CN103242164B - Continuous preparation process for environment-friendly plasticizer and device used in process - Google Patents
Continuous preparation process for environment-friendly plasticizer and device used in process Download PDFInfo
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- CN103242164B CN103242164B CN201310173895.4A CN201310173895A CN103242164B CN 103242164 B CN103242164 B CN 103242164B CN 201310173895 A CN201310173895 A CN 201310173895A CN 103242164 B CN103242164 B CN 103242164B
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- 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 relates to a continuous preparation process for an environment-friendly plasticizer and a device used in the process. The process comprises the following steps of: enabling solid terephthalic acid and isooctyl alcohol which serve as raw materials to react in the existence of an esterification catalyst and an antioxidant for continuously preparing dioctyl terephthalate (DOTP); pulpifying the solid terephthalic acid in the isooctyl alcohol until the particle size of the solid terephthalic acid reaches 5 to 20 mu m; adding the isooctyl alcohol so as to adjust the mole ratio of alcohol to acid in pulp liquid as 2:1 to 4:1; adding into a slurry tank, preheating, and entering a reaction kettle from the bottom; reacting with the preheated isooctyl alcohol which enters from the bottom of the reaction kettle in the reaction kettle in the existence of the esterification catalyst and/or the antioxidant; reacting until an acid value decreases to be below 2, and continuously feeding the raw materials namely the solid terephthalic acid and the isooctyl alcohol; and adding the DOTP which is generated in reaction from the upper part of the reaction kettle to a product tank, condensing the isooctyl alcohol which does not completely reacts and the generated steam through a condenser on the top of the reaction kettle, separating through an oil water separator, and entering an octyl alcohol tank for recirculation.
Description
Technical field
The present invention relates to and use a kind of novel fluidized bed serialization synthesis DOTP(dioctyl terephthalate) method, belong to plasticizer technical field.Be specifically related to the synthesis technique of raw material pulp and reaction bed design and DOTP.
Background technology
As everyone knows, being increase its plasticity-, mobility the material making finished product have snappiness to add during the high polymer molding such as softening agent is processing rubber, plastics, coating, is the requisite interpolation auxiliary agent of plastics industry.China's annual capacity reaches 2800kt, has become the production and consumption big country that beats the world, and continues to present growth.The ratio of this wherein phthalic ester and terephthalate occupies more than 90% again.But research shows that adjacent benzene class softening agent has potential carinogenicity, and the agent of the green plasticization such as epoxy grease and citric acid ester type is also difficult to meet huge market demand in short-term in output, so will be also the main products on market in future to benzene class softening agent, but traditional synthesis technique length consuming time, energy consumption is high.
As 3.1 the 4th articles of " terephthalic acid granularity is on the impact of terephthalic acid transformation efficiency " (in literary composition page number 11-12) in document " the reaction mechanism research of Di-2-ethylhexyl terephthalate synthesis " describe particle diameter to transformation efficiency without impact in research before.So always all nobody to reaction Raw particle diameter carried out control.
Summary of the invention
In order to solve the synthesis technique length consuming time that prior art exists, the shortcoming that energy consumption is high, the invention provides a kind of method of novel fluidized bed serialization synthesis DOTP, first react after raw material pulp, sufficient reacting, the time is short, energy consumption is low again, and can realize continuous prodution.
Technical scheme of the present invention is: a kind of environment-friendlyplasticizer plasticizer continuous preparation process, DOTP is prepared for raw material reacts serialization under the existence of esterifying catalyst and antioxidant with solid terephthalic acid and isooctyl alcohol, solid terephthalic acid first in isooctyl alcohol pulp to the particle diameter of terephthalic acid reach 5 ~ 20 microns, then adding in slurry tank after the molar ratio of alcohol to acid in slurries is adjusted to 2 ︰ 1 ~ 4 ︰ 1 by interpolation isooctyl alcohol enters in reactor by bottom after preheating, react with the preheated isooctyl alcohol entered bottom reactor under the existence of ester catalyst and/or antioxidant in reactor, when reaction is down to below 2 to acid value, continually pass into raw material terephthalic acid and isooctyl alcohol, the dioctyl terephthalate generated in reaction flows into products pot from the top of reactor, and the water vapour of unreacted isooctyl alcohol and generation completely circulates again via entering in octanol tank after being separated by water-and-oil separator after the condenser condenses at reactor top together.
