WO2022161163A1 - Production process for industrial prenol - Google Patents

Production process for industrial prenol Download PDF

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WO2022161163A1
WO2022161163A1 PCT/CN2022/071497 CN2022071497W WO2022161163A1 WO 2022161163 A1 WO2022161163 A1 WO 2022161163A1 CN 2022071497 W CN2022071497 W CN 2022071497W WO 2022161163 A1 WO2022161163 A1 WO 2022161163A1
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prenol
paraformaldehyde
isobutene
basic
depolymerization
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PCT/CN2022/071497
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French (fr)
Chinese (zh)
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王济群
刘世杰
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天津安德胜科技服务有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/02—Acyclic alcohols with carbon-to-carbon double bonds
    • C07C33/025—Acyclic alcohols with carbon-to-carbon double bonds with only one double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
    • C07C45/513—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an etherified hydroxyl group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
    • C07C47/04—Formaldehyde

Definitions

  • the invention belongs to the technical field of organic synthesis, and in particular relates to a production process of industrialized prenol.
  • Prenol namely 3-Methyl-3-buten-1-ol (3-Methyl-3-buten-1-ol), relative molecular weight 86.13, density 0.851g/cm 3 (20°C), boiling point 130 ⁇ 132°C(760mmHg), flash point 42°C, colorless transparent liquid.
  • Isopentenol is mainly used in the synthesis of methyl beating acid, the intermediate of high-efficiency and low-toxic pesticide pyrethroid insecticides, and its downstream products, permethrin, DV chrysanthyl chloride (dichlorochrysanthemum chloride), etc., isopentyl Enols are also raw materials and intermediates for the production of citral, menthol and vitamin E. With the continuous research and maturity of the synthesis process of prenol, and the continuous deepening of application development, its application scope in pesticides will continue to expand, and the market demand will also increase significantly.
  • C5 olefins are by-products of the high-temperature cracking of petroleum hydrocarbons to produce ethylene.
  • the rapid development of my country's ethylene industry makes C5 olefins increasingly important resources that cannot be ignored.
  • the utilization of C5 resources has reached 2.37 million tons.
  • Actively exploring the application fields of single components in C5 olefins such as isoprene is an effective way to realize high-value utilization of C5 fractions, and improving the utilization rate of C5 resources has good economic and social benefits.
  • Prenol is the raw material for the preparation of methyl beating acid, an important intermediate of pyrethroid pesticides.
  • the basic chemical raw material C5 is used to synthesize prenol, which finds a new way for the efficient utilization of C5 resources.
  • the rapid development of pyrethroids has provided a greater market demand for enol products with high purity and low price.
  • the synthetic process routes of prenol can be divided into the following three categories: the Prins method (Prins), the isoprene method, and the methyl butenol isomerization method.
  • the current three synthetic routes have their own lengths and shortcomings.
  • the isoprene method is more suitable for my country's national conditions, but this process requires catalytic hydrogenation in the presence of precious metals, the process is more complicated, and the production cost is higher than the above two methods. Therefore, it is particularly important to study a process with simple process and good product quality.
  • the object of the present invention is to provide a kind of production technique of industrialized prenyl alcohol, the production technique in the present invention does not use catalyzer, and can be produced continuously, the yield of the prenyl alcohol product obtained is high, the purity is high, especially isoprenol The color of the pentenol product is excellent.
  • the invention provides a kind of production process of industrialized prenol, comprising the following steps:
  • the basic isobutene includes isobutene and an alkaline medium, and the pH value of the basic isobutene is 7.4-7.8.
  • the degree of polymerization of the paraformaldehyde is 5-40, and the particle size of the paraformaldehyde is 300-900 ⁇ m.
  • the temperature of depolymerization in the step A) is 120-220° C.; the pressure of depolymerization is 0.6 ⁇ 10 7 to 1.4 ⁇ 10 7 Pa; and the time of depolymerization is 30-80 min.
