CN108976117B - Method for preparing high-carbon alcohol phthalate through ester exchange continuous reaction - Google Patents
Method for preparing high-carbon alcohol phthalate through ester exchange continuous reaction Download PDFInfo
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- CN108976117B CN108976117B CN201710408372.1A CN201710408372A CN108976117B CN 108976117 B CN108976117 B CN 108976117B CN 201710408372 A CN201710408372 A CN 201710408372A CN 108976117 B CN108976117 B CN 108976117B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention relates to a method for preparing high carbon alcohol phthalate through ester exchange continuous reaction, which is characterized in that in a fixed bed reactor, low carbon alcohol phthalate such as dimethyl phthalate, diethyl phthalate and dibutyl phthalate and high carbon alcohol such as isononyl alcohol, isodecyl alcohol and 2-propyl heptanol are used as raw materials, one or more of magnesium calcium aluminate, sodium aluminosilicate, potassium aluminosilicate, magnesium aluminosilicate, calcium aluminosilicate, aluminum magnesium titanate, magnesium calcium titanate and aluminum magnesium zirconate are used as catalysts, the molar ratio of the high carbon alcohol to the low carbon alcohol phthalate is 2.1-4.0, the reaction temperature is 160-220 ℃, and the volume space velocity is 0.5-2 h‑1The conversion rate of the phthalic acid low-carbon alcohol ester and the selectivity of the phthalic acid high-carbon alcohol ester are more than 99 percent at most. The invention has the following advantages: the raw material storage and transportation stability is good, and the feeding is convenient; the side reaction is less, and the raw material consumption is low; the catalyst is corrosion-free and can be continuously used; the process is clean and energy-saving, and no wastewater is generated and discharged; the reaction is continuously carried out in the fixed bed reactor, and the efficiency is high.
Description
Technical Field
The invention belongs to the field of organic chemical industry, and particularly relates to a method for preparing high-carbon alcohol phthalate through ester exchange continuous reaction.
Background
The plasticizer is a necessary auxiliary agent for producing products such as polyester, plastic, rubber and the like, and is used for weakening the acting force among macromolecules, increasing the mobility of molecular chains and reducing the crystallinity, thereby improving the comprehensive properties such as plasticity, flexibility, stretchability and the like of the high molecular polymer. Low-end plasticizers such as Dibutyl Phthalate (DBP) and Dioctyl Phthalate (DOP) which are easy to migrate and separate out and have large environmental influence are mainly used in China. DBP, DOP, etc. have been restricted to production and use in Japan, European Union, etc., and have been mainly replaced with higher alcohol phthalates such as Diisononyl Phthalate (DINP), diisodecyl Phthalate (DIDECYL Phthalate, DIDP), Di (2-propylheptyl) Phthalate (Di-2-propylhexyl Phthalate, DPHP), etc. The structural formulas of DBP, DOP, DINP, DIDP and DPHP are shown as the following figures:
the comprehensive performance of the DPHP is particularly superior, and the DPHP has the following advantages: (1) the steam pressure is low, the volatilization is difficult, and the temperature resistance grade of the product is high; (2) the plasticizer has low toxicity and is one of main plasticizer varieties in the fields of Japan, America, European Union and the like; (3) the polymer has good compatibility with polyvinyl chloride, polystyrene, nitrocellulose, nitrile rubber, chloroprene rubber and the like, and is not easy to separate out; (4) the durability, the fogging resistance, the weather resistance and the color stability are good; (5) the rubber and plastic product added with DPHP has smooth surface, good flexibility, difficult fracture, long service life, excellent aging resistance, high volume resistance and good water resistance and oil resistance (Zhang, Zhao civilization, plastic additive 2012, 1, 51-52).
