CN105315158A - Combined process method for preparing naphthenic base dioctyl phthalate dibasic ester - Google Patents
Combined process method for preparing naphthenic base dioctyl phthalate dibasic ester Download PDFInfo
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- CN105315158A CN105315158A CN201510746947.1A CN201510746947A CN105315158A CN 105315158 A CN105315158 A CN 105315158A CN 201510746947 A CN201510746947 A CN 201510746947A CN 105315158 A CN105315158 A CN 105315158A
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- C07—ORGANIC CHEMISTRY
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
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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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Abstract
The invention provides a combined process method for preparing naphthenic base dioctyl phthalate dibasic ester. The combined process method is characterized by including the following steps: (1) placing esterification raw materials in an esterification unit for esterification, so as to obtain an esterified product with the acid value lower than 0.5 mg KOH/g; then washing in a washing kettle to remove an esterification catalyst, and performing dewatering and drying on an organic phase obtained after washing; (2), performing hydrogenation reaction on an organic phase dried product after washing obtained in step (1) in a hydrogenation reactor, wherein the hydrogenation technology condition is controlled as follows: the reaction temperature is 80-250 DEG C, the reaction pressure is 3.0-17.0 MPa, the hydrogen ester molar ratio is 10-300, and the liquid space velocity is 0.1-0.5 h<-1>; (3) after the hydrogenation reaction is finished, performing refining treatment on the product obtained after hydrogenation reaction to obtain the naphthenic base dioctyl phthalate dibasic ester product. The process method provided by the invention is simplified in technological process, and device investment, power consumption and the like are remarkably reduced.
Description
Technical field
The present invention relates to softening agent preparation field, be specifically related to phthalic anhydride esterification and prepare the combined technique that phthalic acid dibasic ester and phthalic acid dibasic ester Hydrogenation combine for 1,2-cyclohexane cyclohexanedimethanodibasic dibasic ester technique.
Background technology
Phthalic acid dibasic ester is used widely in CONTINENTAL AREA OF CHINA as softening agent, wherein based on dimixo-octyl phthalate (DOP or DEHP), dibutyl phthalate (DBP).Well-known reason, this kind of softening agent with aromatic ring has certain carcinogenic, environmental risk.Because this kind of softening agent output is large, manufacturer is numerous, for reply environmental protection policy, regulation day by day harsh, need to upgrade to such softening agent.One of preferred plan carries out hydrogenation for such softening agent, and in molecule, aromatic ring is completely saturated is cycloalkyl, and most is representational is CN101242895A, US6284917, US7361714, CN101406840 etc.Existing patent for raw material, adopts different hydrogenation process conditions to obtain corresponding cycloalkyl product with phthalic acid dibasic ester.CN101417950 discloses the method that one prepares 1,2-cyclohexane cyclohexanedimethanodibasic dibasic ester, its reaction conditions: temperature of reaction 100 ~ 250 DEG C, reaction pressure 3.0 ~ 12.0MPa, hydrogen ester mol ratio 50 ~ 450, liquid air speed 0.1 ~ 2.5h
-1.
Need in phthalic acid dibasic ester preparation process to carry out a series of refinement treatment after esterification terminates, and after hydrogenation process, there is the side reactions such as cracking in phthalic acid dibasic ester and corresponding cycloalkyl product heats process, generate corresponding acid, acid anhydrides, alcohol, also need to carry out refinement treatment and could meet the requirement of softening agent index of correlation, therefore, overall craft is complicated, and energy consumption is high.
Summary of the invention
For above-mentioned technical problem, the invention provides a kind of combined technique preparing cycloalkyl cyclohexanedimethanodibasic dibasic ester.Present invention process method, esterification after product, does not need to carry out de-impurity treatment, but product is after catalyzer is removed in washing, directly enters hydrogenation reaction section.
