CN102206156B - Method for comprehensive recycling of crude terephthalic acid (CTA) residue - Google Patents
Method for comprehensive recycling of crude terephthalic acid (CTA) residue Download PDFInfo
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- CN102206156B CN102206156B CN 201110056079 CN201110056079A CN102206156B CN 102206156 B CN102206156 B CN 102206156B CN 201110056079 CN201110056079 CN 201110056079 CN 201110056079 A CN201110056079 A CN 201110056079A CN 102206156 B CN102206156 B CN 102206156B
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- ester
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- dealcoholysis
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
Abstract
The invention discloses a method for comprehensive recycling of crude terephthalic acid (CTA) residue. The method comprises: esterifying the CTA residue to obtain mixed diisooctyl phthalate, isooctyl methyl benzoate and isooctyl benzoate; and separating to obtained mixed diisooctyl phthalate, which serves as a heavy component, and a mixture of isooctyl methyl benzoate and isooctyl benzoate, which serves as a light component, wherein the mixed diisooctyl phthalate is a plasticizer that can be used directly; and the mixture of isooctyl methyl benzoate and isooctyl benzoate can be formed into a mixture of (methyl) benzoic acid diethylene glycol ester by interesterification; the mixture of (methyl) benzoic acid diethylene glycol ester is also a high-performance plasticizer; and thus, all CTA residue is used for producing plastic products, the comprehensive recycling of the CTA residue is realized, and high economic benefit and social benefit are created.
Description
Technical field
The present invention relates to chemical field, relate to particularly in the PTA production process, the method for CTA residue as resources comprehensive utilization.
Background technology
Pure terephthalic acid (PTA) is one of main raw material(s) of polyester slice, polyster fibre, and domestic production capacity surpasses 1,200 ten thousand ton/years, and also has huge growth space.The Main By product that produces in the PTA production process is the CTA residue of p-Xylol chemical industry section, account for 3/1000ths to 5/1000ths of PTA output, main component in the residue is pure mixed phthalic acid, and tolyl acid, phenylformic acid etc., conventional method for innocent treatment are burning method and sewage treatment.These two kinds of methods all exist inconvenient operation, power consumption, investment greatly and have the shortcomings such as risk of secondary pollution.
Summary of the invention
The object of the present invention is to provide a kind of method of CTA residue as resources comprehensive utilization, to solve the above-mentioned problems in the prior art.
Technical scheme provided by the invention is as follows:
The CTA residue generally contains dibenzoic acid, adjacent dibenzoic acid, between dibenzoic acid, and tolyl acid, a kind of benzene mixed formic acid, the method of comprehensive utilization of resources of the present invention, first the esterification of CTA residue is become the pure mixed phthalic acid di-isooctyl, the different monooctyl ester of tolyl acid, the different monooctyl ester of phenylformic acid, and then separated, recombinating to divide is the pure mixed phthalic acid di-isooctyl, and light constituent is the mixture of the different monooctyl ester of tolyl acid and the different monooctyl ester of phenylformic acid, and restructuring divides directly to be used as softening agent, light constituent is made the mixture of tolyl acid binaryglycol ester and phenylformic acid binaryglycol ester again through transesterify, this mixture uses as softening agent.
The method of aforesaid comprehensive utilization of resources may further comprise the steps:
The first step CTA residue and excessive different monooctyl ester reaction preparation mix the different monooctyl ester of organism;
Second step reclaims the excessive isooctyl alcohol in the thick ester;
The 3rd step is by distillation, with the different monooctyl ester of tolyl acid with close the phthalic acid di-isooctyl separately;
The thick ester of the 4th step pure mixed phthalic acid di-isooctyl is refining;
The transesterify of the different monooctyl ester of the 5th step (methyl) phenylformic acid becomes (methyl) phenylformic acid binaryglycol ester;
The 6th step (methyl) phenylformic acid binaryglycol ester is refining.
In preferred embodiment of the present invention, the first step step is: CTA residue, catalyzer and excessive isooctyl alcohol are dropped in the reactor be warming up to 220-240 ℃, insulation reaction, backflow 8-12 hour, survey acid number, until acid number≤0.5mg KOH/g, termination reaction is produced the thick ester that obtains and is entered second step.