  • the molar ratio of the basic isobutylene to the paraformaldehyde is (10-30):1.
  • the temperature of the Prince reaction is 200 to 295° C.
  • the pressure of the Prince reaction is 1.0 ⁇ 10 7 to 1.5 ⁇ 10 7 Pa
  • the time of the Prince reaction is 50 to 100 min.
  • the alkaline medium is sodium hydroxide and/or potassium hydroxide.
  • a suspension of paraformaldehyde particles is formed in liquid alkaline isobutylene, followed by depolymerization and Prince reaction.
  • the depolymerization is carried out in a first plug flow reactor, and the Prince reaction is carried out in a second plug flow reactor.
  • the height of the first plug flow reactor is 3-9 meters, and the diameter is 1-2 meters;
  • the height of the second plug flow reactor is 15-20 meters, and the diameter is 1-2 meters.
  • the invention provides an industrialized production process for prenol, comprising the following steps: A) depolymerizing paraformaldehyde to generate free formaldehyde; B) contacting the free formaldehyde with alkaline isobutylene to carry out Prince The reaction is carried out to obtain prenol; the basic isobutene includes isobutene and an alkaline medium, and the pH value of the basic isobutene is 7.4-7.8.
  • the raw material of the present invention is basic isobutene, and the alkali in the basic isobutene can neutralize the formic acid generated by the disproportionation of formaldehyde in the addition reaction, and effectively prevent the side reaction of isobutene dimerization to generate dimethylhexene and trimethylcyclopentane ; thereby improving the chromaticity of the prenol product to obtain colorless and transparent prenol.
  • the production technique in the present invention also has the following advantages:
  • the process in the present invention has high selectivity, high yield and no pollutants.
  • the prenol production process provided by the present invention has no solvent, no organic matter and no aqueous solution. Such a process can obtain a high-purity and pollution-free product by avoiding the separation of prenol.
  • the prenol production process of the present invention has no reaction catalyst.
  • the operation of separating the catalyst from the mixture of the prenol and the catalyst is avoided, and the use of an expensive catalyst is also avoided, which greatly reduces the production cost.
  • the present invention is the production of prenol in a simple apparatus. Operating parameters (temperature and pressure only) are easy to control and modify. Continuous recovery of unreacted material in the reactor optimizes material consumption.
  • alkali is added to isobutene to make the generated prenol colorless and transparent.
  • the production process of the present invention can make the production continuous, and make the device simple and easy to operate and maintain.
  • Fig. 1 is the process flow diagram of the production technique of industrialized prenyl alcohol in the present invention
  • 10 is the material tank
  • 12 and 14 are the feeding lines
  • 40 is the first heat exchanger
  • 20 is the first reactor
  • 22 is the bottom inlet of the first reactor
  • 24 is the top outlet of the first reactor
  • 50 is the first reactor.
  • Two heat exchangers 30 is the second reactor
  • 32 is the bottom inlet of the second reactor
  • 34 is the top of the second reactor
  • 36 is the top outlet of the second reactor.
  • the invention provides a kind of production process of industrialized prenol, comprising the following steps:
  • the basic isobutene includes isobutene and an alkaline medium, and the pH value of the basic isobutene is 7.4-7.8.
  • the production process in the present invention mainly includes two stages:
  • the first stage depolymerization of paraformaldehyde to generate free formaldehyde;
  • the second stage isobutene reacts with formaldehyde to generate prenol.
  • the production process of the present invention including the above two stages is carried out using the production device shown in FIG. 1 .
  • the alkaline isobutylene solution and the paraformaldehyde are added into the material tank 10 through the pipeline 12 and the pipeline 14, respectively.
  • the alkaline isobutylene-paraformaldehyde suspension forms a uniform phase
  • the material tank 10 is connected to the pump to increase the pressure in the storage tank.
  • the pressure reaches a certain value, the suspension is added to the depolymerization reactor.