The present invention is a kind of combined technique preparing cycloalkyl cyclohexanedimethanodibasic dibasic ester, and this processing method, comprises the steps:
(1) esterification feed is inserted esterification unit and carry out esterification, obtain the esterification products of acid number lower than 0.5mgKOH/g, then enter washing kettle washing to remove esterifying catalyst, the organic phase that washing obtains is through dehydrating;
(2) the dry thing of washing organic phase that step (1) obtains enters in hydrogenator and carries out hydrogenation reaction, controls hydrogenation process conditions: temperature of reaction 80 ~ 250 DEG C, reaction pressure 3.0 ~ 17.0MPa, hydrogen ester mol ratio 10 ~ 300, liquid air speed 0.1 ~ 0.5h
-1;
(3), after hydrogenation reaction terminates, hydrogenation reaction product enters refinement treatment and obtains cycloalkyl cyclohexanedimethanodibasic dibasic ester products.
In the above-mentioned processing method of the present invention, described cyclohexane cyclohexanedimethanodibasic dibasic ester comprises cyclohexane cyclohexanedimethanodibasic dibutylester, cyclohexane cyclohexanedimethanodibasic di-n-octyl, cyclohexane cyclohexanedimethanodibasic di-isooctyl, cyclohexane cyclohexanedimethanodibasic two ester in the ninth of the ten Heavenly Stems, cyclohexane cyclohexanedimethanodibasic didecyl.
State on the invention in processing method, in described hydrogenator, Primary Catalysts top loading protective material, avoids the titanium compound carried secretly in esterification logistics to cover noble metal catalyst surface, reduces catalyst activity; Described protective material using nickel as active ingredient, elemental nickel content 0.1wt% ~ 5wt%.
In the above-mentioned processing method of the present invention, the catalyzer that described esterification reaction process adopts is non-acid catalyst, preferred titanium isopropylate, tetrabutyl titanate.
In the above-mentioned processing method of the present invention, the hydrogenation catalyst adopted in step (2) is noble metal catalyst or nickel catalyzator, described noble metal catalyst is the aromatic hydrocarbon saturation catalyst containing precious metals such as Pt, Pd, Ru, Rh, Hydrobon catalyst disclosed in CN101850265.Nickel catalyzator is the catalyzer of dipping nickel salt reduction.
In the above-mentioned processing method of the present invention, in step (3), described refinement treatment step is preferably: hydrogenation reaction product is carried out dealcoholation treatment and is less than 1wt% through high-pressure separator, light pressure separator, thick dealcoholize column to alcohol content successively, and then after alkali cleaning still, washing kettle carry out alkali cleaning, washing, through the dealcoholysis of stripping tower coupling vacuum stripping with remove remaining alcohol and low-boiling by-products, then enter drying tower, dehydrate to after qualified, enter bleaching tower to decolour, obtain product.
Combined technique provided by the invention, 1) technological process is with phthalic anhydride, alcohol for raw material, and after esterification, washing, enter hydrogenation unit, hydrogenation products, through thick dealcoholysis, alkali cleaning, washing, drying, decolouring, obtains product cyclohexyldicarboxylic acids dibasic ester.With existing technics comparing, simplify the operation links such as the dealcoholysis after esterification, alkali cleaning, stripping dealcoholysis, drying, decolouring, technical process simplifies, and plant investment, energy consumption etc. obviously reduce.
2) esterification process because of alcohol content excessive, effectively can suppress the temperature rise of hydrogenation process reactor bed, thus reduce the pyrolysis side reaction of raw material and product, improve product yield, reduce post-processing difficulty;
3) stripping dealcoholysis process overhead product is capable of circulation to esterification section after dehydration, avoids by-product and reclaims problem.
4) in this process integration, hydrogenation section and conventional plasticizers production process be combined with each other, and can switch between the ester containing aromatic ring and cycloalkyl ester two kinds of products, and when namely producing the ester product containing aromatic ring, logistics can realize without hydrogenation unit.When preparing cyclohexyldicarboxylic acids ester, esterification products is entered hydrogenation unit, under certain reaction conditions, aromatic ring is all saturated, and hydrogenation products can obtain cyclohexyldicarboxylic acids dibasic ester through operating units such as thick dealcoholysis, alkali cleaning, washing, stripping dealcoholysis, drying, decolourings again.
