 99.996%, malonic methyl ether acetate product with purity of 99.991%, cyclopentanone recovery of 96.4%, malonic methyl ether acetate recovery of 95%, chromaticity and other indexes of the product reaching electronic grade standards, and acetone water content of 10-20% is sold as fraction. The scraper evaporator has light yellow resin residual liquid and less resin residual liquid.
The recovery rate of cyclopentanone and malonate methyl ether acetate is slightly higher under the condition of reduced pressure rectification, in particular to the recovery rate of malonate methyl ether acetate.
Using example 1 as a purification system, the recovery rate of propylene glycol methyl ether acetate was slightly lower than that of example 2, and the recovery rate of cyclopentanone was similar.
Electronic grade standards for cyclopentanone and malonic methyl ether acetate:
the purity of cyclopentanone is more than or equal to 99.85%, the moisture is less than or equal to 500ppm, the acidity is less than or equal to 0.3, and the chromaticity is less than or equal to 20; the purity of the methyl malonate acetate is more than or equal to 99.85%, the moisture is less than or equal to 500ppm, the acidity is less than or equal to 0.3, and the chromaticity is less than or equal to 20.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that it will be apparent to those skilled in the art that several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the scope of the invention.
Claims (2)
1. A refining process of acetic ester recovery liquid containing cyclopentanone and propylene glycol methyl ether is characterized in that,
the main components of the recovery liquid are as follows by weight percent: 1.2% of water, 50% of cyclopentanone, 35% of propylene glycol methyl ether acetate, 3.8% of resin and metal impurities and 2% of acetone-containing low-boiling organic solvent;
the refining process comprises the following steps:
the raw materials enter a pre-treatment kettle, magnesium hydroxide is added, stirring is carried out to neutralize the raw materials to a pH value of 7.0-8.0, and the raw materials enter the middle part of a first rectifying tower;
acetone is extracted from the top of the first rectifying tower, the temperature of the top of the tower is 56.5+/-2 ℃, the temperature of the bottom of the tower is 135-138 ℃, and the light component removing recovery liquid extracted from the bottom of the tower enters the middle part of the second rectifying tower;
feeding cyclopentanone-water fraction extracted from the top of the second rectifying tower into the middle part of the third rectifying tower, wherein the temperature of the top of the second rectifying tower is 110-125 ℃, the temperature of the bottom of the second rectifying tower is 135-140 ℃, and propylene glycol methyl ether acetate heavy components extracted from the bottom of the second rectifying tower are introduced into the middle part of the fourth rectifying tower;
the top of the third rectifying tower produces water with the temperature of 100-110 ℃, the bottom of the third rectifying tower produces cyclopentanone with the temperature of 130-132 ℃;
propylene glycol methyl ether acetate products are extracted from the top of the fourth rectifying tower, the extraction temperature is 146-147 ℃, the bottom temperature is 155-160 ℃, and the bottom heavy components are introduced into a scraper evaporator;
the gas phase substances of the scraper evaporator enter a tower kettle of a fourth rectifying tower, the gas phase temperature is 155-160 ℃, and the bottom of the evaporator is discharged to form black sticky resin residual liquid;
the first rectifying tower, the second rectifying tower, the third rectifying tower and the fourth rectifying tower are all atmospheric rectification.
2. A refining process of acetic ester recovery liquid containing cyclopentanone and propylene glycol methyl ether is characterized in that,
the main components of the recovery liquid are as follows by weight percent: 0.7% of water, 55% of cyclopentanone, 40% of propylene glycol methyl ether acetate, 1.3% of resin and metal impurities and 0.7% of low-boiling-point organic solvent containing acetone;
the raw materials enter a pre-treatment kettle, activated carbon is added, stirred and filtered, and then enter the middle part of a first rectifying tower;
acetone is extracted from the top of the first rectifying tower, the temperature of the top of the tower is 10-12 ℃, the temperature of the bottom of the tower is 58-60 ℃, and the light component removing recovery liquid extracted from the bottom of the tower enters the middle part of the second rectifying tower;
cyclopentanone-water fraction extracted from the top of the second rectifying tower enters the middle part of the third rectifying tower, the temperature of the top of the second rectifying tower is 60-75 ℃, and the temperature of the bottom of the second rectifying tower is 85-88 ℃;
the top of the third rectifying tower produces water with the temperature of 50-60 ℃ and the bottom of the third rectifying tower with the temperature of 82-86 ℃, and the bottom produces cyclopentanone; propylene glycol methyl ether acetate heavy components extracted from the bottom of the second rectifying tower are introduced into the middle part of the fourth rectifying tower;
propylene glycol methyl ether acetate products are produced from the top of the fourth rectifying tower, the temperature is 96-97 ℃, the temperature at the bottom of the tower is 105-110 ℃, and heavy components at the bottom of the tower enter a scraper evaporator;
the gas phase substances of the scraper evaporator enter a tower kettle of a fourth rectifying tower, the gas phase temperature is 105-110 ℃, and resin residual liquid is discharged from the bottom of the evaporator;
the first rectifying tower, the second rectifying tower, the third rectifying tower, the fourth rectifying tower and the scraper evaporator are all subjected to reduced pressure rectification, and the pressure is 0.09-0.095 MPa.
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| CN112608235A (en) * | 2020-12-30 | 2021-04-06 | 深圳市环保科技集团有限公司 | PGMEA recovery method |
| CN112592276A (en) * | 2020-12-30 | 2021-04-02 | 深圳市环保科技集团有限公司 | PGMEA recovery method |
| CN113185390A (en) * | 2021-04-07 | 2021-07-30 | 厦门中坤化学有限公司 | Method for continuously separating propylene glycol methyl ether, cyclopentanone and propylene glycol methyl ether acetate |
| CN114262269B (en) * | 2021-12-30 | 2023-09-26 | 宁波南大光电材料有限公司 | Preparation method of propylene glycol methyl ether acetate |
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