CN102898309A - Method for preparing 1, 2-cyclohexane dioctyl phthalate diisooctyl by hydrogenation - Google Patents
Method for preparing 1, 2-cyclohexane dioctyl phthalate diisooctyl by hydrogenation Download PDFInfo
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- CN102898309A CN102898309A CN201210453430XA CN201210453430A CN102898309A CN 102898309 A CN102898309 A CN 102898309A CN 201210453430X A CN201210453430X A CN 201210453430XA CN 201210453430 A CN201210453430 A CN 201210453430A CN 102898309 A CN102898309 A CN 102898309A
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Abstract
The invention relates to a method for preparing 1, 2-cyclohexane dioctyl phthalate diisooctyl by hydrogenation. The method is characterized in that a reaction system consists of the components of: phthalic acid diisooctyl, hydrogen and catalyst; and the reaction condition is that the reaction temperature is 100-250 DEG C, the reaction pressure is 5-18MPa, the volume ratio between H2 and the phthalic acid diisooctyl is (2000-200):1, and the liquid air space velocity of the phthalic acid diisooctyl is 0.1-2.5h-1. The catalyst takes Al2O3 as a carrier, an active component is selected from one or a plurality out of Ru, Pd and Ni, and the bearing capacity of the active component is 1-3% of the weight of the catalyst; and the catalyst is subjected to in-situ reduction by the H2 and is activated before use.
Description
Technical field
The present invention relates to a kind ofly by phthalic acid dibasic ester Hydrogenation 1, the method for 2-cyclohexane cyclohexanedimethanodibasic dibasic ester particularly is the process of 1,2-cyclohexane cyclohexanedimethanodibasic di-isooctyl by the dimixo-octyl phthalate hydrocracking.
Background technology
China's softening agent main products is phthalate, wherein take phthalic acid two (2-ethyl hexyl) ester (DOP or DEHP), dibutyl phthalate (DBP) as main, especially phthalic acid two (2-ethyl hexyl) ester accounts for about 70% of aggregate consumption.But in recent years, every country and area are investigated the performances such as toxicity, carinogenicity and biological degradability of phthalic ester plasticizer, discovery is in long-term use, because the impact of phenyl ring in the structure, that phthalic ester has is carcinogenic, teratogenecity, in human body, can put aside, the shortcoming such as biological degradability is poor.Therefore, the Application Areas of conventional plasticizers is restricted, and researching and developing nontoxic green plasticization agent product has become the current research focus.The superior performances such as heat-resisting, cold-resistant, the anti-UV of 1,2-cyclohexanedicarboxyester ester class, anti-combustion.Compatible with multiple polymers such as PVC, urethane, acrylic resin, resol, do not bring out the peroxysome hyperplasia through the animal experiment proof, do not bring out liver tumor, many countries have been approved for the food product pack, medicine equipment and the toy for children that directly contact with human body.Voluntarily biological degradation in physical environment does not cause environmental pollution, the hygienic safety that is beneficial to man.
The method of preparation great majority 1,2 cyclohexane cyclohexanedimethanodibasic dibasic ester is with the benzene ring hydrogenation in the corresponding phthalic acid dibasic ester at present.US Patent No. 6,284, the process that the 917 dimethyl phthalate classes that disclose employing loading type Ru catalyzer are produced corresponding fats dioctyl phthalate dimethyl ester, its reaction conditions is 70 ~ 220 ℃, 2 ~ 30MPa.US Patent No. 7,361,714 have reported at loading type Ru, Pt, Rh, Pa, aromatics dioctyl phthalate dimethyl ester is at 100 ~ 200 ℃ on Co or the Ni catalyzer, and hydrocracking is the reaction process of corresponding fats dioctyl phthalate dimethyl ester under 5 ~ 20MPa condition.Chinese patent CN101406840 and two pieces of patent Introductions of CN101417950 be used for phthalic acid dibasic ester Hydrogenation 1, the catalyzer of 2-cyclohexane cyclohexanedimethanodibasic dibasic ester and reaction process thereof.But technology exists temperature of reaction higher at present, the not high deficiency of the transformation efficiency of reaction or selectivity.
Summary of the invention
Purpose of the present invention has just provided a kind of phthalic acid dibasic ester hydrogenation and has produced 1, the method of 2-cyclohexane cyclohexanedimethanodibasic dibasic ester, present method can significantly reduce temperature of reaction and energy consumption, improve phthalic acid dibasic ester Hydrogenation 1, the transformation efficiency of the process of 2-cyclohexane cyclohexanedimethanodibasic dibasic ester and selectivity.
For achieving the above object, preparation 1 provided by the invention, the method for 2-cyclohexane cyclohexanedimethanodibasic di-isooctyl is 1,2-cyclohexane cyclohexanedimethanodibasic di-isooctyl with raw material dimixo-octyl phthalate hydrocracking.
