CN104496818A - Method or producing DBP by utilizing composite Lewis acid catalysis method - Google Patents
Method or producing DBP by utilizing composite Lewis acid catalysis method Download PDFInfo
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- CN104496818A CN104496818A CN201410791282.1A CN201410791282A CN104496818A CN 104496818 A CN104496818 A CN 104496818A CN 201410791282 A CN201410791282 A CN 201410791282A CN 104496818 A CN104496818 A CN 104496818A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
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- 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
Abstract
The invention provides a method or producing DBP by utilizing a composite Lewis acid catalysis method. Composite Lewis acid is taken as a catalyst and is a quite good catalyst in an esterification process; the acid becomes a sulfate when the reaction is nearly completed; no acid exists during the process, so generation of unmanageable waste liquid is avoided, the production process is optimized, technological processes such as neutralization, water washing, decolorization and dehydration after the reaction are saved, and the technological processes are simplified, so that no neutralization wastewater is generated in the technological processes, and the comprehensive cost is greatly lowered; the composite Lewis acid does not belong to a quite dangerous chemic product and is better than concentrated sulfuric acid; compared with an original process, the process of the method disclosed by the invention has the advantages of reducing the reaction temperature, reducing the danger level of the reaction and shortening the production period, namely increasing the yield in unit time and reducing the energy consumption; the method disclosed by the invention has positive significance at the economic aspect and at the environmental protection aspect as well.
Description
Technical field
The present invention relates to field of fine chemical, specifically a kind of method utilizing composite road Lewis acid catalysis method to produce DBP.
Background technology
Rubber industry develop rapidly in recent years, the requirement of softening agent is large.Softening agent is in the market dioctyl phthalate (DOP) (DOP) mainly, dibutyl phthalate (DBP).Most domestic DOP, DBP manufacturer all adopts sulfuric acid as catalyzer, find in very long one section of practice process, have many good qualities as catalyzer with sulfuric acid, catalytic activity is high, consumption is few, price is low, conveniently be easy to get, but also there are many shortcomings, production unit is corrosive, esterification products color is darker, product acid number is higher, poor heat resistance, in building-up process, temperature of reaction is higher, sometimes dehydration is caused, oxidation, the side reactions such as polymerization, spanning tree resinous material, also must through neutralization after reaction, washing, decolouring, dewatering process process, particularly water washing process has waste water to produce pollution.So, there is significant limitation with sulfuric acid as Catalyst Production quality products.
Summary of the invention
There are as Catalyst Production DBP process problems such as production unit being corrosive, esterification products color is comparatively dark, product acid number is higher, temperature of reaction is high in poor heat resistance, building-up process, spanning tree resinous material is many for above-mentioned sulfuric acid, the invention provides a kind of method utilizing composite road Lewis acid catalysis method to produce DBP.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
1. utilize composite road Lewis acid catalysis method to produce a method of DBP, comprise the following steps:
1) according to weight parts, get 0.4 ~ 0.6 part of titanium sulfate, 0.4 ~ 0.6 part of ferric sulfate slowly adds in 3.5 ~ 4.5 parts of water and stir 40min, obtain composite road Lewis acid, for subsequent use;
2) according to weight parts, get 15 ~ 25 parts of phthalic anhydrides and mix with 50 ~ 55 parts of butanols, be then slowly warming up to 75 ~ 85 DEG C, stir 20 ~ 30min, for subsequent use;
3) the compound Louis acid of at least 1 part of step 1) gained to be added in step 2) in the mixed solution of gained, slowly be warming up to 130 ~ 150 DEG C, sample detection reaction after 3 ~ 4h whether to reach home, question response is cooled to 55 ~ 65 DEG C after reaching terminal, suction filtration, filtrate enters dealcoholysis essence and reserves finished product workshop section, obtains DBP finished product;
In described step 1), the parts by weight of each component are: titanium sulfate 0.5 part, 0.5 part, ferric sulfate, 4 parts, water;
Described step 2) in get parts by weight be that 20 parts of phthalic anhydrides mix with 52 parts of butanols, be then slowly warmed up to 80 DEG C, stir 30min;
In described step 3), the compound Louis acid of 1 part of step 1) gained to be added in step 2) in the mixed solution of gained, slowly be warming up to 140 DEG C, sample detection reaction after 3.5h whether to reach home, question response is cooled to 60 DEG C after reaching terminal, suction filtration, filtrate enters dealcoholysis essence and reserves finished product workshop section, obtains DBP finished product.
