Preparation method of environment-friendly plasticizer cyclohexane 1, 2-diisononyl phthalate
阅读说明：本技术 环保增塑剂环己烷1,2-二甲酸二异壬酯的制备方法 (Preparation method of environment-friendly plasticizer cyclohexane 1, 2-diisononyl phthalate ) 是由 王海云 王少东 王建刚 于 2021-09-16 设计创作，主要内容包括：本发明属于有机化学合成技术领域,具体涉及一种环保增塑剂环己烷1,2-二甲酸二异壬酯的制备方法,以邻苯二甲酸二异壬酯和氢气为原料,在金属负载催化剂作用下加氢反应,得到环保增塑剂环己烷1,2-二甲酸二异壬酯；所述的金属负载催化剂以模板剂改性的氧化铝为载体,通过雾状喷涂将活性组分Rh或Ru负载于载体之上。本发明改进了催化剂的活性组分负载方式,简化了负载过程,缩短了催化剂制备的时长,降低了催化剂制备的能耗；同时,催化剂保持较高的活性及选择性,产物中副产物含量少,有效地降低了后续产品提纯难度及能耗。在本发明催化剂的作用下,反应中DINP转化率可达到100％,DINCH的选择性可达到99.9％。(The invention belongs to the technical field of organic chemical synthesis, and particularly relates to a preparation method of an environment-friendly plasticizer cyclohexane 1, 2-diisononyl phthalate, which takes diisononyl phthalate and hydrogen as raw materials to carry out hydrogenation reaction under the action of a metal supported catalyst to obtain the environment-friendly plasticizer cyclohexane 1, 2-diisononyl phthalate; the metal supported catalyst takes alumina modified by a template as a carrier, and an active component Rh or Ru is loaded on the carrier through mist spraying. The invention improves the active component loading mode of the catalyst, simplifies the loading process, shortens the time length of catalyst preparation and reduces the energy consumption of catalyst preparation; meanwhile, the catalyst keeps higher activity and selectivity, the content of byproducts in the product is low, and the purification difficulty and energy consumption of subsequent products are effectively reduced. Under the action of the catalyst, the DINP conversion rate in the reaction can reach 100%, and the DINCH selectivity can reach 99.9%.)
1. A preparation method of cyclohexane 1, 2-diisononyl phthalate as an environment-friendly plasticizer is characterized by comprising the following steps: taking diisononyl phthalate and hydrogen as raw materials, and carrying out hydrogenation reaction under the action of a metal supported catalyst to obtain cyclohexane 1, 2-diisononyl phthalate serving as an environment-friendly plasticizer;
the metal supported catalyst takes alumina modified by a template as a carrier, and an active component Rh or Ru is loaded on the carrier through mist spraying.
2. The method for preparing cyclohexane 1, 2-dicarboxylic acid diisononyl ester as an environmentally friendly plasticizer according to claim 1, wherein: the template agent is n-butylamine or ethylenediamine, and the mass ratio of the alumina to the template agent is 100: 1-5.
3. The method for preparing cyclohexane 1, 2-dicarboxylic acid diisononyl ester as an environmentally friendly plasticizer according to claim 1, wherein: the dosage of the active component is 0.5-1.5% of the mass of the carrier.
4. The method for preparing cyclohexane 1, 2-dicarboxylic acid diisononyl ester as an environmentally friendly plasticizer according to claim 1, wherein: the hydrogenation reaction temperature is 90-160 ℃, and the hydrogenation reaction pressure is 4-6 MPa.
5. The method for preparing cyclohexane 1, 2-dicarboxylic acid diisononyl ester as an environmentally friendly plasticizer according to claim 1, wherein: the liquid airspeed of the diisononyl phthalate is 0.2-1 h-1。
6. The method for preparing cyclohexane 1, 2-dicarboxylic acid diisononyl ester as an environmentally friendly plasticizer according to claim 1, wherein: the volume ratio of the hydrogen to the diisononyl phthalate is 100-300: 1.