The present invention is the method for standby 1, the 2-cyclohexane cyclohexanedimethanodibasic di-isooctyl of a kind of Hydrogenation, it is characterized in that:
Reaction system is comprised of dimixo-octyl phthalate, hydrogen and catalyzer, and reaction conditions is:
Temperature of reaction is 100 ~ 250 ℃, and reaction pressure is 5 ~ 18MPa, H
2With the volume ratio of dimixo-octyl phthalate be 2000 ~ 200: 1,
The liquid air speed of dimixo-octyl phthalate is 0.1 ~ 2.5h
-1
Described catalyzer is with Al
2O
3Be carrier, active ingredient is selected from and is among Ru, Pd, the Ni one or more, and the loading of active ingredient is the 1-3% of catalyst weight; Catalyzer is used H before use
2In-situ reducing activates.
According to method of the present invention, it is characterized in that: reaction conditions is:
Temperature of reaction is 160 ~ 190 ℃; Reaction pressure is 12 ~ 16MPa; H
2With the volume ratio of dimixo-octyl phthalate be 1000 ~ 400:1; The liquid air speed of dimixo-octyl phthalate is 0.2 ~ 0.8h
-1
Described catalyzer is with Al
2O
3Be carrier, active ingredient Ru is or/and Pd, and the loading of active ingredient is the 1.5-2.5% of catalyst weight.
The essential distinction of the present invention and prior art is, has significantly reduced temperature of reaction and energy consumption, improves phthalic acid dibasic ester Hydrogenation 1, the transformation efficiency of the process of 2-cyclohexane cyclohexanedimethanodibasic dibasic ester and selectivity.
Embodiment
The invention provides a kind of by dimixo-octyl phthalate Hydrogenation 1, the method for 2-cyclohexane cyclohexanedimethanodibasic di-isooctyl, reaction system is comprised of dimixo-octyl phthalate, hydrogen and catalyzer.Dimixo-octyl phthalate is converted into 1,2-cyclohexane cyclohexanedimethanodibasic di-isooctyl with high reactivity, highly selective after catalyzer contacts certain hour under certain temperature and hydrogen pressure in above-mentioned system.
The present invention can be directly be pumped into the dimixo-octyl phthalate of liquid state and enters into fixed-bed reactor in the preheater after the preheating.Need not to add any solvent in this process dissolves or dilutes.
Reaction process of the present invention can adopt fixed-bed reactor, also can adopt fluidized-bed reactor or trickle-bed reactor, preferred fixed-bed reactor.
Catalyzer of the present invention can activate by hydrogen treat before using.Better condition with the hydrogen deactivated catalyst is: GHSV=1000 ~ 2000h
-1, normal pressure ~ 1.0MPa, 250 ~ 450 ℃, 5 ~ 12 hours recovery times.
The present invention will be further described below by specific embodiment.
Embodiment 1
The catalyzer that adopts is Pd-Ru/Al
2O
3Catalyst weight consists of: Pd=0.5%, and Ru=1%, all the other are carrier A l
2O
3By conventional pickling process catalyst activity component Pd and Ru are supported on carrier A l
2O
3On.Through the hydrogen activation, activation condition is 10 gram catalyzer: GHSV=1000 ~ 2000h before reaction
-1, normal pressure ~ 1.0MPa, 250 ~ 450 ℃, 5 ~ 12 hours recovery times.Select trickle-bed reactor.Temperature of reaction is 175 ℃, and hydrogen pressure is 15MPa, and H2/ ester mol ratio is 600, and the volume space velocity of dimixo-octyl phthalate is 0.4h
-1,, reaction times 24h, sampling analysis.Vapor-phase chromatography is adopted in the analysis of product and raw material, and actual conditions is: nitrogen is carrier gas, and flow is 1.5mL/min., and sample size is 4 microlitres; Adopt the FID hydrogen flame ionization detector, HP-5 post, 260 ℃ of column temperatures.
Embodiment 2
Adopting the volume space velocity of dimixo-octyl phthalate is 0.3h
-1, other conditions are identical with embodiment 1.
Embodiment 3
Adopting the volume space velocity of dimixo-octyl phthalate is 0.5h
-1, other conditions are identical with embodiment 1.
Embodiment 4
Adopting temperature of reaction is 160 ℃, and other conditions are identical with embodiment 1.
Embodiment 5
Adopting temperature of reaction is 190 ℃, and other conditions are identical with embodiment 1.
Embodiment 6
The employing hydrogen pressure is 13MPa, and other conditions are identical with embodiment 1.
Embodiment 7
The employing hydrogen pressure is 16MPa, and other conditions are identical with embodiment 1.
Embodiment 8
Adopting H2/ ester mol ratio is 800, and other conditions are identical with embodiment 1.
Embodiment 9
Adopting H2/ ester mol ratio is 400, and other conditions are identical with embodiment 1.