Beneficial effect of the present invention:
The method utilizing composite road Lewis acid catalysis method to produce DBP provided by the invention, select two kinds of mineral sulfatess as catalyzer, utilize it can generate Lewis acid in water, this acid is fabulous catalyzer in esterification process, when reaction completes soon, become vitriol again, owing to there is no acid among process, do not generate unmanageable waste liquid, optimize production technique, after deducting reaction, through the technological process of neutralization, washing, decolouring, dehydration, technological process must be simplified, make not produce neutralized wastewater in technological process, comprehensive cost reduces greatly; The acid of compound Louis does not belong to danger close chemical, is better than the vitriol oil; Compared with former technique, reduce temperature of reaction, reduce the hazard level of reaction; Shorten the production cycle, being equivalent to the unit time improves output, reduces energy consumption; No matter economically the present invention, or has positive effect from environmental protection.
Embodiment
Below in conjunction with embodiment, the present invention is further elaborated.
Embodiment 1
Utilize composite road Lewis acid catalysis method to produce a method of DBP, comprise the following steps:
1) according to weight parts, get 0.5 part of titanium sulfate, 0.5 part of ferric sulfate slowly adds in 4 parts of water and stir 40min, obtain composite road Lewis acid, for subsequent use;
2) according to weight parts, get 20 parts of phthalic anhydrides and mix with 52 parts of butanols, be then slowly warming up to 80 DEG C, stir 30min, for subsequent use;
3) the compound Louis acid of 1 part of step 1) gained to be added in step 2) in the mixed solution of gained, be slowly warming up to 140 DEG C, sample detection reaction after 3.5h and whether reach home, question response is cooled to 60 DEG C after reaching terminal, suction filtration, filtrate enters dealcoholysis essence and reserves finished product workshop section, obtains DBP finished product;
Above each material and supplies add all with weight parts, all parts by weight are according to same ratio standard.
Embodiment 2
Utilize composite road Lewis acid catalysis method to produce a method of DBP, comprise the following steps:
1) according to weight parts, get 0.4 part of titanium sulfate, 0.6 part of ferric sulfate slowly adds in 4.5 parts of water and stir 40min, obtain composite road Lewis acid, for subsequent use;
2) according to weight parts, get 15 parts of phthalic anhydrides and mix with 50 parts of butanols, be then slowly warmed up to 75 DEG C, stir 20min, for subsequent use;
3) the compound Louis acid of 2 parts of step 1) gained to be added in step 2) in the mixed solution of gained, be slowly warming up to 130 DEG C, sample detection reaction after 3h and whether reach home, question response is cooled to 55 DEG C after reaching terminal, suction filtration, filtrate enters dealcoholysis essence and reserves finished product workshop section, obtains DBP finished product;
Above each material and supplies add all with weight parts, all parts by weight are according to same ratio standard.
Embodiment 3
Utilize composite road Lewis acid catalysis method to produce a method of DBP, comprise the following steps:
1) according to weight parts, get 0.6 part of titanium sulfate, 0.4 part of ferric sulfate slowly adds in 3.5 parts of water and stir 40min, obtain composite road Lewis acid, for subsequent use;
2) according to weight parts, get 25 parts of phthalic anhydrides and mix with 55 parts of butanols, be then slowly warmed up to 85 DEG C, stir 25min, for subsequent use;
3) the compound Louis acid of 1 part of step 1) gained to be added in step 2) in the mixed solution of gained, be slowly warming up to 150 DEG C, sample detection reaction after 4h and whether reach home, question response is cooled to 65 DEG C after reaching terminal, suction filtration, filtrate enters dealcoholysis essence and reserves finished product workshop section, obtains DBP finished product;
Above each material and supplies add all with weight parts, all parts by weight are according to same ratio standard.
