CN115232007A - Production method of plasticizer - Google Patents
Production method of plasticizer Download PDFInfo
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- CN115232007A CN115232007A CN202210687851.2A CN202210687851A CN115232007A CN 115232007 A CN115232007 A CN 115232007A CN 202210687851 A CN202210687851 A CN 202210687851A CN 115232007 A CN115232007 A CN 115232007A
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- Prior art keywords
- alcohol
- esterification
- plasticizer
- dealcoholization
- sulfuric acid
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- 239000004014 plasticizer Substances 0.000 title claims abstract description 62
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 126
- 238000005886 esterification reaction Methods 0.000 claims abstract description 117
- 230000032050 esterification Effects 0.000 claims abstract description 82
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 65
- 150000002148 esters Chemical class 0.000 claims abstract description 22
- 238000004458 analytical method Methods 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 8
- 238000003825 pressing Methods 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 4
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 4
- 238000004064 recycling Methods 0.000 claims abstract description 4
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 claims description 28
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 11
- BJAJDJDODCWPNS-UHFFFAOYSA-N dotp Chemical compound O=C1N2CCOC2=NC2=C1SC=C2 BJAJDJDODCWPNS-UHFFFAOYSA-N 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 54
- 239000002699 waste material Substances 0.000 abstract description 13
- 230000007613 environmental effect Effects 0.000 abstract description 8
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 13
- 238000004042 decolorization Methods 0.000 description 11
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical group CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 5
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 4
- 239000002932 luster Substances 0.000 description 4
- 239000011265 semifinished product Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/60—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for producing a plasticizer, which relates to the technical field of plasticizer production and comprises the following steps: s1, placing acid or acid anhydride, alcohol and a catalyst in an esterification kettle to perform esterification reaction; s2, after the esterification reaction is finished, carrying out alcohol sulfuric acid chromaticity analysis on alcohol in the esterification phase separator, and if the alcohol sulfuric acid chromaticity exceeds the standard, carrying out rectification treatment; s3, carrying out alcohol-sulfuric acid chromaticity analysis on the alcohol after rectification again, and if the alcohol-sulfuric acid chromaticity is less than or equal to # 20, recycling the alcohol into the esterification kettle as recovered alcohol; and S4, neutralizing, dealcoholizing and filter-pressing crude ester generated in the esterification reaction in the step S1 to obtain a plasticizer product. The production method of the plasticizer can effectively improve the esterification color quality, and can control the esterification color number within the range of 15-30# under the condition of decoloring without adding activated carbon, thereby effectively avoiding the generation of waste activated carbon and further lightening the environmental protection pressure.
Description
Technical Field
The invention relates to the technical field of plasticizer production, in particular to a method for producing a plasticizer.
Background
The plasticizer is a polymer material additive widely used in industry, and the flexibility of the plasticizer is enhanced by adding the plasticizer in plastic processing, so that the plasticizer is easy to process and can be widely applied to industrial application. There are many types of plasticizers, and most of the plasticizers used are phthalic acid esters such as dibutyl phthalate (DBP), diisobutyl phthalate (DIBP), and the like. The plasticizer produced by the prior art inevitably generates various pigment impurities in the reaction and synthesis process, and the pigment impurities cannot be removed by simple neutralization and water washing, so that the step of decoloring is required in the production process of the plasticizer. At present, the decolorization process mainly adopts activated carbon to an esterification kettle or decolorizes the esterification kettle, a large amount of waste activated carbon is often generated in the decolorization process, and the waste activated carbon cannot be well recovered, so that waste and pollution are caused, and the environmental protection pressure is increased.
Disclosure of Invention
1. Technical problem to be solved by the invention
The invention provides a plasticizer production method, which can effectively avoid the generation of waste activated carbon and further reduce the environmental protection pressure on the premise of ensuring the quality of a plasticizer without decoloring by activated carbon, aiming at the technical problems that a large amount of waste activated carbon is generated in the production process of the existing plasticizer, so that the waste and the pollution are caused and the environmental protection pressure is further increased.