In preferred embodiment of the present invention, second step reclaims a minute normal pressure dealcoholysis, decompression dealcoholysis and three processes of water vapor stripping dealcoholysis, the normal pressure dealcoholysis namely steams the alcohol in the thick ester come at atmospheric pressure state, the decompression dealcoholysis refers to distill dealcoholysis under vacuum state, the dealcoholysis of water vapor stripping then is to utilize voltage divider principle that the alcohol of trace in the thick ester of decompression after the dealcoholysis is purified to greatest extent, to satisfy the requirement of end product quality.
In preferred embodiment of the present invention, the thick ester after the 3rd step dealcoholysis carries out underpressure distillation, first the different monooctyl ester of the lower tolyl acid of boiling point is separated, and enters next step transesterify operation; Next pure mixed phthalic acid and different monooctyl ester distills, enter next step refining step; Slag is got rid of outside the still at the bottom of last a small amount of still, does the solid waste harmless treatment.
In preferred embodiment of the present invention, the 4th step operation comprises five processes such as neutralization, washing, stripping, vacuum-drying, press filtration.
In preferred embodiment of the present invention, the 5th step added excessive glycol ether in the crude product of the different monooctyl ester of (methyl) phenylformic acid, carry out transesterify under the condition of normal pressure.
In preferred embodiment of the present invention, refining the comprising of the 6th step (methyl) phenylformic acid binaryglycol ester:
(1), polycondensation: owing to the excessive Diethylene Glycol of adding in the transesterify operation, so certainly exist a large amount of monoesters in the reactant, utilize the method for decompression polycondensation that unnecessary Diethylene Glycol is got rid of, make the thick ester of (methyl) phenylformic acid Diethylene Glycol.
(2), the thick ester of (methyl) phenylformic acid Diethylene Glycol is refining: this treating process is identical with thick ester treating process of the 4th step.
Reaction formula
1, the reaction formula of pure mixed phthalic acid di-isooctyl
In the formula: C8H17OH represents two isooctyl alcohol
HOOC-R-COOH represents phthalic acid (being terephthalic acid, phthalic acid, m-phthalic acid)
2, the reaction formula of the different monooctyl ester of tolyl acid
In the formula: HOOC-R-CH3 represent methylidene phenylformic acid
3, the reaction formula of the different monooctyl ester of phenylformic acid:
In the formula, R-COOH represents phenylformic acid
4, utilize the reaction formula of ester-interchange method preparation (methyl) phenylformic acid binaryglycol ester:
In the formula: R-COOH represents phenylformic acid and tolyl acid, and HO-R '-OH represents glycol ether.
In aforementioned each reaction, employed catalyzer is tetrabutyl titanate.
Seen from the above description, the present invention becomes the pure mixed phthalic acid di-isooctyl with the esterification of CTA residue elder generation, the different monooctyl ester of tolyl acid, the different monooctyl ester of phenylformic acid, and then separated, recombinate to divide and be the pure mixed phthalic acid di-isooctyl, light constituent is the mixture of the different monooctyl ester of tolyl acid and the different monooctyl ester of phenylformic acid, the former is a kind of softening agent that can directly use, and the latter makes the mixture of (methyl) phenylformic acid binaryglycol ester through transesterify, and this mixture also is a kind of softening agent of excellent property, like this, the CTA residue is realized comprehensive utilization of resources all for the production of the softening agent product, has very high economic benefit and social benefit.
Embodiment
Embodiment one
The preparation of the first step CTA residue mixes the different monooctyl ester of organism
To be warming up to 225 ℃ in CTA residue 4kg, catalyzer and the isooctyl alcohol 9.1kg input reactor, insulation reaction refluxed about 10 hours, surveyed acid number, until acid number≤0.5mg koh/g, termination reaction is produced the thick ester that obtains and entered subsequent processing.
The second step dealcoholysis
Isooctyl alcohol in the thick ester is reclaimed, in lower batch production, use, reclaim a minute normal pressure dealcoholysis, decompression dealcoholysis and three processes of water vapor stripping dealcoholysis.The normal pressure dealcoholysis namely steams the alcohol in the thick ester come at atmospheric pressure state, the decompression dealcoholysis refers to distill dealcoholysis under vacuum state, the dealcoholysis of water vapor stripping then is to utilize voltage divider principle that the alcohol of trace in the thick ester of decompression after the dealcoholysis is purified to greatest extent, to satisfy the requirement of end product quality.