Accompanying drawing explanation
The joint process schematic diagram of cyclohexane cyclohexanedimethanodibasic ester is prepared in Fig. 1 embodiment of the present invention.
1-esterification feed in figure; 2-esterification unit; 3-washing kettle; 4-pump; 6-hydrogenator; 7-high-pressure separator; 8-light pressure separator; The thick dealcoholize column of 9-; 10-alkali cleaning still; 11-washing kettle; 12-stripping tower; 13-drying tower; 14-decolours still; 15-filtering unit; 16-product
Embodiment
Below in conjunction with drawings and Examples, the combined technique that the present invention prepares cycloalkyl cyclohexanedimethanodibasic dibasic ester is described further.
As shown in Figure 1, esterification feed 1 (phthalic anhydride, alkyl alcohol mixture and catalyzer) enter esterification unit 2, after esterification, obtain the logistics of acid number lower than 0.5mgKOH/g, enter washing kettle 3, remove esterifying catalyst, washing organic phase is through dehydrating, hydrogenator 6 is pumped into after pump 4, hydrogenation reaction product is through high-pressure separator 7, light pressure separator 8, thick dealcoholize column 9, after dealcoholysis to alcohol content is less than 1%, through alkali cleaning still 10, washing kettle 11, product enters stripping tower 12 dealcoholysis, product after dealcoholysis enters drying tower 13 imurity-removal water, decolour through decolouring still 14 again, finally enter filtering unit 15 filtering solid contaminants, obtain qualified product 16.
When producing phthalate product, esterification feed 1 (phthalic anhydride, alkyl alcohol mixture and catalyzer) enters esterification unit 2, after esterification, obtain the logistics of acid number lower than 0.5mgKOH/g, enter washing kettle, remove esterifying catalyst, washing organic phase enters thick dealcoholize column 9 through pipeline, after dealcoholysis to alcohol content is less than 1%, through alkali cleaning still 10, washing kettle 11, product enters stripping tower 12 dealcoholysis, dealcoholysis logistics enters drying tower 13 imurity-removal water, the still 14 that enters to decolour decolours, and enters filtering unit 15 filtering solid contaminants, obtains qualified product 16.
Below by embodiment, further illustrate the present invention program and effect.
For the purpose of cycloalkyl dicarboxylic acid esters during product, raw material phthalic anhydride, isooctyl alcohol esterification, product acid number is lower than 0.5mgKOH/g, after washing, enter hydrogenator, enter hydrogenator material composition and flow be: dimixo-octyl phthalate 10.0t/h, isooctyl alcohol 0.5t/h, free phthalic acid is ignored.Catalyst protective agent and hydrogenation agent grading loading in hydrogenator, protective material is Ni/Al
2o
3, elemental nickel content 2%, hydrogenation catalyst is Ru/Pd catalyzer, main technologic parameters: temperature of reaction: 150 DEG C, hydrogen partial pressure: 15MPa, volume space velocity: 0.3h
-1, hydrogen-oil ratio: 600.Hydrogenation logistics enters high score and is separated gas phase and liquid phase, and liquid product mainly forms and flow: cyclohexane cyclohexanedimethanodibasic di-isooctyl 9.95t/h; Isooctyl alcohol 0.51t/h; The different monooctyl ester 0.03t/h of cyclohexanecarboxylic acid.Liquid phase enters low point and is separated after a small amount of gas by-product, and liquid phase enters to reduce pressure dealcoholize column, and dealcoholysis is less than 1% to isooctyl alcohol content, enters alkali cleaning still, and alkali lye is Na
2cO
3solution, prevailing operating conditions is: temperature of reaction 90 DEG C, Na
2cO