2. Technical scheme
In order to solve the problems, the technical scheme provided by the invention is as follows:
a method of producing a plasticizer comprising the steps of:
s1, placing acid or acid anhydride, alcohol and a catalyst in an esterification kettle to perform esterification reaction;
s2, after the esterification reaction is finished, carrying out alcohol sulfuric acid chromaticity analysis on alcohol in the esterification phase separator, and if the alcohol sulfuric acid chromaticity exceeds the standard, carrying out rectification treatment;
s3, carrying out alcohol-sulfuric acid chromaticity analysis on the alcohol after rectification again, and if the alcohol-sulfuric acid chromaticity is less than or equal to 20#, recycling the alcohol into the esterification kettle as recovered alcohol;
and S4, neutralizing, dealcoholizing and filter-pressing crude ester generated in the esterification reaction in the step S1 to obtain a plasticizer product.
In the method, alcohol sulfuric acid chromaticity analysis is carried out on alcohol in an esterification phase separator, if the alcohol sulfuric acid chromaticity exceeds the standard, rectification treatment is carried out to remove a small amount of low-boiling-point substances, and when the sulfuric acid chromaticity of the alcohol after rectification treatment is less than or equal to 20#, the alcohol is used as recovered alcohol to circularly enter an esterification kettle to participate in esterification reaction; and the content of alcohol in the recovered alcohol can be improved, impurities such as light-boiling substances, ether and the like can be effectively reduced to enter the esterification reaction, the esterification color quality is improved, and the esterification color number is controlled within the range of 15-30# under the condition of not adding activated carbon for decolorization. Therefore, the production method of the plasticizer can effectively improve the esterification color quality, and can control the esterification color number within the range of 15-30# under the condition of not adding activated carbon for decolorization, thereby effectively avoiding the generation of waste activated carbon and further reducing the environmental protection pressure.
Optionally, in the step S4, the content of ester in the recovered alcohol obtained through dealcoholization is less than or equal to 1.5%.
Optionally, in the step S4, the neutralized crude ester enters a dealcoholization tower to perform dealcoholization, and the alcohol generated after dealcoholization circulates into the esterification reactor as recovered alcohol.
Optionally, a wire mesh demister is arranged at the top of the dealcoholization tower, and the dealcoholization temperature in the dealcoholization tower is less than 160 ℃.
Optionally, the plasticizer product is any one of DOTP, DBP and DIBP.
Optionally, when the plasticizer product is DOTP, the catalyst is a non-acidic catalyst, and the esterification finishing temperature is less than 210 ℃; when the plasticizer product is DBP or DIBP, the esterification end temperature is less than 150 ℃.
Optionally, in the step S1, the mass ratio of the acid anhydride to the alcohol is 1:1.2-1.5.
Optionally, in the step S2, a rectifying tower is adopted for rectifying treatment, and the temperature of the top of the rectifying tower is 100-125 ℃.
Optionally, in the step S1, the alcohol includes fresh alcohol, recovered alcohol in the step S3, and recovered alcohol obtained through dealcoholization in the step S4.
Optionally, the fresh alcohol make-up per cycle is reduced to 2% -4% of the fresh alcohol make-up from the previous time.
3. Advantageous effects
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
(1) According to the production method of the plasticizer provided by the embodiment of the application, alcohol sulfuric acid chromaticity analysis is carried out on alcohol in an esterification phase separator, if the alcohol sulfuric acid chromaticity exceeds the standard, rectification treatment is carried out to remove a small amount of low-boiling-point substances, and when the sulfuric acid chromaticity of the alcohol after rectification treatment is less than or equal to 20#, the alcohol is used as recovered alcohol to circularly enter an esterification kettle to participate in esterification reaction; and the content of alcohol in the recovered alcohol can be improved, impurities such as light-boiling substances, ether and the like can be effectively reduced to enter the esterification reaction, the esterification color quality is improved, and the esterification color number is controlled within the range of 15-30# under the condition of not adding activated carbon for decolorization. Therefore, the production method of the plasticizer can effectively improve the esterification color quality, and can control the esterification color number within the range of 15-30# under the condition of not adding activated carbon for decolorization, thereby effectively avoiding the generation of waste activated carbon and further reducing the environmental protection pressure.