7. The method for preparing cyclohexane 1, 2-dicarboxylic acid diisononyl ester as an environmentally friendly plasticizer according to claim 1, wherein: the preparation of the metal supported catalyst comprises the following steps:
(1) grinding alumina, mixing with a template agent, pressing for forming, drying, roasting, cooling and sieving to obtain modified alumina;
(2) atomizing and spraying chloride of the active component on the surface of the modified alumina, drying and roasting to obtain a catalyst precursor; and reducing the catalyst precursor in a hydrogen atmosphere to obtain the metal supported catalyst.
8. The method for preparing cyclohexane 1, 2-dicarboxylic acid diisononyl ester as an environmentally friendly plasticizer according to claim 7, wherein: in the step (1), the drying temperature is 110-130 ℃, and the drying time is 1-3 hours; the roasting temperature is 500-600 ℃, and the roasting time is 3-5 hours; the mesh number of the sieve is 10-20 meshes.
9. The method for preparing cyclohexane 1, 2-dicarboxylic acid diisononyl ester as an environmentally friendly plasticizer according to claim 7, wherein: in the step (2), the chloride of the active component is ruthenium chloride or rhodium chloride.
10. The method for preparing cyclohexane 1, 2-dicarboxylic acid diisononyl ester as an environmentally friendly plasticizer according to claim 7, wherein: in the step (2), the drying temperature is 110-130 ℃, and the drying time is 3-5 hours; the roasting temperature is 350-450 ℃, and the roasting time is 3-5 hours; the reduction temperature is 280-320 ℃, and the reduction time is 3-5 hours.
Technical Field
The invention belongs to the technical field of organic chemical synthesis, and particularly relates to a preparation method of cyclohexane 1, 2-diisononyl phthalate serving as an environment-friendly plasticizer.
Background
Asia is the area with the largest usage amount of the plasticizer in the world, China is the major producing and using country of the plasticizer, and the annual output and usage are the first world. There are over 500 kinds of plasticizers commercialized worldwide, among which phthalate esters are the most used plasticizers in the market at present, accounting for about 80% of the total amount of the plasticizer market, and mainly include dibutyl phthalate (DBP), di (2-ethylhexyl) phthalate (DOP), diisononyl phthalate (DINP), and the like. However, for many years, researches show that the phthalate dibasic ester plasticizer is easy to pollute the environment, food and the like due to large addition amount and poor migration resistance and extraction resistance, generates enrichment in organisms, causes certain harm to human health, is subject to more and more blame and doubt, is gradually eliminated, and is more limited or forbidden to be used for plastic products such as medical instruments, food, toys for children and the like in many countries in recent years.
Cyclohexane 1, 2-diisononyl phthalate (DINCH) is a non-phthalate plasticizer specially developed for sensitive application of PVC, and the product has no environmental toxicity, carcinogenicity, peroxide body proliferation, biological accumulation and reproductive toxicity, is mainly applied to production of toys for children under three years old, medical supplies, PVC plastic particles, cable and wire materials and the like, is more and more important in food contact PVC such as food packaging, preservative films and the like, and is a plasticizer which has good performance and is environment-friendly and nontoxic. The development of the environment-friendly plasticizer has important significance for promoting the structure adjustment and the healthy development of the plastic industrial chain in China.
There are two main methods for synthesizing DINCH: one is acid (anhydride) alcohol esterification, i.e. the trans-substitution reaction of 1, 2-cyclohexane dicarboxylic acid (anhydride) and isononyl alcohol to produce cyclohexane 1, 2-dicarboxylic acid diisononyl ester and water. However, the reaction is a reversible reaction, the esterification is incomplete, a large amount of alcohol needs to be excessive in the reaction process, water needs to be removed at any time in the reaction process, the reaction temperature is high (230-250 ℃), ethers are easily generated in the reaction process, a large amount of byproducts are generated, and the separation energy consumption is high. The other is a catalytic hydrogenation method, namely, diisononyl phthalate (DINP) and hydrogen are used as raw materials, and DINCH is synthesized by hydrogenation under the action of a catalyst. The method has simple process, is environment-friendly and easy to industrialize, and is the mainstream direction of future development.