3strength of solution 3%, liquid oil quality compare 1:10, enter washing kettle, washing conditions is: temperature 90 DEG C, water oil quality compare 2:10, after washing, enter stripping tower dealcoholysis, stripping tower prevailing operating conditions: material temperature 140 DEG C, column bottom temperature: 155 DEG C, tower top 135 DEG C, quality of gasoline ratio: 1:20, stripper top product is through being separated, organic phase mixes with thick dealcoholysis overhead stream, enter esterifying kettle, stripping tower bottom overhead product enters drying tower, drying tower prevailing operating conditions: material temperature 150 DEG C, dewatered product enters to decolour after still decolours and filters, and obtains product.Product physico-chemical property is as follows:
| Project | Index |
| State | Transparent, without visible foreign |
| Cyclohexane cyclohexanedimethanodibasic di-isooctyl content, % >= | 99.0 |
| Colourity, (platinum-cobalt) number≤ | 40 |
| Density (20 DEG C), kg/m 3 | 954～956 |
| Acidity (in phthalic acid), %≤ | 0.015 |
| Water-content, %≤ | 0.1 |
| Flash-point, DEG C >= | 192 |
For the purpose of phthalic acid dibasic ester during product, after raw material phthalic anhydride, isooctyl alcohol esterification, directly enter thick dealcoholize column, last handling process is the same.
As can be seen from above-described embodiment, feature of the present invention is that esterification material does not need to refine, namely the Ester that there is part isooctyl alcohol and incomplete double esterification is allowed in material, eliminate the refining stage of esterification products, example is synthesized with DOP, typical case's refining stage comprises: the operation workshop sections such as thick dealcoholysis, alkali cleaning, washing, smart dealcoholysis, drying, decolouring, therefore the present invention greatly reduces the total facility investment of device, process cost and sewage disposal expense.Also solve the process problem of stripping tower top isooctyl alcohol-cyclohexane cyclohexanedimethanodibasic ester mixture simultaneously.
Claims (6)
1. prepare a combined technique for cycloalkyl cyclohexanedimethanodibasic dibasic ester, it is characterized in that, comprise the steps:
(1) esterification feed is inserted esterification unit and carry out esterification, obtain the esterification products of acid number lower than 0.5mgKOH/g, then enter washing kettle washing to remove esterifying catalyst, the organic phase that washing obtains is through dehydrating;
(2) the dry thing of washing organic phase that step (1) obtains enters in hydrogenator and carries out hydrogenation reaction, controls hydrogenation process conditions: temperature of reaction 80 ~ 250 DEG C, reaction pressure 3.0 ~ 17.0MPa, hydrogen ester mol ratio 10 ~ 300, liquid air speed 0.1 ~ 0.5h
-1;
(3), after hydrogenation reaction terminates, hydrogenation reaction product enters refinement treatment and obtains cycloalkyl cyclohexanedimethanodibasic dibasic ester products.
2. combined technique according to claim 1, it is characterized in that, described cycloalkyl cyclohexanedimethanodibasic dibasic ester comprises cyclohexane cyclohexanedimethanodibasic dibutylester, cyclohexane cyclohexanedimethanodibasic di-n-octyl, cyclohexane cyclohexanedimethanodibasic di-isooctyl, cyclohexane cyclohexanedimethanodibasic two ester in the ninth of the ten Heavenly Stems, cyclohexane cyclohexanedimethanodibasic didecyl.
3. combined technique according to claim 1, is characterized in that, in described hydrogenator, adopts protective material and Primary Catalysts grading loading, described protective material using nickel as active ingredient, elemental nickel content 0.1wt% ~ 5wt%.
4. combined technique according to claim 1, is characterized in that, the catalyzer that described esterification reaction process adopts is titanium isopropylate, tetrabutyl titanate.
5. combined technique according to claim 1, it is characterized in that, the hydrogenation catalyst adopted in step (2) is noble metal catalyst or nickel catalyzator, and described noble metal catalyst is the aromatic hydrocarbon saturation catalyst containing Pt, Pd, Ru, Rh precious metal; Nickel catalyzator is the catalyzer of dipping nickel salt reduction.