(2) According to the plasticizer production method provided by the embodiment of the application, the content of the ester in the recovered alcohol obtained through dealcoholization is controlled to be less than or equal to 1.5%, the content of the alcohol in the recovered alcohol can be increased, the generation of side reactions of the ester in an esterification reaction is reduced, the deepening of the esterification color is avoided, and the decoloring treatment by adopting activated carbon is avoided.
(3) According to the plasticizer production method provided by the embodiment of the application, the wire mesh demister is arranged at the top of the dealcoholization tower, so that the treatment of recovered alcohol after dealcoholization can be reduced, and the ester content in the recovered alcohol can be reduced.
(4) According to the plasticizer production method provided by the embodiment of the application, the temperature collected from the top of the rectifying tower is controlled to be 100-125 ℃, so that substances affecting color and luster such as low-boiling-point substances can be effectively removed, the quality of recovered alcohol is improved, and the decolorization treatment by using activated carbon is avoided.
(5) According to the method for producing the plasticizer, provided by the embodiment of the application, the amount of the fresh alcohol circularly supplemented each time is reduced to 2% -4% of the amount of the fresh alcohol supplemented in the previous time, so that the recovered alcohol is continuously reduced while the recovered alcohol participates in the esterification reaction, the treatment amount and the heating amount are reduced, and the waste of energy is reduced.
Detailed Description
In order to further understand the content of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
It should be noted that the percentages referred to in this application refer to mass percentages.
The application provides a plasticizer production method, which comprises the following steps:
s1, placing acid or acid anhydride, alcohol and a catalyst in an esterification kettle to perform esterification reaction; wherein the mass ratio of the acid anhydride to the alcohol is 1:1.2-1.5, the esterification color and luster quality can be further improved by setting the mass ratio of the acid anhydride to the alcohol; further, the alcohol comprises fresh alcohol, recovered alcohol in the step S3 and recovered alcohol obtained by dealcoholization in the step S4; furthermore, the fresh alcohol replenished in each circulation is reduced to 2% -4% of the fresh alcohol replenished in the previous circulation, and the arrangement can ensure that the recovered alcohol is continuously reduced while the recovered alcohol participates in the esterification reaction, thereby reducing the treatment amount and the heating amount and reducing the waste of energy.
S2, after the esterification reaction is finished, carrying out alcohol sulfuric acid chromaticity analysis on the alcohol in the esterification phase separator, and if the alcohol sulfuric acid chromaticity exceeds the standard, carrying out rectification treatment; wherein, a rectifying tower is adopted for rectifying treatment, and the temperature of the top of the rectifying tower is 100-125 ℃. The device can effectively remove substances such as low-boiling-point substances and the like which influence color and luster, and improve the quality of recovered alcohol.
And S3, carrying out alcohol sulfuric acid chromaticity analysis on the alcohol after rectification again, and if the alcohol sulfuric acid chromaticity is less than or equal to 20#, recycling the alcohol into the esterification kettle as recovered alcohol.
S4, neutralizing the crude ester generated in the esterification reaction in the step S1 by using alkali liquor, carrying out vacuum dealcoholization through a dealcoholization tower, recovering alcohol after dealcoholization, returning the recovered alcohol to the esterification kettle, and carrying out filter pressing on the dealcoholized semi-finished product in a filter press to obtain a plasticizer product; wherein, the neutralized crude ester enters a dealcoholization tower for dealcoholization, and the alcohol generated after dealcoholization circularly enters an esterification kettle as recovered alcohol; meanwhile, the content of ester in the recovered alcohol obtained by dealcoholization is less than or equal to 1.5 percent. The device improves the content of alcohol in the recovered alcohol, reduces the side reaction of ester in the alcohol in the esterification reaction, avoids deepening the esterification color and avoids adopting activated carbon for decolorization treatment; furthermore, a wire mesh demister is arranged at the top of the dealcoholization tower, and the dealcoholization temperature in the dealcoholization tower is less than 160 ℃. The device can reduce the treatment of recovered alcohol after dealcoholization and reduce the ester content in the recovered alcohol.