Initial reaction stage, interim response temperature in the kettle are 200 DEG C ~ 240 DEG C, and reaction pressure is-0.02 ~ 0.3MPa.
Described esterifying catalyst and the addition of antioxidant are respectively 0.1% ~ 5% of alkyd total mass.
Described ester catalyst is organic titanium, organotin, and described antioxidant is inferior sodium phosphate.
The described pond that raw material terephthalic acid comprises solid pure terephthalic acid, production process produces material, land material or pipeline material etc.
The reaction later stage is decompressed to-0.001 ~-0.02MPa when octanol quantity of reflux obviously reduces in reactor.
The temperature of reactor evaporator overhead condenser is greater than 100 DEG C.
For the device in described environment-friendlyplasticizer plasticizer continuous preparation process, comprise reactor, be composed in series by slurry tank, fresh feed pump, reactor, products pot successively, reactor and recycle pump composition loop line, reactor, water-and-oil separator, octanol tank, reflux pump form loop line together with preheater, described reactor top is provided with discharge port, top is provided with byproduct discharge, byproduct discharge is funnel-form, neck stretches into reactor bottom, and reactor top is connected with packing tower and condenser.
Described reactor is one or more being in series.
Preheater is provided with between fresh feed pump and reactor.
Beneficial effect:
Raw material terephthalic acid be have passed through pulp process by the present invention before the reaction, to realize large specific surface sum pipeline flow.The present invention finds that granularity is relevant with reaction conversion ratio and pulp can effectively reduce system granularity, thus promotes that reaction is carried out; Material in reactor replaces stirring to realize Homogeneous phase mixing by circulation, and reduces energy consumption; The pressurize of reaction initial period is not conducive to reaction system higher than 0.3MPa and enters the main reaction stage as early as possible, makes temperature reach optimal reaction temperature the soonest, about 210 DEG C, improves speed of reaction; The negative pressure in reaction later stage makes reaction shift to positive dirction, and increase isooctyl alcohol quantity of reflux and rate of water loss promote speed of reaction, and suitably can reduce temperature of reaction.
Gas-liquid heat exchange is passed through in described octanol backflow, control the head temperature of reflux exchanger, temperature control is more than 100 DEG C, and the octanol after the also preheating that realizes refluxing enters reactor by the end of reactor, avoid cold burden and enter the impact of still on temperature, and add the stop reaction times of octanol in still.
Described raw material, comprises solid pure terephthalic acid, and pond material, the starting material such as material and pipeline material that land that production process produces.
When in still, material acid value is down to below 2, by volume pump, from bottom, continuous constant flow enters deployed slurry material, still upper outlet, can realize DOTP continuous operations.
Accompanying drawing explanation
Fig. 1 is fluidized-bed sketch of the present invention.
Wherein 1 is slurry tank, and 2 is fresh feed pump, and 3 is preheater, and 4 is recycle pump, 5 reactors, and 6 is reflux pump, and 7 is octanol tank, and 8 is water-and-oil separator, and 9 is products pot.
Fig. 2 pulp is on the impact of system.In figure, A is the appearance that isooctyl alcohol just put into by raw material, and B is the picture of pulp after 1 hour, and C is the picture after pulp evenly.
Fig. 3 pulp and non-pulp are to the influence curve of transformation efficiency.
Embodiment
Be described as follows by reference to the accompanying drawings.
As shown in Figure 1, a kind of method of novel fluidized bed serialization synthesis DOTP, by solid terephthalic acid pulp in octanol; Add alcohol and the molar ratio of alcohol to acid in slurries is adjusted to 2 ︰ 1 to 4 ︰ 1, and add slurry tank; Squeeze into reactor with volume pump, add 0.1% ~ 5%(account for alkyd total mass ratio) esterifying catalyst and antioxidant, heating cycle esterification; React the octanol steamed and at the bottom of still, enter reactor circulating reaction by preheating after water-and-oil separator is separated; When in still, material acid value is down to below 2, enter deployed slurry material by the continuous constant flow of volume pump, still ejects material, can realize continuous operations.