High-carbon alcohol phthalate such as DINP, DIDP, DPHP and the like is mainly prepared by esterification reaction of phthalic anhydride (phthalic anhydride) and high-carbon alcohol such as isononyl alcohol, isodecyl alcohol, 2-propyl heptanol and the like by taking sulfuric acid, titanate and the like as catalysts, and has the following defects: (1) the storage and transportation stability of the raw material phthalic anhydride is poor, moisture absorption and agglomeration are easy, feeding is inconvenient, and the irritation to human bodies is strong; (2) strong acid catalysts such as sulfuric acid are adopted, equipment is seriously corroded, side reactions such as dehydration and etherification of high-carbon alcohols such as isononyl alcohol, isodecyl alcohol and 2-propyl heptanol are easy to occur, and raw material consumption is high; (3) the reaction byproduct is water with the same mole as the phthalic anhydride, so that the water separation cost is increased, and waste water is generated; (4) catalysts such as sulfuric acid, titanate and the like cannot be recycled, and are removed by alkali washing, water washing and the like after reaction, so that a large amount of wastewater is generated; (5) the intermittent kettle type reaction is adopted, and the efficiency is low (yellow war, Xujie, high advance, Miao hong, Su Ying, a method for preparing di (2-propyl heptyl) phthalate, ZL 201310374032.3).
Disclosure of Invention
In order to solve the problems that the storage and transportation stability of the raw material phthalic anhydride is poor, the feeding is inconvenient and the irritation to human body is strong in the process of preparing phthalic acid higher alcohol ester plasticizers such as DINP, DIDP and DPHP by the existing phthalic anhydride esterification method; the side reaction is more, and the raw material consumption is high; the catalyst has strong corrosivity and can not be recycled, and needs to be removed by alkali washing, water washing and other processes, so that a large amount of wastewater is generated; the reaction is a gap reaction, the efficiency is low, and the like, and the invention aims to: the method for preparing the high-carbon alcohol phthalate such as DINP, DIDP, DPHP and the like by ester exchange continuous reaction has the following advantages: (1) the raw materials are dimethyl phthalate, diethyl phthalate, dibutyl phthalate and other low-carbon alcohol phthalate esters instead of phthalic anhydride, so that the storage and transportation stability is good, and the feeding is convenient; (2) the ester exchange method is adopted to prepare the high carbon alcohol phthalate, and no water is generated in the reaction, so that not only can the water separation energy consumption be reduced, but also the generation and the discharge of process wastewater can be avoided; (3) the developed ester exchange catalyst has no corrosion, can be continuously used, has less side reaction and low raw material consumption; (4) the reaction is continuously carried out in the fixed bed reactor, and the efficiency is high.
In order to achieve the purpose, the invention adopts the technical scheme that: as shown in the following formula, in a fixed bed reactor, low carbon alcohol phthalate and high carbon alcohol are used as raw materials, and in the presence of a catalyst, high carbon alcohol phthalate is prepared through ester exchange continuous reaction.
The phthalic acid low carbon alcohol ester is one or more than two of dimethyl phthalate, diethyl phthalate and dibutyl phthalate; the higher alcohol is one or more than two of isononyl alcohol, isodecyl alcohol and 2-propyl heptanol; the higher alcohol ester phthalate is one or more of diisononyl phthalate, diisodecyl phthalate and di (2-propyl heptyl) phthalate
According to the invention, the catalyst is of great importance. Without the catalyst, the conversion rate of the lower alcohol phthalate and the selectivity of the higher alcohol phthalate are both very low. When the activity of the catalyst is low, the conversion rate of the phthalic acid low carbon alcohol ester is low, and the main product is phthalic acid single low carbon alcohol single high carbon alcohol ester. When the catalyst activity is high, the high conversion rate of the phthalic acid low carbon alcohol ester and the high selectivity of the phthalic acid high carbon alcohol ester can be obtained. The reaction is carried out in a fixed bed reactor, and the catalyst must be insoluble in the reactants, products, intermediates and by-products and be capable of continuous use. The ester exchange reaction catalyst researched and developed by the invention is one or more than two of magnesium calcium aluminate, sodium aluminosilicate, potassium aluminosilicate, magnesium aluminosilicate, calcium aluminosilicate, magnesium aluminum titanate, magnesium calcium titanate and magnesium aluminum zirconate.