In the United states of BASF corporationIn the national patent US6184917, Ru supported catalyst is adopted, so that the industrial production of catalytic synthesis DINCH is realized under the condition of 20MPa, and the method becomes the largest DINCH producer in the world. German patent DE2823165 discloses a method for preparing aliphatic dimethyl diformate by hydrogenation on a supported Ni, Ru or Pd catalyst, wherein the process conditions are 70-250 ℃ and 3-20 MPa. U.S. Pat. No. 3,73, 714 discloses a method for converting phthalic polyacid polybasic ester into cyclohexane polyacid polybasic ester by hydrogenation of benzene ring, the catalyst active component used in the method comprises at least one VIII group transition metal alone or at least one I or VII group transition metal, and the reaction is carried out under 8-10 MPa. U.S. Pat. No. 3,7355084 discloses a process for the preparation of 1, 2-cyclohexanedicarboxylic acid diisononyl ester from DINP with a reaction catalyst of 3% Ru/Silica (SiO)2) The reaction is carried out at 120 ℃ and 20MPa, the conversion rate of DINP reaches 100 percent, and the selectivity of 1, 2-cyclohexane dicarboxylic acid diisononyl ester exceeds 99 percent. U.S. Pat. No. 4,7786201 discloses a method for preparing 1, 2-cyclohexane dicarboxylic acid diisononyl ester, the active components of the catalyst used in the method comprise at least one VIII group transition metal and optionally at least one II, III, IV, V, VI group transition metal, the reaction is carried out at 60-200 ℃ and 3-25 MPa, and the conversion rate of diisononyl phthalate can reach more than 99.9%.
Chinese patent CN101417950A discloses a method for preparing cyclohexane 1, 2-dicarboxylic acid dibasic ester, which is carried out at 100-250 ℃ and 3-12 MPa, and Al is used as a catalyst2O3、ZrO2、TiO2Or SiO2-Al2O3The active component can be ruthenium, palladium, platinum, rhodium, iron, cobalt, nickel and copper, and the method can be used for preparing cyclohexane 1, 2-diisononyl phthalate, cyclohexane 1, 2-diisooctyl phthalate or cyclohexane 1, 2-dibutyl phthalate. Chinese patent CN102675109A discloses a preparation method of cyclohexane-1, 2-diisooctyl phthalate, which takes diisooctyl phthalate as a raw material, isooctanol as a solvent and ruthenium as a catalyst to prepare the diisooctyl cyclohexane-1, 2-dicarboxylate at the temperature of 160-200 ℃ and the pressure of 4-10 MPa, and the method has the advantages of easily obtained raw materials, product selectivity of more than 98 percent and purity of more than 99 percent.
In the method for preparing DINCH by catalytic hydrogenation in the aforementioned patent, multiple times of impregnation, multiple times of drying and multiple times of calcination are generally required in the active component loading process, so that on one hand, the catalyst preparation process is time-consuming and low in efficiency, and the catalyst preparation energy consumption is high due to multiple times of drying and calcination; on the other hand, the impregnation process generates impregnation waste liquid.
Disclosure of Invention
The invention aims to provide a preparation method of cyclohexane 1, 2-diisononyl phthalate as an environment-friendly plasticizer, which is a metal-loaded catalyst taking modified alumina as a carrier and Rh or Ru as an active component and adopts a mist spraying mode to load the active component, wherein the catalyst has high activity and selectivity.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the preparation method of the environment-friendly plasticizer cyclohexane 1, 2-diisononyl phthalate takes diisononyl phthalate and hydrogen as raw materials, and the diisononyl phthalate is subjected to hydrogenation reaction under the action of a metal supported catalyst to obtain the environment-friendly plasticizer cyclohexane 1, 2-diisononyl phthalate;
the metal supported catalyst takes alumina modified by a template as a carrier, and the specific surface area of the carrier is improved, the internal pore structure of the carrier is improved, the mass transfer process of reactants and products in the reaction process is favorably improved, and the selectivity of the catalyst is favorably improved.