  • the amount of basic isobutene in the suspension must be far greater than the amount of paraformaldehyde.
  • basic isobutene In addition to reacting with formaldehyde, basic isobutene is also a carrier for transporting paraformaldehyde to the depolymerization reactor, and excess basic isobutene can also ensure delivery. At the same time, basic isobutylene has an effective dispersing effect on paraformaldehyde.
  • the alkaline isobutene is added with an alkaline medium in isobutene to form an alkaline isobutene solution with a pH value between 7.4 and 7.8.
  • the alkaline medium is preferably sodium hydroxide and/or potassium hydroxide.
  • the present invention has no particular limitation on the amount of the alkaline medium, and the pH value of the isobutene solution can be adjusted within the range of 7.4-7.8.
  • the paraformaldehyde is solid paraformaldehyde, and the degree of polymerization of the paraformaldehyde is preferably 4-50, more preferably 10-40, most preferably 20-30, preferably, in the present invention In the embodiment of , it can be 30; the particle size of the paraformaldehyde is preferably 300-900 ⁇ m, more preferably 400-800 ⁇ m, and most preferably 500-700 ⁇ m.
  • the polymerization grade and particle size of paraformaldehyde affect the depolymerization reaction. Because high molecular weight polymer depolymerization requires a higher reactor to depolymerize all paraformaldehyde, do not choose too high molecular weight paraformaldehyde.
  • the depolymerization of paraformaldehyde in the depolymerization reactor should reach more than 90%, and a small amount of unreacted polymer should be left to avoid the direct polymerization of formaldehyde and basic isobutylene in the depolymerization reactor.
  • the particle size of paraformaldehyde has an effect on the concentration of paraformaldehyde, which in turn affects the average yield of prenol.
  • the experimental results show that when the concentration of paraformaldehyde is 91%, the average yield of prenol is the best.
  • the molar ratio of the basic isobutene to paraformaldehyde is (10-30):1, preferably (12-25):1, more preferably (15-20):1, specifically, In an embodiment of the present invention, it may be 12:1.
  • the temperature of the alkaline isobutylene and paraformaldehyde suspension increases in the heat exchanger 40, Part of the paraformaldehyde is depolymerized into free formaldehyde.
  • the temperature of the suspension is 120-220°C. At this temperature, the suspension enters the reactor from the bottom end 22 of the first reactor, and paraformaldehyde is depolymerized into free formaldehyde in the first reactor.
  • the outlet temperature of the reaction mixture of the reactor 20 is between 120 and 190°C.
  • the temperature of the alkaline isobutylene-paraformaldehyde suspension entering the reactor did not have much effect on the outlet temperature.
  • the first reactor 20 is preferably a plug flow reactor, and the design of the depolymerization reactor takes into account the depolymerization power and higher productivity, and the annual production capacity of 3,000 to 5,000 tons of prenyl alcohol
  • the designed length of the depolymerization reactor is between 3 meters and 9 meters, preferably between 4 and 8 meters, and more preferably between 5 and 7 meters. Specifically, in the embodiment of the present invention, it can be 5.5 meters. ; the corresponding diameter is between 1 m and 2 m, preferably 1.5 m.
  • the length and height of the depolymerization reactor at the above-mentioned yield should be selected within this range, and the depolymerization reaction can proceed in the correct direction.
  • the first reactor uses pneumatic bubbling combined with mechanical stirring to promote the mixing and contact of materials.
  • the depolymerization temperature is preferably 120-220°C, more preferably 150-200°C, and most preferably 160-190°C;
  • the depolymerization pressure is preferably 0.6 ⁇ 10 7 ⁇ 1.4 ⁇ 10 7 Pa, more preferably 0.8 ⁇ 10 7 to 1.2 ⁇ 10 7 Pa, most preferably 0.9 ⁇ 10 7 to 1.0 ⁇ 10 7 Pa, specifically, in the embodiment of the present invention, it can be 0.7 ⁇ 10 7 Pa;
  • the depolymerization time is preferably 30 to 80 minutes, more preferably 40 to 70 minutes, and most preferably 50 to 60 minutes. Specifically, in the embodiment of the present invention, it may be 50 minutes.