According to the invention, the ester exchange reaction is a reversible reaction, in order to make the reaction proceed toward the direction of generating higher alcohol phthalate, higher alcohols such as isononyl alcohol, isodecyl alcohol, 2-propyl heptanol and the like are slightly excessive, and the reaction system is separated out in time by utilizing the low boiling point of the generated lower alcohols such as methanol, ethanol, butanol and the like. The molar ratio of the high-carbon alcohol to the phthalic acid low-carbon alcohol ester is 2.1-4.0, preferably 3.0-4.0.
According to the invention, the reaction temperature is 160-220 ℃, and preferably 200-220 ℃; the reaction volume airspeed is 0.5-2.0 h-1Preferably 0.5 to 1.0 hour-1。
The invention has the beneficial effects that:
(1) the method for preparing the high carbon alcohol phthalate by adopting the ester exchange method has the following advantages: the raw material storage and transportation stability is good, and the feeding is convenient; the side reaction is less, and the raw material consumption is low; the process is clean and energy-saving, and no wastewater is generated and discharged; the catalyst is corrosion-free and can be continuously used; the reaction is continuously carried out in the fixed bed reactor, and the efficiency is high.
(2) The highest conversion rate of the phthalic acid low-carbon alcohol ester and the highest selectivity of the phthalic acid high-carbon alcohol ester can reach more than 99 percent.
Detailed Description
The following examples are provided to aid in the understanding of the present invention, but the present disclosure is not limited thereto.
TABLE 1 preparation of higher alcohol phthalate by ester interchange continuous reaction
Example 1
100ml of magnesium calcium aluminate catalyst is filled into a fixed bed reactor, 2-propyl heptanol/dimethyl phthalate (DMP) mixed liquor with the molar ratio of 3 is pumped after the temperature of a reaction tube rises to 220 ℃, and the flow rate is set to be 100ml/h (the volume space velocity is 1 h)-1) After the reaction is continuously operated for 4 hours, sampling is carried out, qualitative and quantitative analysis is carried out by gas chromatography-mass spectrometry, and the conversion rate of the DMP as the raw material and the selectivity of the DPHP as the product are both more than 99 percent. After the reaction is continuously operated for 24 hours, sampling and analyzing are carried out again, and the DMP conversion rate and the DPHP selectivity reach more than 99 percent.
Examples 2 to 10
The specific procedures of examples 2-10 are similar to those of example 1, and the specific reaction conditions and the reaction results after 24h of continuous operation are shown in Table 1. The method is characterized in that sodium aluminosilicate, potassium aluminosilicate, magnesium aluminosilicate, calcium aluminosilicate, magnesium aluminum titanate, magnesium calcium titanate, magnesium aluminum zirconate and magnesium calcium aluminate are used as catalysts, low-carbon alcohol phthalate such as dimethyl phthalate, diethyl phthalate and dibutyl phthalate are subjected to transesterification with high-carbon alcohols such as 2-propyl heptanol, isononyl alcohol and isodecyl alcohol, the molar ratio of the high-carbon alcohol to the low-carbon alcohol phthalate is 2.1-4.0, the reaction temperature is 160-220 ℃, and the volume space velocity is 0.5-2 h-1The conversion rate of the phthalic acid low-carbon alcohol ester and the selectivity of the phthalic acid high-carbon alcohol ester can both reach over 90 percent.
Comparative examples 11 to 17
To investigate the effect of the catalyst composition on the reaction, comparative experiments were performed. The reaction was carried out under the same conditions as in example 1 using DMP and 2-propylheptanol as raw materials and alumina, magnesia, calcium oxide, magnesium aluminate, calcium aluminate, etc. as catalysts, and the specific procedure was similar to example 1, and the results are shown in table 2.