The distillation of the 3rd step
Thick ester after the dealcoholysis is carried out underpressure distillation, first the different monooctyl ester of the lower tolyl acid of boiling point is separated, enter next step transesterify operation.Next pure mixed phthalic acid and different monooctyl ester distills, enter next step refining step.Slag is got rid of outside the still at the bottom of last a small amount of still, does the solid waste harmless treatment.
The 4th step, thick ester was refining
The dimixo-octyl phthalate (DOP) of this operation and routine or the thick ester treating process of terephthalic acid di-isooctyl (DOTP) are identical, namely pass through five processes such as neutralization, washing, stripping, vacuum-drying, press filtration, these are prior art, no longer describe in detail.
The transesterify of the different monooctyl ester of the 5th step (methyl) phenylformic acid
In the crude mixture of the different monooctyl ester of tolyl acid and the different monooctyl ester of phenylformic acid, add excessive glycol ether (excessive approximately 20%), carry out transesterify under the condition of normal pressure, purpose is that the different monooctyl ester of (methyl) phenylformic acid is converted into softening agent (methyl) phenylformic acid binaryglycol ester with low cost, excellent property.Judge that reaction end can be by calculating the amount of the isooctyl alcohol that transesterify should generate.
Making with extra care of the 6th step (methyl) phenylformic acid binaryglycol ester
1, polycondensation
Owing to add excessive Diethylene Glycol in the transesterify operation, so certainly exist a large amount of monoesters in the reactant, the present invention utilizes the method for decompression polycondensation that unnecessary Diethylene Glycol is got rid of, and makes the thick ester of (methyl) phenylformic acid Diethylene Glycol.
2, the thick ester of (methyl) phenylformic acid Diethylene Glycol is refining
This treating process is identical with the thick ester treating process of DOP, no longer describes in detail here.The product made from extra care out is exactly two (methyl) phenylformic acid binaryglycol ester of product of the present invention.
Embodiment two
Basic identical with embodiment one, difference is, in the first step be: CTA residue 4kg, catalyzer and isooctyl alcohol 9.45kg are dropped in the reactor be warming up to 240 ℃, insulation reaction, refluxed about 8 hours, and surveyed acid number, until acid number≤0.5mg koh/g, termination reaction is produced the thick ester that obtains and is entered subsequent processing.
Embodiment three
Basic identical with embodiment one, difference is, in the first step be: CTA residue 4kg, catalyzer and isooctyl alcohol 9.8kg are dropped in the reactor be warming up to 220 ℃, insulation reaction, refluxed about 12 hours, and surveyed acid number, until acid number≤0.5mg koh/g, termination reaction is produced the thick ester that obtains and is entered subsequent processing.
Embodiment four
Basic identical with embodiment one, difference is, in the first step be: CTA residue 4kg, catalyzer and isooctyl alcohol 10.1kg are dropped in the reactor be warming up to 225 ℃, insulation reaction, refluxed about 10 hours, and surveyed acid number, until acid number≤0.5mg koh/g, termination reaction is produced the thick ester that obtains and is entered subsequent processing.
Embodiment five
Basic identical with embodiment one, difference is, in the first step be: CTA residue 4kg, catalyzer and isooctyl alcohol 10.5kg are dropped in the reactor be warming up to 225 ℃, insulation reaction, refluxed about 10 hours, and surveyed acid number, until acid number≤0.5mg koh/g, termination reaction is produced the thick ester that obtains and is entered subsequent processing.
Embodiment
| CTA residue (dry measure) kg | Isooctyl alcohol kg | Catalyzer accounts for CTA residue mass ratio | |
| Embodiment one | ?4 | 9.1 | ?2/1000 |
| Embodiment two | ?4 | 9.45 | ?2/1000 |
| Embodiment three | ?4 | 9.8 | ?2/1000 |
| Embodiment four | ?4 | 10.1 | ?2/1000 |
| Embodiment five | ?4 | 10.5 | ?2/1000 |
The result:
1, CTA residue and isocaprylic acid esterification reaction was finished in 16 hours;
2, (methyl) phenylformic acid isooctyl alcohol ester and Diethylene Glycol transesterify were finished in 8 hours, and the ester exchange offspring that contains monoesters was finished polycondensation at 4 hours, generated the finished product (methyl) phenylformic acid binaryglycol ester.
3, through esterification, transesterify, two softening agent products after the operation such as refining is processed, namely pure mixed phthalic acid di-isooctyl (Project Product one) and the product quality indicator of mixing (methyl) phenylformic acid binaryglycol ester (Project Product two) all meet or exceed the product quality indicator of conventional plasticizer DOP.