  • the basic isobutylene and formaldehyde mixture at a temperature of 120-190°C (below this temperature, no Prince reaction of olefins and aldehydes occurs) enters the second heat exchanger 50 to further increase the temperature to 200-290°C °C, when the pressure is 1.0 ⁇ 10 7 to 1.5 ⁇ 10 7 Pa, the basic isobutene-formaldehyde mixture enters the second reactor 30 for the addition reaction of isobutene and formaldehyde to generate prenol.
  • the mixture enters the reactor 30 from the bottom 32 of the reactor. This condition is favorable for the formation of prenol and minimizes the formation of by-products.
  • the second reactor 30 is preferably a plug flow reactor.
  • the length of the reactor is 15-20 meters, and the diameter is 1-2 meters, preferably 1.3-1.5 meters.
  • the addition reaction occurs under adiabatic conditions.
  • the addition reaction is an exothermic process, and a slight increase in the temperature at the end of the reaction facilitates the further formation of prenol.
  • the top 34 of the second reactor 30 produces a mixture containing prenol, unreacted isobutene, a small amount of unreacted formaldehyde, and a very small amount of side reactants.
  • the generated prenyl alcohol and the above-mentioned unreacted raw material mixture are sent out from the outlet 36 of the second reactor 30, and the separation of the mixture is easier, because the main components in the raw material mixture are basic isobutene and formaldehyde, without catalyst or solvent;
  • the feed mixture return system can optimize the use of process feedstocks.
  • the prenol is separated from the mixture at the outlet of the reactor 30, mainly by reducing the temperature of the mixture to below the boiling point of the prenol.
  • the temperature of the mixture is lowered to ⁇ 130°C to liquefy the prenol.
  • the other reactants are still in the gas phase.
  • the prenol containing the heavy components is sent to distillation and purification.
  • the temperature of the Prince reaction is preferably 200-295°C, more preferably 230-280°C, most preferably 250-270°C, specifically, in the embodiment of the present invention, it can be 270°C °C;
  • the pressure of the Prince reaction is 1.0 ⁇ 10 7 to 1.5 ⁇ 10 7 Pa, more preferably 1.1 ⁇ 10 7 to 1.4 ⁇ 10 7 Pa, most preferably 1.2 ⁇ 10 7 to 1.3 ⁇ 10 7 Pa, Specifically, in the embodiment of the present invention, it can be 1.15 ⁇ 10 7 Pa;
  • the time of the Prince reaction is 50-100 min, more preferably 60-90 min, and most preferably 70-80 min. In the embodiment of the present invention, it may be 75min.
  • the invention provides an industrialized production process for prenol, comprising the following steps: A) depolymerizing paraformaldehyde to generate free formaldehyde; B) contacting the free formaldehyde with alkaline isobutylene to carry out Prince The reaction is carried out to obtain prenol; the basic isobutene includes isobutene and an alkaline medium, and the pH value of the basic isobutene is 7.4-7.8.
  • the raw material of the present invention is basic isobutene, and the alkali in the basic isobutene can neutralize the formic acid generated by the disproportionation of formaldehyde in the addition reaction, and effectively prevent the side reaction of isobutene dimerization to generate dimethylhexene and trimethylcyclopentane ; thereby improving the chromaticity of the prenol product to obtain colorless and transparent prenol.
  • the production technique in the present invention also has the following advantages:
  • the process in the present invention has high selectivity, high yield and no pollutants.
  • the prenol production process provided by the present invention has no solvent, no organic matter and no aqueous solution. Such a process can obtain a high-purity and pollution-free product by avoiding the separation of prenol.
  • the prenol production process of the present invention has no reaction catalyst.