Raw material terephthalic acid be have passed through pulp process by the present invention before the reaction, to realize large specific surface sum pipeline flow.With reference to the raw material that A in accompanying drawing 2, figure is amplification 60 times, B is the system that reaction 1 as a child amplified 60, and C amplifies the system of 200 times after pulp, as can be seen here granularity with react relevant and pulp can effectively reduce system granularity, thus promotion reaction is carried out; Material in reactor replaces stirring to realize Homogeneous phase mixing by circulation, and reduces energy consumption; By preheating charging reuse at the bottom of still after the octanol separatory of reactive evaporation, avoid cold burden and enter the impact of still on temperature, and add the stop reaction times of octanol in still; Can simultaneously charging, discharging, achieve the possibility of DOTP serialization.Can be found out after pulp by accompanying drawing 3, reaction conversion ratio effectively improves.Have the funnel stretched into close to bottom in reactor 5, the octanol being conducive to condensation is from charging at the bottom of still.Connect the octanol after can conveying water separation by pipe between water-and-oil separator 8 and octanol tank 7 and enter octanol tank.
Embodiment 1:
Raw material: terephthalic acid, isooctyl alcohol, tetrabutyl titanate;
Be after reaching 10 micron grain sizes after the isooctyl alcohol of 2.2 ︰ 1 and terephthalic acid defibrination by mol ratio, inject head tank and open stirring and prevent sedimentation, reactor is filled by fresh feed pump, and add the ester catalyst tetrabutyl titanate of 1%, open water of condensation, heating up and opening recycle pump makes Matter Transfer react, pressurize 0.3MPa to 230 DEG C of pressure release; Automatically, after dividing water when there being cut to steam, the isooctyl alcohol of backflow is reached 190 DEG C and again enters reactor from still rising pouring by unlatching reflux pump and preheater; When material acid value is down to 2mgKOH/g in still, fresh feed pump can be opened and discharge port realizes successive reaction.
Embodiment 2:
Raw material: terephthalic acid, isooctyl alcohol, isopropyl titanate, inferior sodium phosphate;
Be inject head tank and open stirring after the isooctyl alcohol of 2.4 ︰ 1 and terephthalic acid defibrination to prevent sedimentation by mol ratio, reactor is filled by fresh feed pump, and add catalyst Ti isopropyl propionate and the antioxidant inferior sodium phosphate of 0.5%, open water of condensation, heating up and opening recycle pump makes Matter Transfer react, pressurize 0.2MPa to 230 DEG C of pressure release and progressively vacuum to-0.005MPa; Automatically, after dividing water when there being cut to steam, the isooctyl alcohol of backflow is reached 180 DEG C and again enters reactor from still rising pouring by unlatching reflux pump and preheater; When material acid value is down to 2mgKOH/g in still, fresh feed pump can be opened and discharge port realizes successive reaction.
Embodiment 3:
Raw material: terephthalic acid, isooctyl alcohol, tetrabutyl titanate, isopropyl titanate;
Be inject head tank and open stirring after the isooctyl alcohol of 2.1 ︰ 1 and terephthalic acid defibrination to prevent sedimentation by mol ratio, reactor is filled by fresh feed pump, and add catalyzer tetrabutyl titanate and the isopropyl titanate that total amount is 1%, open water of condensation, heating up and opening recycle pump makes Matter Transfer react; Automatically, after dividing water when there being cut to steam, the isooctyl alcohol of backflow is reached 220 DEG C and again enters reactor from still rising pouring by unlatching reflux pump and preheater; When material acid value is down to 1mgKOH/g in still, fresh feed pump can be opened and discharge port realizes successive reaction.
Claims (8)
1. an environment-friendlyplasticizer plasticizer continuous preparation process, DOTP is prepared for raw material reacts serialization under the existence of esterifying catalyst and antioxidant with solid terephthalic acid and isooctyl alcohol, it is characterized in that, solid terephthalic acid first in isooctyl alcohol pulp to the particle diameter of terephthalic acid reach 5 ~ 20 microns, then add and enter in reactor (5) by bottom after adding the middle preheating of slurry tank (1) after the molar ratio of alcohol to acid in slurries is adjusted to 2 ︰ 1 ~ 4 ︰ 1 by isooctyl alcohol, react with the preheated isooctyl alcohol entered from reactor (5) bottom under the existence of ester catalyst and antioxidant in reactor (5), when reaction is down to below 2 to acid value, continually pass into raw material terephthalic acid and isooctyl alcohol, the dioctyl terephthalate generated in reaction flows into products pot (9) from the top of reactor, and the water vapour of unreacted isooctyl alcohol and generation completely circulates again via entering in octanol tank (7) after being separated by water-and-oil separator (8) after the condenser condenses at reactor (5) top together.