Further, the plasticizer product is any one of DOTP, DBP and DIBP. Further, when the plasticizer product is DOTP, the catalyst is a non-acidic catalyst, and the esterification finishing temperature is less than 210 ℃; when the plasticizer product is DBP or DIBP, the esterification end temperature is less than 150 ℃. By controlling the esterification finishing temperature, the side reaction of the ester in the esterification reaction can be effectively reduced, the color and luster are prevented from being deepened, and the decoloration treatment by adopting activated carbon is avoided. In practice, the non-acidic catalyst is TIPT (tetraisopropyl titanate) or TBT (tetraisobutyl titanate).
In the method, alcohol sulfuric acid chromaticity analysis is carried out on alcohol in an esterification phase separator, if the alcohol sulfuric acid chromaticity exceeds the standard, rectification treatment is carried out to remove a small amount of low-boiling-point substances, and when the sulfuric acid chromaticity of the alcohol after rectification treatment is less than or equal to 20#, the alcohol is used as recovered alcohol to circularly enter an esterification kettle to participate in esterification reaction; the content of alcohol in the recovered alcohol can be improved, impurities such as light-boiling residues and ether can be effectively reduced to enter the esterification reaction, the esterification color quality is improved, and the esterification color number is controlled within the range of 15-30# under the condition of not adding activated carbon for decolorization. Therefore, the production method of the plasticizer can effectively improve the esterification color quality, and the esterification color number is controlled within the range of 15-30# under the condition that activated carbon is not added for decoloring, so that the generation of waste activated carbon is effectively avoided, and the environmental protection pressure is relieved.
Example 1
Putting terephthalic acid, 2-ethyl hexanol and tetraisopropyl titanate into an esterification kettle to perform esterification reaction; wherein the mass ratio of terephthalic acid to 2-ethylhexanol is 1:1.2; after the esterification reaction is finished, carrying out alcohol-sulfuric acid chromaticity analysis on alcohol in the esterification phase separator, and if the alcohol-sulfuric acid chromaticity exceeds the standard, carrying out rectification treatment by using a rectification tower, wherein the extraction temperature at the top of the rectification tower is 110 ℃; and then, carrying out alcohol-sulfuric acid chromaticity analysis on the alcohol after rectification treatment again, wherein the alcohol-sulfuric acid chromaticity is No. 15, and the alcohol is recycled into the esterification kettle as recovered alcohol to carry out esterification reaction. Meanwhile, the crude ester generated by the esterification reaction is neutralized by alkali liquor, vacuum dealcoholization is carried out by a dealcoholization tower, the recovered alcohol after dealcoholization returns to the esterification kettle, and the ester content in the recovered alcohol obtained by dealcoholization is 1.2 percent; and (3) carrying out filter pressing on the dealcoholized semi-finished product in a filter press to obtain a DOTP (dioctyl terephthalate) plasticizer product, wherein the esterification time is 7 hours and 10 minutes, and the esterification color number is 30#.