  • the operation of separating the catalyst from the mixture of the prenol and the catalyst is avoided, and the use of an expensive catalyst is also avoided, which greatly reduces the production cost.
  • the present invention is the production of prenol in a simple apparatus. Operating parameters (temperature and pressure only) are easy to control and modify. Continuous recovery of unreacted material in the reactor optimizes material consumption.
  • alkali is added to isobutene to make the generated prenol colorless and transparent.
  • the production process of the present invention can make the production continuous, and make the device simple and easy to operate and maintain.
  • the basic isobutylene and paraformaldehyde mixture enters the storage tank, wherein the paraformaldehyde has a medium degree of polymerization of 30 and a particle size of 400-800 microns.
  • the molar ratio of basic isobutylene and paraformaldehyde was 12:1.
  • the mixed suspension of basic isobutylene and paraformaldehyde is kept in a stirred state in the tank, and the mixture is sent to a heat exchanger by a pump to make the temperature of the mixture reach 190 °C, and the heated suspension is sent to a height of 5.5 meters and a diameter of 1.5 meters.
  • the mixture When the mixture enters the second heat exchanger and is heated to 270°C, it is sent to the second plug flow reactor with a height of 20 meters and a diameter of 1.3 meters, in which isobutene and formaldehyde Prince react to form isobutene. Pentenol, alkali neutralizes formic acid and reduces the side reaction of isobutene dimerization.
  • the Prince reaction was carried out at a pressure of 115 bar for 75 minutes.
  • the end point of the Prince reaction is to obtain a basic isobutene and prenol heavy component mixture at a temperature of 270°C at the top of the reactor.
  • the mixture contains unreacted basic isobutene, prenol and unreacted formaldehyde.
  • the yield of prenol based on isobutene is equal to 89%, the unreacted residual formaldehyde in the mixture is 11% (based on isobutene)
  • the mixture containing prenol can be separated from the mixture when the temperature is cooled to 25°C Prenol.
  • the purity of the prenol in the reacted material is 98.5-99 percent, contains 1.5-1 percent of impurities, and is transparent in color.
  • Prenyl alcohol was prepared according to the method in Example 1, except that the temperature and pressure of depolymerization were carried out according to Table 1.
  • Prenyl alcohol was prepared according to the method in Example 1, except that the particle size and concentration of paraformaldehyde in Examples 5-8 were carried out according to Table 2.
  • Example Paraformaldehyde size ( ⁇ m) Paraformaldehyde concentration (%) Average yield of prenol (%) 5 >1500 97 ⁇ 80 6 900 ⁇ 1500 94.2 83 7 300 ⁇ 900 91 90 8 ⁇ 300 ⁇ 91 **
  • the concentration of paraformaldehyde with particle size larger than 900 microns is too high, and the concentration of paraformaldehyde below 300 microns is low.
  • the concentration of paraformaldehyde is 91.0%; the particle size of paraformaldehyde has an effect on the concentration of paraformaldehyde; the concentration of paraformaldehyde has an effect on the average yield of prenol.
  • Prenyl alcohol was prepared according to the method in Example 1, except that the raw material in Comparative Example 1 was isobutene without alkali.
  • the purity of prenol in the reacted material was 98%, containing 2% impurities, and the color was yellow.

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Abstract

The present invention provides a production process for industrial prenol, comprising the following steps: A) performing depolymerization on polyoxymethylene to generate free formaldehyde; and B) contacting the free formaldehyde with basic isobutylene for performing the Prins reaction to obtain prenol, wherein the basic isobutylene consists of isobutylene and an alkaline medium, and a pH value of the basic isobutylene is 7.4-7.8. The raw material of the present invention is basic isobutylene, and the base in basic isobutylene can neutralize formic acid generated by means of the disproportionation of formaldehyde in an addition reaction and effectively prevent a side reaction of the dimerization of isobutylene by which dimethylhexene and trimethylcyclopentane are generated, thereby improving the chroma of a prenol product to yield colorless and transparent prenol.