6. combined technique according to claim 1, it is characterized in that, refinement treatment in step (3) is: carry out dealcoholation treatment and be less than 1wt% through high-pressure separator, light pressure separator, thick dealcoholize column to alcohol content successively, and then after alkali cleaning still, washing kettle carry out alkali cleaning, washing, through the dealcoholysis of stripping tower coupling vacuum stripping and the alcohol and the low-boiling by-products that remove remnants, then enter drying tower, after dehydration is extremely qualified, enter bleaching tower to decolour, obtain product.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106748774A (en) * | 2016-11-13 | 2017-05-31 | 中海油天津化工研究设计院有限公司 | A kind of process for purification of cyclohexane cyclohexanedimethanodibasic ester plasticizer |
| CN110437067A (en) * | 2018-05-02 | 2019-11-12 | 湖南长岭石化科技开发有限公司 | The method for preparing cyclohexane cyclohexanedimethanodibasic ester |
| CN110483295A (en) * | 2019-09-09 | 2019-11-22 | 安徽香枫新材料股份有限公司 | A kind of DINP catalytic hydrogenation prepares the refining methd of DINCH |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1285815A (en) * | 1997-12-19 | 2001-02-28 | 巴斯福股份公司 | Method for hydrogenating benzene polycarboxylic acids or derivatives thereof by using catalyst containing macropores |
| CN101417950A (en) * | 2008-10-27 | 2009-04-29 | 中国科学院大连化学物理研究所 | Method for preparing 1,2-cyclohexane cyclohexanedimethanol dibasic ester |
| CN102153469A (en) * | 2011-02-28 | 2011-08-17 | 南亚塑胶工业股份有限公司 | Method for preparing cyclohexane carboxylic ester from benzene polycarboxylic ester |
| CN103687832A (en) * | 2011-07-29 | 2014-03-26 | 伊士曼化工公司 | Integrated process for the preparation of 1,4-cyclohexanedimethanol from terephtalic acid |
-
2015
- 2015-11-05 CN CN201510746947.1A patent/CN105315158B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1285815A (en) * | 1997-12-19 | 2001-02-28 | 巴斯福股份公司 | Method for hydrogenating benzene polycarboxylic acids or derivatives thereof by using catalyst containing macropores |
| CN101417950A (en) * | 2008-10-27 | 2009-04-29 | 中国科学院大连化学物理研究所 | Method for preparing 1,2-cyclohexane cyclohexanedimethanol dibasic ester |
| CN102153469A (en) * | 2011-02-28 | 2011-08-17 | 南亚塑胶工业股份有限公司 | Method for preparing cyclohexane carboxylic ester from benzene polycarboxylic ester |
| CN103687832A (en) * | 2011-07-29 | 2014-03-26 | 伊士曼化工公司 | Integrated process for the preparation of 1,4-cyclohexanedimethanol from terephtalic acid |
Non-Patent Citations (1)
| Title |
|---|
| 欧远辉等: "环保增塑剂环己烷-１,２- 二甲酸二异辛酯的合成与应用", 《中国塑料》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106748774A (en) * | 2016-11-13 | 2017-05-31 | 中海油天津化工研究设计院有限公司 | A kind of process for purification of cyclohexane cyclohexanedimethanodibasic ester plasticizer |
| CN106748774B (en) * | 2016-11-13 | 2020-07-24 | 中海油天津化工研究设计院有限公司 | Refining method of cyclohexane diformate plasticizer |
| CN110437067A (en) * | 2018-05-02 | 2019-11-12 | 湖南长岭石化科技开发有限公司 | The method for preparing cyclohexane cyclohexanedimethanodibasic ester |
| CN110483295A (en) * | 2019-09-09 | 2019-11-22 | 安徽香枫新材料股份有限公司 | A kind of DINP catalytic hydrogenation prepares the refining methd of DINCH |
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