Example 2
Placing phthalic anhydride, n-butyl alcohol and dilute sulfuric acid in an esterification kettle to perform esterification reaction; wherein the mass ratio of the phthalic anhydride to the n-butyl alcohol is 1:1.3; after the esterification reaction is finished, carrying out alcohol-sulfuric acid chromaticity analysis on alcohol in the esterification phase separator, if the alcohol-sulfuric acid chromaticity exceeds the standard, carrying out rectification treatment by using a rectification tower, wherein the extraction temperature at the top of the rectification tower is 118 ℃; and then, carrying out alcohol-sulfuric acid chromaticity analysis on the alcohol after rectification treatment again, wherein the alcohol-sulfuric acid chromaticity is 20#, and the alcohol is recycled as recovered alcohol to enter the esterification kettle for esterification reaction. Meanwhile, the crude ester generated by the esterification reaction is neutralized by alkali liquor, vacuum dealcoholization is carried out by a dealcoholization tower, the recovered alcohol after dealcoholization returns to the esterification kettle, and the ester content in the recovered alcohol obtained by dealcoholization is 1.0 percent; and (3) carrying out filter pressing on the dealcoholized semi-finished product in a filter press to obtain a DBP (dibutyl phthalate) plasticizer product, wherein the esterification time is 3 hours and 25 minutes, and the esterification color number is 20#.
Example 3
Placing phthalic anhydride, isobutanol and dilute sulphuric acid in an esterification kettle to carry out esterification reaction; wherein the mass ratio of the phthalic anhydride to the n-butyl alcohol is 1:1.4; after the esterification reaction is finished, carrying out alcohol-sulfuric acid chromaticity analysis on alcohol in the esterification phase separator, and if the alcohol-sulfuric acid chromaticity exceeds the standard, carrying out rectification treatment by using a rectification tower, wherein the extraction temperature at the top of the rectification tower is 110 ℃; and then, carrying out alcohol-sulfuric acid chromaticity analysis on the alcohol after rectification treatment again, wherein the alcohol-sulfuric acid chromaticity is No. 15, and the alcohol is recycled into the esterification kettle as recovered alcohol to carry out esterification reaction. Meanwhile, the crude ester generated by the esterification reaction is neutralized by alkali liquor, vacuum dealcoholization is carried out by a dealcoholization tower, the recovered alcohol after dealcoholization returns to the esterification kettle, and the ester content in the recovered alcohol obtained by dealcoholization is 1.5%; and (3) the dealcoholized semi-finished product enters a filter press for filter pressing to obtain a DIBP (diisobutyl phthalate) plasticizer product, wherein the esterification time is 4 hours and 20 minutes, and the esterification color number is 15#.
Comparative example 1
Comparative example 1 a DOTP (dioctyl terephthalate) plasticizer product was prepared according to the conventional method, except that 2.5kg of activated carbon was added to the esterification tank in comparative example 1, sulfuric acid color analysis and rectification of the alcohol in the esterification phase separator were not performed, and the other conditions were the same as in example 1. DOTP (dioctyl terephthalate) plasticizer obtained in comparative example 1 has an esterification time of 7 hours and 15 minutes and an esterification color number of 35#.
Comparative example 2
Comparative example 2 a DBP (dibutyl phthalate) plasticizer product was prepared according to the conventional method, which is different from example 2 in that 2kg of activated carbon was added to the esterification tank in comparative example 2, and the alcohol in the esterification phase separator was not subjected to sulfuric acid colorimetric analysis and rectification treatment, and the other conditions were the same. The DBP (dibutyl phthalate) plasticizer obtained in comparative example 2 had an esterification time of 3 hours and 30 minutes and an esterification color number of 25#.
Comparative example 3
Comparative example 3 a DIBP (diisobutyl phthalate) plasticizer product was prepared according to the conventional method, except that in comparative example 3, 5kg of activated carbon was added to the esterification tank, and the alcohol in the esterification phase separator was not subjected to sulfuric acid color analysis and rectification treatment, and the other conditions were the same as in example 3. The DIBP (diisobutyl phthalate) plasticizer obtained in comparative example 3 had an esterification time of 4 hours and 30 minutes and an esterification color number of # 30.