Description

一种工业化异戊烯醇的生产工艺A kind of production technology of industrialized prenol
本申请要求于2021年01月26日提交中国专利局、申请号为202110103340.7、发明名称为“一种工业化异戊烯醇的生产工艺”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application filed on January 26, 2021 with the application number 202110103340.7 and the invention titled "An Industrialized Production Process of Prenol", the entire contents of which are incorporated by reference in in this application.
技术领域technical field
本发明属于有机合成技术领域，尤其涉及一种工业化异戊烯醇的生产工艺。The invention belongs to the technical field of organic synthesis, and in particular relates to a production process of industrialized prenol.
背景技术Background technique
异戊烯醇，即3-甲基-3-丁烯-1-醇(3-Methyl-3-buten-1-ol)，相对分子量86.13，密度0.851g/cm 3(20℃)，沸点130～132℃(760mmHg)，闪点42℃，为无色透明液体。异戊烯醇主要用于合成高效低毒农药拟除虫菊酯杀虫剂的中间体贲亭酸甲酯，以及其下游产品二氯菊酸酯、DV菊酰氯(二氯菊酰氯)等，异戊烯醇也是生产柠檬醛，薄荷醇及维生素E的原料及中间体。随着异戊烯醇合成工艺的不断研究与成熟，以及应用开发的不断深入，其在农药中的应用范围将不断扩大，市场需求量也将大幅上升。 Prenol, namely 3-Methyl-3-buten-1-ol (3-Methyl-3-buten-1-ol), relative molecular weight 86.13, density 0.851g/cm 3 (20℃), boiling point 130 ～132℃(760mmHg), flash point 42℃, colorless transparent liquid. Isopentenol is mainly used in the synthesis of methyl beating acid, the intermediate of high-efficiency and low-toxic pesticide pyrethroid insecticides, and its downstream products, permethrin, DV chrysanthyl chloride (dichlorochrysanthemum chloride), etc., isopentyl Enols are also raw materials and intermediates for the production of citral, menthol and vitamin E. With the continuous research and maturity of the synthesis process of prenol, and the continuous deepening of application development, its application scope in pesticides will continue to expand, and the market demand will also increase significantly.
C5烯烃是石油烃高温裂解制取乙烯过程中的副产品，我国乙烯工业的高速发展使得C5烯烃日益成为不可忽视的重要资源。2010年C5资源的利用量已达到237万吨。积极开拓异戊二烯等C5烯烃中单组份的应用领域，是实现C5馏分高值化利用的有效途径，提高C5资源的利用率具有很好的经济效益和社会效益。异戊烯醇是制备拟除虫菊酯类农药重要中间体贲亭酸甲酯的原料，用基础化工原料C5来合成异戊烯醇，为C5资源的高效利用找到了新的途径。拟除虫菊酯的快速发展，为纯度高、价格低的烯醇产品提供了更大的市场需求。C5 olefins are by-products of the high-temperature cracking of petroleum hydrocarbons to produce ethylene. The rapid development of my country's ethylene industry makes C5 olefins increasingly important resources that cannot be ignored. In 2010, the utilization of C5 resources has reached 2.37 million tons. Actively exploring the application fields of single components in C5 olefins such as isoprene is an effective way to realize high-value utilization of C5 fractions, and improving the utilization rate of C5 resources has good economic and social benefits. Prenol is the raw material for the preparation of methyl beating acid, an important intermediate of pyrethroid pesticides. The basic chemical raw material C5 is used to synthesize prenol, which finds a new way for the efficient utilization of C5 resources. The rapid development of pyrethroids has provided a greater market demand for enol products with high purity and low price.