Table 1 is dimixo-octyl phthalate Hydrogenation 1 of the present invention, 2-cyclohexane cyclohexanedimethanodibasic di-isooctyl reaction evaluating result:
Claims (2)
1. the method for standby 1, the 2-cyclohexane cyclohexanedimethanodibasic di-isooctyl of a Hydrogenation is characterized in that:
Reaction system is comprised of dimixo-octyl phthalate, hydrogen and catalyzer, and reaction conditions is:
Temperature of reaction is 100 ~ 250 ℃, and reaction pressure is 5 ~ 18MPa, H
2With the volume ratio of dimixo-octyl phthalate be 2000 ~ 200: 1,
The liquid air speed of dimixo-octyl phthalate is 0.1 ~ 2.5h
-1
Described catalyzer is with Al
2O
3Be carrier, active ingredient is selected from and is among Ru, Pd, the Ni one or more, and the loading of active ingredient is the 1-3% of catalyst weight; Catalyzer is used H before use
2In-situ reducing activates.
2. method according to claim 1, it is characterized in that: reaction conditions is:
Temperature of reaction is 160 ~ 190 ℃; Reaction pressure is 12 ~ 16MPa; H
2With the volume ratio of dimixo-octyl phthalate be 1000 ~ 400:1; The liquid air speed of dimixo-octyl phthalate is 0.2 ~ 0.8h
-1
Described catalyzer is with Al
2O
3Be carrier, active ingredient Ru is or/and Pd, and the loading of active ingredient is the 1.5-2.5% of catalyst weight.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210453430XA CN102898309A (en) | 2012-11-13 | 2012-11-13 | Method for preparing 1, 2-cyclohexane dioctyl phthalate diisooctyl by hydrogenation |
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|---|---|---|---|
| CN201210453430XA CN102898309A (en) | 2012-11-13 | 2012-11-13 | Method for preparing 1, 2-cyclohexane dioctyl phthalate diisooctyl by hydrogenation |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924277A (en) * | 2012-11-20 | 2013-02-13 | 中国海洋石油总公司 | Method for preparing cyclohexane dioctyl phthalate dibasic esters through hydrogenation |
| CN103240101A (en) * | 2013-05-24 | 2013-08-14 | 中国海洋石油总公司 | Preparation method of catalyst for hydrogenation of phthalic acid dicarboxylic ester |
| CN103304418A (en) * | 2013-06-09 | 2013-09-18 | 中国海洋石油总公司 | Method for preparing environment-friendly plasticizer cyclohexane dicarboxylic acid ester |
| CN106984310A (en) * | 2017-03-27 | 2017-07-28 | 常州大学 | A kind of method for preparing catalyst of phthalic ester plasticizer hydrogenation and application |
| CN109970559A (en) * | 2019-03-19 | 2019-07-05 | 凯凌化工(张家港)有限公司 | A kind of preparation method of 1,4- cyclohexane dicarboxylic acid di-isooctyl |
| CN110152564A (en) * | 2018-06-15 | 2019-08-23 | 宁波浙铁江宁化工有限公司 | A kind of preparation method of reactor and reactor production catalyst |
| CN112321427A (en) * | 2020-10-28 | 2021-02-05 | 中国石油化工股份有限公司 | Dioctyl phthalate hydrogenation catalyst and use method thereof |
| CN113651694A (en) * | 2021-09-16 | 2021-11-16 | 淄博晟亿弘新材料科技有限公司 | Preparation method of environment-friendly plasticizer cyclohexane 1, 2-diisononyl phthalate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7361714B2 (en) * | 2002-06-10 | 2008-04-22 | Oxeno Olefinchemie Gmbh | Catalyst and method for hydrogenating aromatic compounds |
| 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 |
-
2012
- 2012-11-13 CN CN201210453430XA patent/CN102898309A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7361714B2 (en) * | 2002-06-10 | 2008-04-22 | Oxeno Olefinchemie Gmbh | Catalyst and method for hydrogenating aromatic compounds |
| 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 |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924277A (en) * | 2012-11-20 | 2013-02-13 | 中国海洋石油总公司 | Method for preparing cyclohexane dioctyl phthalate dibasic esters through hydrogenation |
| CN103240101A (en) * | 2013-05-24 | 2013-08-14 | 中国海洋石油总公司 | Preparation method of catalyst for hydrogenation of phthalic acid dicarboxylic ester |
| CN103304418A (en) * | 2013-06-09 | 2013-09-18 | 中国海洋石油总公司 | Method for preparing environment-friendly plasticizer cyclohexane dicarboxylic acid ester |
| CN106984310A (en) * | 2017-03-27 | 2017-07-28 | 常州大学 | A kind of method for preparing catalyst of phthalic ester plasticizer hydrogenation and application |
| CN110152564A (en) * | 2018-06-15 | 2019-08-23 | 宁波浙铁江宁化工有限公司 | A kind of preparation method of reactor and reactor production catalyst |
| CN109970559A (en) * | 2019-03-19 | 2019-07-05 | 凯凌化工(张家港)有限公司 | A kind of preparation method of 1,4- cyclohexane dicarboxylic acid di-isooctyl |
| CN112321427A (en) * | 2020-10-28 | 2021-02-05 | 中国石油化工股份有限公司 | Dioctyl phthalate hydrogenation catalyst and use method thereof |
| CN113651694A (en) * | 2021-09-16 | 2021-11-16 | 淄博晟亿弘新材料科技有限公司 | Preparation method of environment-friendly plasticizer cyclohexane 1, 2-diisononyl phthalate |
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Application publication date: 20130130 |