TABLE 2 results of the comparative examples for DPHP production by transesterification
Reaction conditions are as follows: the molar ratio of 2-propyl heptanol to DMP is 3, the reaction temperature is 220 ℃, and the volume space velocity is 1.0h-1。
In example 1, the conversion rate of DMP and the selectivity of DPHP both reach more than 99 percent by taking calcium magnesium aluminate as a catalyst. However, it is understood from comparative examples 11 to 14 that the DMP conversion and DPHP selectivity are much lower than those of example 1 under the same reaction conditions, regardless of whether alumina, magnesia or calcia are used alone or in combination as the catalyst. From comparative examples 15 to 17, it can be seen that, even though magnesium aluminate or calcium aluminate is used as a catalyst or a mixture thereof is used as a catalyst, the DMP conversion and DPHP selectivity are much lower than those of example 1 under the same reaction conditions, indicating that the composition of the catalyst has a great influence on the reaction results of the present invention.
In the invention, one or more of calcium magnesium aluminate, sodium aluminosilicate, potassium aluminosilicate, magnesium aluminosilicate, calcium aluminosilicate, magnesium titanate, magnesium calcium titanate and aluminum magnesium zirconate is used as a catalyst in a fixed bed reactor, the low carbon alcohol phthalate such as dimethyl phthalate, diethyl phthalate and dibutyl phthalate and the high carbon alcohols such as isononyl alcohol, isodecyl alcohol and 2-propyl heptanol are subjected to ester exchange reaction, and the conversion rate of the low carbon alcohol phthalate and the selectivity of the high carbon alcohol phthalate can reach more than 99%. The invention has the following advantages: the raw material storage and transportation stability is good, and the feeding is convenient; the side reaction is less, and the raw material consumption is low; the catalyst is corrosion-free and can be continuously used; the process is clean and energy-saving, and no wastewater is generated and discharged; the reaction is continuously carried out in the fixed bed reactor, and the efficiency is high.
Claims (2)
1. A method for preparing high-carbon alcohol phthalate through ester exchange continuous reaction is characterized in that: in a fixed bed reactor, preparing phthalic acid high carbon alcohol ester by taking phthalic acid low carbon alcohol ester and high carbon alcohol as raw materials in the presence of a catalyst;
the phthalic acid low carbon alcohol ester is one or more than two of dimethyl phthalate, diethyl phthalate and dibutyl phthalate; the higher alcohol is one or more than two of isononyl alcohol, isodecyl alcohol and 2-propyl heptanol; the higher alcohol phthalate is one or more than two of diisononyl phthalate, diisodecyl phthalate and di (2-propyl heptyl) phthalate; the catalyst is one or more than two of magnesium calcium aluminate, sodium aluminosilicate, potassium aluminosilicate, magnesium aluminosilicate, calcium aluminosilicate and aluminum magnesium zirconate.
2. The method of claim 1, wherein: in a fixed bed reactor, the molar ratio of the high-carbon alcohol to the phthalic acid low-carbon alcohol ester is 2.1-4.0; the reaction temperature is 160-220% oC; the reaction volume airspeed is 0.5-2.0 h-1。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3507905A (en) * | 1965-06-09 | 1970-04-21 | Rhone Poulenc Sa | Continuous preparation of glycol phthalates |
| CN102675102A (en) * | 2012-04-27 | 2012-09-19 | 孝感市易生新材料有限公司 | Continuous production method of high-content high-optical-purity lactate |
| CN104418747A (en) * | 2013-08-22 | 2015-03-18 | 中国科学院大连化学物理研究所 | Method for preparation of phthalate di(2-propyl heptyl) ester |
| CN105646229A (en) * | 2014-12-04 | 2016-06-08 | 中国科学院大连化学物理研究所 | Method used for preparing higher aliphatic phthalates via ester exchange |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3507905A (en) * | 1965-06-09 | 1970-04-21 | Rhone Poulenc Sa | Continuous preparation of glycol phthalates |
| CN102675102A (en) * | 2012-04-27 | 2012-09-19 | 孝感市易生新材料有限公司 | Continuous production method of high-content high-optical-purity lactate |
| CN104418747A (en) * | 2013-08-22 | 2015-03-18 | 中国科学院大连化学物理研究所 | Method for preparation of phthalate di(2-propyl heptyl) ester |
| CN105646229A (en) * | 2014-12-04 | 2016-06-08 | 中国科学院大连化学物理研究所 | Method used for preparing higher aliphatic phthalates via ester exchange |
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