The metal loaded catalyst is prepared by loading active components Rh or Ru on a carrier in a mist spraying mode. In the general impregnation method, in the active component loading process, in order to achieve the purpose of uniform distribution of the active components, multiple times of impregnation, multiple times of drying and multiple times of roasting are required, the loading process is long in time consumption and high in energy consumption, and impregnation waste liquid can be generated. And the active component loading can be completed by only one-time spraying by adopting a mist spraying mode, the loading process is simple, only one-time spraying, drying and roasting are needed, the preparation time of the catalyst is shortened, the energy consumption in the loading process is reduced, and meanwhile, the method can ensure that the active components are more uniformly distributed on the surface and in the pore channels of the carrier, so that the catalyst can keep higher activity and selectivity.
Wherein:
the template agent is n-butylamine or ethylenediamine, and the mass ratio of the alumina to the template agent is 100: 1-5.
The dosage of the active component is 0.5-1.5% of the mass of the carrier.
And (2) carrying out hydrogenation reaction by adopting a fixed bed hydrogenation reactor, wherein the hydrogenation reaction temperature is 90-160 ℃, and the hydrogenation reaction pressure is 4-6 MPa.
The liquid airspeed of the diisononyl phthalate is 0.2-1 h-1。
The volume ratio of the hydrogen to the diisononyl phthalate is 100-300: 1.
The preparation of the metal supported catalyst comprises the following steps:
(1) grinding alumina, mixing with a template agent, pressing for forming, drying, roasting, cooling and sieving to obtain modified alumina;
(2) atomizing and spraying chloride of the active component on the surface of the modified alumina, drying and roasting to obtain a catalyst precursor; and reducing the catalyst precursor in a hydrogen atmosphere to obtain the metal supported catalyst.
In the step (1), the drying temperature is 110-130 ℃, and preferably 120 ℃; the drying time is 1-3 hours, preferably 2 hours; the roasting temperature is 500-600 ℃, and preferably 550 ℃; the roasting time is 3-5 hours, preferably 4 hours; the mesh number of the sieve is 10-20 meshes.
In the step (2), the chloride of the active component is ruthenium chloride or rhodium chloride.
In the step (2), the drying temperature is 110-130 ℃, and preferably 120 ℃; the drying time is 3-5 hours, preferably 4 hours; heating to the roasting temperature of 350-450 ℃, and preferably 400 ℃; the roasting time is 3-5 hours, preferably 4 hours; the reduction temperature is 280-320 ℃, and the reduction time is 3-5 hours, preferably 4 hours.
The raw materials adopted by the invention are all commercial products.
The invention has the following beneficial effects:
the invention takes diisononyl phthalate and hydrogen as raw materials, and performs hydrogenation reaction under the action of a metal loaded catalyst which takes modified alumina as a carrier and Rh or Ru as an active component to obtain the environment-friendly plasticizer cyclohexane 1, 2-diisononyl phthalate. The catalyst adopts template agent to Al2O3After the carrier is treated, the chloride solution of Rh and Ru is loaded on the carrier in a mist spraying mode, and the metal loaded catalyst is obtained after roasting and reduction. The specific surface area of the carrier is improved, the pore structure in the carrier is improved through the modification of the template, the mass transfer process of reactants and products in the reaction process is favorably improved, and the selectivity of the catalyst is favorably improved.