2. environment-friendlyplasticizer plasticizer continuous preparation process as claimed in claim 1, it is characterized in that, initial reaction stage, interim response still (5) interior temperature are 200 DEG C ~ 240 DEG C, and reaction pressure is-0.02 ~ 0.3MPa.
3. environment-friendlyplasticizer plasticizer continuous preparation process as claimed in claim 1, it is characterized in that, described esterifying catalyst and the addition of antioxidant are respectively 0.1% ~ 5% of alkyd total mass.
4. environment-friendlyplasticizer plasticizer continuous preparation process as claimed in claim 1, it is characterized in that, described ester catalyst is organic titanium, organotin, and described antioxidant is inferior sodium phosphate.
5. environment-friendlyplasticizer plasticizer continuous preparation process as claimed in claim 1, is characterized in that, the described pond that raw material terephthalic acid comprises solid pure terephthalic acid, production process produces material, lands material or pipeline material.
6. environment-friendlyplasticizer plasticizer continuous preparation process as claimed in claim 1, is characterized in that, the reaction later stage is decompressed to-0.001 ~-0.02MPa when octanol quantity of reflux obviously reduces in reactor.
7. environment-friendlyplasticizer plasticizer continuous preparation process as claimed in claim 1, it is characterized in that, the temperature of reactor evaporator overhead condenser is greater than 100 DEG C.
8. environment-friendlyplasticizer plasticizer continuous preparation process as claimed in claim 1, it is characterized in that, described reactor (5) is in series for one or more.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018211338A1 (en) * | 2017-05-19 | 2018-11-22 | Sabic Global Technologies B.V. | Method of producing plasticizer and reducing energy consumption |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435488B (en) * | 2013-09-04 | 2015-03-25 | 中国林业科学研究院林产化学工业研究所 | Process for producing environment-friendly plasticizer employing conical fluidized bed and device thereof |
| CN104610063A (en) * | 2015-01-08 | 2015-05-13 | 宜兴市阳洋塑料助剂有限公司 | Novel preparation method of dioctyl terephthalate |
| TWI624454B (en) * | 2017-06-19 | 2018-05-21 | Nanya Plastics Corp | Method for improving reaction efficiency of terephthalate plasticizer |
| CN107281776B (en) * | 2017-07-21 | 2019-07-12 | 中国林业科学研究院林产化学工业研究所 | A kind of process of environmental protection treatment DOTP production waste residue recovered plasticizer |
| CN108329206A (en) * | 2018-01-23 | 2018-07-27 | 宜兴市阳洋塑料助剂有限公司 | A kind of preparation method of environment-friendlyplasticizer plasticizer dioctyl terephthalate |
| CN108752202B (en) * | 2018-07-04 | 2021-08-10 | 南通百川新材料有限公司 | Method for preparing trimellitic acid triester by continuous esterification method |
| CN111732510A (en) * | 2020-07-03 | 2020-10-02 | 山东朗晖石油化学股份有限公司 | Continuous production equipment and process for DOTP plasticizer |
| CN111889059B (en) * | 2020-08-29 | 2022-12-02 | 浙江工业大学 | Reaction device and process for preparing DOTP |
| CN112266325A (en) * | 2020-09-24 | 2021-01-26 | 山东润林新材料科技有限公司 | Continuous distillation system for producing DOTP by regenerating PTA |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB684334A (en) * | 1949-12-16 | 1952-12-17 | Fred Dean | Improvements in and relating to the production of esters from solid acids or anhydrides |
| CN101469059A (en) * | 2007-12-29 | 2009-07-01 | 厦门翔鹭化纤股份有限公司 | Preparation of flame-retardant copolymerization modified poly(trimethylene terephthalate) |
| CN201990614U (en) * | 2011-01-27 | 2011-09-28 | 潍坊市元利化工有限公司 | Continuous dealcoholizing device used for dicapryl phthalate |
| CN102153467B (en) * | 2011-03-11 | 2013-08-07 | 江苏强林生物能源有限公司 | Process for preparing benzoic ether plasticizer by using slurry method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2018211338A1 (en) * | 2017-05-19 | 2018-11-22 | Sabic Global Technologies B.V. | Method of producing plasticizer and reducing energy consumption |
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