The product quality indicator table look-up
| Project | Project Product one | Project Product two |
| Outward appearance | The yellow transparent oily liquids | Faint yellow transparent oily liquid |
| Relative density (20 ℃) | 0.983±0.003 | 1.17±0.01 |
| Ester content % 〉= | 99 | 99 |
| Weight loss on heating %≤ | 0.2 | 0.3 |
| Volume resistivity/20 ℃, Ω cm | 1.0*10 11 | 2.0*10 11 |
| Flash-point/℃ (open cup?) 〉= | 195 | 205 |
| Acid number/mgKOH≤ | 0.06 | 0.1 |
Above-mentioned only is specific embodiments of the invention, but design concept of the present invention is not limited to this, allly utilizes this design that the present invention is carried out the change of unsubstantiality, all should belong to the behavior of invading protection domain of the present invention.
Claims (8)
1. the method for CTA residue as resources comprehensive utilization is characterized in that: may further comprise the steps:
The first step CTA residue and excessive isooctyl alcohol reaction preparation mix the different monooctyl ester of organism;
Second step reclaims the excessive isooctyl alcohol in the thick ester;
The 3rd step is by distillation, with the different monooctyl ester of tolyl acid, the different monooctyl ester of phenylformic acid and pure mixed phthalic acid di-isooctyl separately;
The thick ester of the 4th step pure mixed phthalic acid di-isooctyl is refining;
The different monooctyl ester of the 5th ground beetle yl benzoic acid and the different monooctyl ester of phenylformic acid become tolyl acid binaryglycol ester and phenylformic acid binaryglycol ester through transesterify;
The 6th ground beetle yl benzoic acid binaryglycol ester and phenylformic acid binaryglycol ester are refining.
2. the method for CTA residue as resources as claimed in claim 1 comprehensive utilization, it is characterized in that: the first step step is:
To be warming up to 220-240 ℃ in CTA residue, catalyzer and the excessive isooctyl alcohol input reactor, insulation reaction, backflow 8-12 hour, survey acid number, until acid number≤0.5mg KOH/g, termination reaction is produced the thick ester that obtains and is entered second step.
3. the method for CTA residue as resources as claimed in claim 1 comprehensive utilization, it is characterized in that: second step comprises normal pressure dealcoholysis, decompression dealcoholysis and three processes of water vapor stripping dealcoholysis, the normal pressure dealcoholysis namely steams the alcohol in the thick ester come at atmospheric pressure state, the decompression dealcoholysis refers to distill dealcoholysis under vacuum state, and the dealcoholysis of water vapor stripping then is to utilize voltage divider principle that the alcohol of trace in the thick ester of decompression after the dealcoholysis is purified to greatest extent.
4. the method for CTA residue as resources as claimed in claim 1 comprehensive utilization, it is characterized in that: in the 3rd step, thick ester after the dealcoholysis is carried out underpressure distillation, first the different monooctyl ester of the lower tolyl acid of boiling point is separated, enter next step transesterify operation; Next the pure mixed phthalic acid di-isooctyl is distilled, enter next step refining step; Slag is got rid of outside the still at the bottom of last a small amount of still, does the solid waste harmless treatment.
5. the method for CTA residue as resources as claimed in claim 1 comprehensive utilization, it is characterized in that: the 4th step comprised neutralization, washing, stripping, vacuum-drying, five processes of press filtration.
6. the method for CTA residue as resources as claimed in claim 1 comprehensive utilization, it is characterized in that: the 5th step added excessive glycol ether in the crude product of the different monooctyl ester of tolyl acid and the different monooctyl ester of phenylformic acid, carry out transesterify under the condition of normal pressure.
7. the method for comprehensive utilization of resources as claimed in claim 1, it is characterized in that: the 6th ground beetle yl benzoic acid binaryglycol ester and the refining of phenylformic acid binaryglycol ester comprise:
(1), polycondensation: utilize the method for decompression polycondensation that unnecessary Diethylene Glycol is got rid of, make the thick ester of tolyl acid Diethylene Glycol and the thick ester of phenylformic acid Diethylene Glycol;
(2), the thick ester of tolyl acid Diethylene Glycol and the thick ester of phenylformic acid Diethylene Glycol is refining: this treating process is identical with thick ester treating process of the 4th step.