根据反应原料的不同，异戊烯醇的合成工艺路线可分为以下三类：普林斯法(Prins)、异戊二烯法、甲基丁烯醇异构法。目前的3种合成路线各有长短，异戊二烯法比较适合我国的国情，但该工艺须在贵金属存在的情况下进行催化加氢，工艺较复杂，生产成本高于以上2种方法。因此，研究一种工艺简单且产品质量好的工艺尤为重要。According to the different reaction raw materials, the synthetic process routes of prenol can be divided into the following three categories: the Prins method (Prins), the isoprene method, and the methyl butenol isomerization method. The current three synthetic routes have their own lengths and shortcomings. The isoprene method is more suitable for my country's national conditions, but this process requires catalytic hydrogenation in the presence of precious metals, the process is more complicated, and the production cost is higher than the above two methods. Therefore, it is particularly important to study a process with simple process and good product quality.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于提供一种工业化异戊烯醇的生产工艺，本发明中的生产 工艺不使用催化剂、且能够连续化生产、得到的异戊烯醇产品收率高、纯度高，尤其是异戊烯醇产品的色度优良。The object of the present invention is to provide a kind of production technique of industrialized prenyl alcohol, the production technique in the present invention does not use catalyzer, and can be produced continuously, the yield of the prenyl alcohol product obtained is high, the purity is high, especially isoprenol The color of the pentenol product is excellent.
本发明提供一种工业化异戊烯醇的生产工艺，包括以下步骤：The invention provides a kind of production process of industrialized prenol, comprising the following steps:
A)多聚甲醛进行解聚生成游离的甲醛；A) depolymerization of paraformaldehyde generates free formaldehyde;
B)将所述游离的甲醛与碱性异丁烯接触，进行普林斯反应，得到异戊烯醇；B) contacting described free formaldehyde with basic isobutene, carries out Prince reaction, obtains prenol;
所述碱性异丁烯为包括异丁烯和碱性介质，所述碱性异丁烯的pH值为7.4～7.8。The basic isobutene includes isobutene and an alkaline medium, and the pH value of the basic isobutene is 7.4-7.8.
优选的，所述多聚甲醛的聚合度为5～40，所述多聚甲醛的粒径为300～900μm。Preferably, the degree of polymerization of the paraformaldehyde is 5-40, and the particle size of the paraformaldehyde is 300-900 μm.
优选的，所述步骤A)中解聚的温度为120～220℃；所述解聚的压力为0.6×10 7～1.4×10 7Pa；所述解聚的时间为30～80min。 Preferably, the temperature of depolymerization in the step A) is 120-220° C.; the pressure of depolymerization is 0.6×10 7 to 1.4×10 7 Pa; and the time of depolymerization is 30-80 min.
优选的，所述碱性异丁烯与多聚甲醛的摩尔比为(10～30)：1。Preferably, the molar ratio of the basic isobutylene to the paraformaldehyde is (10-30):1.
优选的，所述普林斯反应的温度为200～295℃，所述普林斯反应的压力为1.0×10 7～1.5×10 7Pa；所述普林斯反应的时间为50～100min。 Preferably, the temperature of the Prince reaction is 200 to 295° C., the pressure of the Prince reaction is 1.0×10 7 to 1.5×10 7 Pa, and the time of the Prince reaction is 50 to 100 min.
优选的，所述碱性介质为氢氧化钠和/或氢氧化钾。Preferably, the alkaline medium is sodium hydroxide and/or potassium hydroxide.
优选的，在液态的碱性异丁烯中形成多聚甲醛颗粒的悬浮液，再进行解聚和普林斯反应。Preferably, a suspension of paraformaldehyde particles is formed in liquid alkaline isobutylene, followed by depolymerization and Prince reaction.
优选的，所述解聚在第一柱塞流反应器内进行，所述普林斯反应在第二柱塞流反应器内进行。Preferably, the depolymerization is carried out in a first plug flow reactor, and the Prince reaction is carried out in a second plug flow reactor.