The metal loaded catalyst is prepared by loading active components Rh or Ru on a carrier in a mist spraying mode. In the general impregnation method, in the active component loading process, in order to achieve the purpose of uniform distribution of the active components, multiple times of impregnation, multiple times of drying and multiple times of roasting are required, the loading process is long in time consumption and high in energy consumption, and impregnation waste liquid can be generated. And the active component loading can be completed by only one-time spraying by adopting a mist spraying mode, the loading process is simple, only one-time spraying, drying and roasting are needed, the preparation time of the catalyst is shortened, the energy consumption in the loading process is reduced, and meanwhile, the method can ensure that the active components are more uniformly distributed on the surface and in the pore channels of the carrier, so that the catalyst can keep higher activity and selectivity.
The invention adopts template agent to modify Al2O3The metal supported catalyst with higher activity and selectivity is prepared by combining the carrier and the mist spraying, so that the DINP conversion rate in the reaction can reach 100 percent, the DINCH selectivity can reach 99.9 percent, and the generation of impregnation waste liquid is avoided; and the content of byproducts in the product is low, so that the purification difficulty and energy consumption of subsequent products are effectively reduced.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
Weighing 100g Al2O3Grinding the mixture into powder, placing the powder in a kneading machine, mixing the powder with 3g of ethylenediamine, kneading the mixture uniformly, then carrying out extrusion forming in a double-screw extruder, placing the mixture in an oven, drying the mixture for 2 hours at the temperature of 120 ℃, placing the dried mixture in a muffle furnace, roasting the roasted mixture for 4 hours at the temperature of 550 ℃, naturally cooling the roasted mixture, and crushing and sieving the cooled mixture to obtain 10-20-mesh particles to obtain the catalyst carrier CA-1.
Example 2
100g of Al are weighed2O3Grinding the mixture into powder, placing the powder in a kneading machine, mixing the powder with 5g of ethylenediamine, kneading the mixture uniformly, extruding the mixture in a double-screw extruder for forming, placing the mixture in an oven for drying at 120 ℃ for 2 hours, placing the dried mixture in a muffle furnace for roasting at 550 ℃ for 4 hours, naturally cooling the roasted mixture, crushing and sieving the cooled mixture to obtain 10-20-mesh particles to obtain the catalyst carrier CA-2.
Example 3
100g of Al are weighed2O3Grinding the mixture into powder, placing the powder in a kneader, mixing the powder with 2g of n-butylamine, kneading the mixture uniformly, extruding the mixture in a double-screw extruder for forming, placing the mixture in an oven for drying at 120 ℃ for 2 hours, placing the dried mixture in a muffle furnace for roasting at 550 ℃ for 4 hours, naturally cooling the product, and crushing and sieving the product to obtain 10-20-mesh particles to obtain the catalyst carrier CA-3.
Example 4
100g of Al are weighed2O3Grinding the mixture into powder, placing the powder in a kneader, mixing the powder with 5g of n-butylamine, kneading the mixture uniformly, extruding the mixture in a double-screw extruder for forming, placing the mixture in an oven for drying at 120 ℃ for 2 hours, placing the dried mixture in a muffle furnace for roasting at 550 ℃ for 4 hours, naturally cooling the product, and crushing and sieving the product to obtain 10-20-mesh particles to obtain the catalyst carrier CA-4.
Example 5
100g of Al are weighed2O3Grinding the mixture into powder, placing the powder in a kneading machine, mixing the powder with 1g of ethylenediamine, kneading the mixture uniformly, extruding the mixture in a double-screw extruder for forming, placing the mixture in an oven for drying at 120 ℃ for 2 hours, placing the dried mixture in a muffle furnace for roasting at 550 ℃ for 4 hours, naturally cooling the roasted mixture, crushing and sieving the cooled mixture to obtain 10-20-mesh particles to obtain the catalyst carrier CA-5.