DBP produces chemical equation:
The reaction formula that Lewis acid is formed: (for titanium sulfate)
The present invention adopts composite road Lewis acid to be catalyzer, and this catalyzer will have following characteristics: consumption is few, and active high, aftertreatment is uncomplicated, is easy to get;
Emphasis of the present invention will solve in DBP production process, and production unit is corrosive, and esterification products color is darker, product acid number is higher, poor heat resistance, and in building-up process, temperature of reaction is high, the problems such as spanning tree resinous material is many, and optimize production technique, also must through neutralization after reacting, washing, decolouring, dewatering process process all eliminates, such process simplification, makes not produce neutralized wastewater in technological process.
Claims (4)
1. utilize composite road Lewis acid catalysis method to produce a method of DBP, it is characterized in that, comprise the following steps:
1) according to weight parts, get 0.4 ~ 0.6 part of titanium sulfate, 0.4 ~ 0.6 part of ferric sulfate slowly adds in 3.5 ~ 4.5 parts of water and stir 40min, obtain composite road Lewis acid, for subsequent use;
2) according to weight parts, get 15 ~ 25 parts of phthalic anhydrides and mix with 50 ~ 55 parts of butanols, be then slowly warming up to 75 ~ 85 DEG C, stir 20 ~ 30min, for subsequent use;
3) the compound Louis acid of at least 1 part of step 1) gained to be added in step 2) in the mixed solution of gained, slowly be warming up to 130 ~ 150 DEG C, sample detection reaction after 3 ~ 4h whether to reach home, question response is cooled to 55 ~ 65 DEG C after reaching terminal, suction filtration, filtrate enters dealcoholysis essence and reserves finished product workshop section, obtains DBP finished product.
2. utilize composite road Lewis acid catalysis method to produce the method for DBP as claimed in claim 1, it is characterized in that: in described step 1), the parts by weight of each component are: titanium sulfate 0.5 part, 0.5 part, ferric sulfate, 4 parts, water.
3. utilize composite road Lewis acid catalysis method to produce the method for DBP as claimed in claim 1, it is characterized in that: described step 2) in get parts by weight be that the phthalic anhydride of 20 parts mixes with the butanols of 52 parts, be then slowly warmed up to 80 DEG C, stirring 30min.
4. utilize composite road Lewis acid catalysis method to produce the method for DBP as claimed in claim 1, it is characterized in that: in described step 3), the compound Louis acid of 1 part of step 1) gained to be added in step 2) in the mixed solution of gained, slowly be warming up to 140 DEG C, sample detection reaction after 3.5h whether to reach home, question response is cooled to 60 DEG C after reaching terminal, suction filtration, filtrate enters dealcoholysis essence and reserves finished product workshop section, obtains DBP finished product.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410791282.1A CN104496818A (en) | 2014-12-19 | 2014-12-19 | Method or producing DBP by utilizing composite Lewis acid catalysis method |
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| CN201410791282.1A CN104496818A (en) | 2014-12-19 | 2014-12-19 | Method or producing DBP by utilizing composite Lewis acid catalysis method |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503831A (en) * | 2011-11-07 | 2012-06-20 | 潍坊市元利化工有限公司 | Continuous esterification production method for plasticizer |
| CN103508892A (en) * | 2013-10-10 | 2014-01-15 | 上海市计量测试技术研究院 | Synthetic method for phthalate compound |
-
2014
- 2014-12-19 CN CN201410791282.1A patent/CN104496818A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503831A (en) * | 2011-11-07 | 2012-06-20 | 潍坊市元利化工有限公司 | Continuous esterification production method for plasticizer |
| CN103508892A (en) * | 2013-10-10 | 2014-01-15 | 上海市计量测试技术研究院 | Synthetic method for phthalate compound |
Non-Patent Citations (4)
| Title |
|---|
| GUI-SHENG ZHANG: "Fe2(S04)3*Xh2o in Synthesis: A Convenient and Efficient Catalyst for the Esterification of Aromatic Carboxylic Acids With Alcohols", 《SYNTHETIC COMMUNICATIONS》 * |
| 李家贵等: "邻苯二甲酸二甲酯的催化合成", 《应用化工》 * |
| 王刚等: "硫酸钛催化合成邻苯二甲酸二异辛酯的研究", 《广西化工》 * |
| 马广宽等: "硫酸铁催化合成邻苯二甲酸二正丁酯", 《锦州师范学院学报（自然科学版）》 * |
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