8. the method for CTA residue as resources as claimed in claim 2 comprehensive utilization, it is characterized in that: employed catalyzer is tetrabutyl titanate.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110056079 CN102206156B (en) | 2011-03-08 | 2011-03-08 | Method for comprehensive recycling of crude terephthalic acid (CTA) residue |
| PCT/CN2012/071753 WO2012119520A1 (en) | 2011-03-08 | 2012-02-29 | Method for preparing plasticizer with cta residue |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201110056079 CN102206156B (en) | 2011-03-08 | 2011-03-08 | Method for comprehensive recycling of crude terephthalic acid (CTA) residue |
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| CN102206156A CN102206156A (en) | 2011-10-05 |
| CN102206156B true CN102206156B (en) | 2013-04-03 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206156B (en) * | 2011-03-08 | 2013-04-03 | 福建天大化工有限公司 | Method for comprehensive recycling of crude terephthalic acid (CTA) residue |
| CN104650332B (en) * | 2014-12-09 | 2017-01-11 | 福建天大化工有限公司 | Preparation method of resin intermediate--phthalic acid diethylene glycol polyester |
| RU2612302C1 (en) * | 2015-10-14 | 2017-03-06 | Общество с ограниченной ответственностью "ХИМТЕХ-ИНЖИНИРИНГ" | Method for dioctyl terephthalate production |
| RU2666739C1 (en) * | 2017-06-15 | 2018-09-12 | Общество с Ограниченной Ответственностью "НПЦ Башкомпаунд" | Method for obtaining a dioxylterephthalate plastifficator from 2-ethylhexanol and technical terephthalic acid distillation residue |
| CN109776313B (en) * | 2019-01-28 | 2023-01-13 | 上海炼升化工股份有限公司 | Mixed ester derived from PTA residue and synthesis method thereof |
| RU2708641C1 (en) * | 2019-07-22 | 2019-12-10 | Сергей Николаевич Лакеев | Method of producing terephthalate and benzoate plasticizers from by-products |
| CN111205182B (en) * | 2020-02-13 | 2020-10-27 | 厦门大学 | Method for preparing mixed plasticizer and environment-friendly plasticizer by using PTA residues |
| CN112851503A (en) * | 2021-01-20 | 2021-05-28 | 江苏福昌环保科技集团有限公司 | Comprehensive utilization process of PTA oxidation residues |
| CN112876357A (en) * | 2021-01-20 | 2021-06-01 | 江苏福昌环保科技集团有限公司 | Production process for producing plasticizer from PTA oxidation residues |
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| US4284793A (en) * | 1977-11-30 | 1981-08-18 | Chisso Corporation | Method for producing plasticizers |
| CN1228411A (en) * | 1998-03-10 | 1999-09-15 | 辽阳市石油化工研究所 | Method for preparing mixed ester terephthalate |
| CN1611481A (en) * | 2003-10-31 | 2005-05-04 | 中国石油化工股份有限公司 | Terephthalic acid and water scrubbing residue recovery and utilization method |
| CN101139293A (en) * | 2007-08-17 | 2008-03-12 | 郭立耀 | Method for producing dioctyl terephthalate |
| CN101811970A (en) * | 2010-05-05 | 2010-08-25 | 江苏强林生物能源有限公司 | Production method of dioctyl terephthalate composite plasticizer |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206156B (en) * | 2011-03-08 | 2013-04-03 | 福建天大化工有限公司 | Method for comprehensive recycling of crude terephthalic acid (CTA) residue |
-
2011
- 2011-03-08 CN CN 201110056079 patent/CN102206156B/en active Active
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2012
- 2012-02-29 WO PCT/CN2012/071753 patent/WO2012119520A1/en active Application Filing
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| US4284793A (en) * | 1977-11-30 | 1981-08-18 | Chisso Corporation | Method for producing plasticizers |
| CN1228411A (en) * | 1998-03-10 | 1999-09-15 | 辽阳市石油化工研究所 | Method for preparing mixed ester terephthalate |
| CN1611481A (en) * | 2003-10-31 | 2005-05-04 | 中国石油化工股份有限公司 | Terephthalic acid and water scrubbing residue recovery and utilization method |
| CN101139293A (en) * | 2007-08-17 | 2008-03-12 | 郭立耀 | Method for producing dioctyl terephthalate |
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| WO2012119520A1 (en) | 2012-09-13 |
| CN102206156A (en) | 2011-10-05 |
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