Example 6
100g of Al are weighed2O3Grinding the mixture into powder, placing the powder in a kneader, mixing the powder with 1g of n-butylamine, kneading the mixture uniformly, extruding the mixture in a double-screw extruder for forming, placing the mixture in an oven for drying at 120 ℃ for 2 hours, placing the dried mixture in a muffle furnace for roasting at 550 ℃ for 4 hours, naturally cooling the product, and crushing and sieving the product to obtain 10-20-mesh particles to obtain the catalyst carrier CA-6.
Examples 7 to 23
Respectively weighing 50g of the carrier obtained in the embodiments 1-6, atomizing 50ml of ruthenium chloride or rhodium chloride with different concentrations in an atomizing chamber, spraying the atomized ruthenium chloride or rhodium chloride on the surface of the carrier, drying for 4 hours at 120 ℃, setting a programmed temperature rise, and roasting for 4 hours at 400 ℃ to obtain catalyst precursors CAT-1-CAT-17 with different active component loading amounts (the proportion of active components in the weight of the carrier), wherein the specific conditions are shown in the following Table 1:
TABLE 1 Material parameters during catalyst preparation in examples 7-23
Examples 24 to 40
10mL of the catalyst precursor obtained in examples 7 to 23 was filled in a container having an inner diameter ofAnd (3) in a fixed bed-pipe reactor, filling the catalyst precursor with quartz sand up and down, introducing hydrogen at the flow rate of 120mL/min under normal pressure, and carrying out reduction activation for 4 hours at 300 ℃ to obtain the metal-supported catalyst. After the reduction was completed, the reaction system was slowly pressurized to the reaction pressure, followed by slowly raising the temperature to the reaction temperature. And (3) pumping the diisononyl phthalate raw material liquid into the reactor by a metering pump after stabilizing the temperature in advance, and contacting the diisononyl phthalate raw material liquid with hydrogen to carry out hydrogenation reaction. The reaction conditions are as follows: the reaction pressure is 6MPa, the bed reaction temperature is 150 ℃, and the liquid space velocity is 0.6h-1(Vol), hydrogen-material ratio of 250(Vol), cooling the hydrogenation mixed product, separating hydrogen in a gas-liquid separation tank to obtain hydrogenation reaction product plasticizer cyclohexane 1, 2-dimethylDiisononyl acid was analyzed and the results are shown in Table 2 below:
TABLE 2 data of the reaction results with different catalysts
Serial number
Catalyst precursor numbering
Conversion/% of DINP
DINCH selectivity/%)
Example 24
CAT-1
90.2
96.8
Example 25
CAT-2
98.6
95.0
Example 26
CAT-3
99.6
97.9
Example 27
CAT-4
90.0
96.5
Example 28
CAT-5
100
96.8
Example 29
CAT-6
90.0
98.2
Example 30
CAT-7
92.6
98.0
Example 31
CAT-8
100
99.9
Example 32
CAT-9
99.4
99.0
Example 33
CAT-10
97.8
98.2
Example 34
CAT-11
99.5
98.8
Example 35
CAT-12
99.0
97.8
Example 36
CAT-13
98.2
98.0
Example 37
CAT-14
99.6
99.1
Example 38
CAT-15
100
99.0
Example 39
CAT-16
100
99.2
Example 40
CAT-17
100
98.9
Examples 41 to 51
The catalyst precursor obtained in example 14 was charged in a fixed bed reactor having an inner diameter ofThe catalyst precursor is filled with inert broken ceramic rings up and down, hydrogen is introduced at the flow rate of 120mL/min under normal pressure, and reduction activation is carried out for 4 hours at the temperature of 280 ℃, so that the metal supported catalyst with the Ru loading of 1.2% is obtained. After the reduction is finished, slowly boosting the pressure of the reaction systemTo reaction pressure and then slowly warmed to reaction temperature. After the temperature is stabilized in advance, pumping diisononyl phthalate raw material liquid into a reactor by a metering pump for reaction, and investigating reaction results under different hydrogenation reaction conditions, wherein the data are shown in a table 3:
TABLE 3 reaction results data for different hydrogenation reaction conditions
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