From the three controls of comparative example 1 and example 1, comparative example 2 and example 2, and comparative example 3 and example 3, it can be seen that the esterification time of the DOTP, DBP and DIBP plasticizer products prepared by the plasticizer production method of the present application is almost affected and the esterification color quality is not reduced without adding activated carbon for decolorization treatment. Therefore, the production method of the plasticizer can effectively improve the esterification color quality, and can control the esterification color number within the range of 15-30# under the condition of not adding activated carbon for decolorization, thereby effectively avoiding the generation of waste activated carbon and further reducing the environmental protection pressure.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention. Those skilled in the art can make various changes, modifications and equivalent arrangements, which are equivalent to the embodiments of the present invention, without departing from the spirit and scope of the present invention, and which may be made by utilizing the techniques disclosed above; meanwhile, any changes, modifications and variations of the above-described embodiments, which are equivalent to those of the technical spirit of the present invention, are within the scope of the technical solution of the present invention.
Claims (10)
1. A method for producing a plasticizer, comprising the steps of:
s1, placing acid or acid anhydride, alcohol and a catalyst in an esterification kettle to perform esterification reaction;
s2, after the esterification reaction is finished, carrying out alcohol sulfuric acid chromaticity analysis on the alcohol in the esterification phase separator, and if the alcohol sulfuric acid chromaticity exceeds the standard, carrying out rectification treatment;
s3, carrying out alcohol-sulfuric acid chromaticity analysis on the alcohol after rectification again, and if the alcohol-sulfuric acid chromaticity is less than or equal to 20#, recycling the alcohol into the esterification kettle as recovered alcohol;
and S4, neutralizing, dealcoholizing and filter-pressing the crude ester generated in the esterification reaction in the step S1 to obtain a plasticizer product.
2. The method for producing a plasticizer according to claim 1, wherein in the step S4, the recovered alcohol obtained by the dealcoholization treatment has an ester content of 1.5% or less.
3. The method for producing a plasticizer according to claim 1, wherein in the step S4, the neutralized crude ester is subjected to dealcoholization in a dealcoholization column, and the alcohol produced after the dealcoholization is recycled to the esterification tank as recovered alcohol.
4. The method for producing a plasticizer according to claim 3, wherein a wire mesh demister is provided at the top of the dealcoholization tower, and the dealcoholization temperature in the dealcoholization tower is less than 160 ℃. DEG C.
5. The method of producing plasticizer according to claim 1, wherein the plasticizer product is any one of DOTP, DBP and DIBP.
6. The method of claim 5, wherein when the plasticizer product is DOTP, the catalyst is a non-acidic catalyst, and the esterification finishing temperature is less than 210 ℃; when the plasticizer product is DBP or DIBP, the esterification end temperature is less than 150 ℃.
7. The method for producing a plasticizer according to claim 1, wherein in the S1 step, the mass ratio of acid anhydride to alcohol is 1:1.2-1.5.
8. The method for producing the plasticizer according to claim 1, wherein in the step S2, a rectifying tower is adopted for rectification, and the temperature of the top of the rectifying tower is 100 to 125 ℃.
9. The method for producing a plasticizer according to claim 1, wherein the alcohol in the step S1 comprises a fresh alcohol, the recovered alcohol in the step S3, and the recovered alcohol obtained by the dealcoholization treatment in the step S4.
10. A process for the production of plasticisers according to claim 9 characterised in that the fresh alcohol make-up per cycle is reduced to between 2% and 4% of the fresh alcohol make-up from the previous make-up.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210687851.2A CN115232007A (en) | 2022-06-16 | 2022-06-16 | Production method of plasticizer |
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| CN102952012A (en) * | 2012-10-17 | 2013-03-06 | 河南启瑞生物科技发展有限公司 | Method for improving quality of plasticizer |
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| CN213131978U (en) * | 2020-07-15 | 2021-05-07 | 浙江建业化工股份有限公司 | Recovery system for recovering isobutanol in alcohol low-boiling-point substance by isobutyl ester plasticizer |
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| CN109942357A (en) * | 2019-04-16 | 2019-06-28 | 营创三征(营口)精细化工有限公司 | A kind of low-boiling point alcohol continuous esterification rectification process |
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