优选的，所述第一柱塞流反应器的高度为3～9米，直径为1～2米；Preferably, the height of the first plug flow reactor is 3-9 meters, and the diameter is 1-2 meters;
所述第二柱塞流反应器的高度为15～20米，直径为1～2米。The height of the second plug flow reactor is 15-20 meters, and the diameter is 1-2 meters.
本发明提供了一种工业化异戊烯醇的生产工艺，包括以下步骤：A)多聚甲醛进行解聚生成游离的甲醛；B)将所述游离的甲醛与碱性异丁烯接触，进行普林斯反应，得到异戊烯醇；所述碱性异丁烯为包括异丁烯和碱性介质，所述碱性异丁烯的pH值为7.4～7.8。本发明的原料为碱性异丁烯，碱性异丁烯中的碱可以中和加成反应中甲醛歧化生成的甲酸，并且有效阻止异丁烯二聚生成二甲基己烯和三甲基环戊烷的副反应；从而提高异戊烯醇产品的色度，得到无色透明的异戊烯醇。The invention provides an industrialized production process for prenol, comprising the following steps: A) depolymerizing paraformaldehyde to generate free formaldehyde; B) contacting the free formaldehyde with alkaline isobutylene to carry out Prince The reaction is carried out to obtain prenol; the basic isobutene includes isobutene and an alkaline medium, and the pH value of the basic isobutene is 7.4-7.8. The raw material of the present invention is basic isobutene, and the alkali in the basic isobutene can neutralize the formic acid generated by the disproportionation of formaldehyde in the addition reaction, and effectively prevent the side reaction of isobutene dimerization to generate dimethylhexene and trimethylcyclopentane ; thereby improving the chromaticity of the prenol product to obtain colorless and transparent prenol.
另外，本发明中的生产工艺还具有以下优点：In addition, the production technique in the present invention also has the following advantages:
1.本发明中的工艺具有高选择性、高收率，没有污染物。1. The process in the present invention has high selectivity, high yield and no pollutants.
2.本发明提供的异戊烯醇生产工艺没有溶剂、没有有机物及水溶液。这样的工艺避免异戊烯醇分离操作即可获得高纯度及无污染的产品。2. The prenol production process provided by the present invention has no solvent, no organic matter and no aqueous solution. Such a process can obtain a high-purity and pollution-free product by avoiding the separation of prenol.
3.本发明异戊烯醇生产工艺没有反应催化剂。避免了异戊烯醇与催化剂混合物中分离催化剂的操作，也避免使用昂贵催化剂，极大降低生产成本。3. The prenol production process of the present invention has no reaction catalyst. The operation of separating the catalyst from the mixture of the prenol and the catalyst is avoided, and the use of an expensive catalyst is also avoided, which greatly reduces the production cost.
4.本发明是在简单的装置中生产异戊烯醇。操作参数(仅温度和压力)容易控制及修改。在反应器中连续回收未反应物，优化物料消耗。4. The present invention is the production of prenol in a simple apparatus. Operating parameters (temperature and pressure only) are easy to control and modify. Continuous recovery of unreacted material in the reactor optimizes material consumption.
5.本发明中异丁烯加碱，使生成的异戊烯醇无色透明。5. In the present invention, alkali is added to isobutene to make the generated prenol colorless and transparent.
6.本发明下生产工艺可以使生产连续化，使装置简单易于操作和维修管理。6. The production process of the present invention can make the production continuous, and make the device simple and easy to operate and maintain.
附图说明Description of drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据提供的附图获得其他的附图。In order to explain the embodiments of the present invention or the technical solutions in the prior art more clearly, the following briefly introduces the accompanying drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only It is an embodiment of the present invention. For those of ordinary skill in the art, other drawings can also be obtained according to the provided drawings without creative work.
图1为本发明中工业化异戊烯醇的生产工艺的工艺流程图；Fig. 1 is the process flow diagram of the production technique of industrialized prenyl alcohol in the present invention;
其中，10为物料罐，12和14为加料管线，40为第一换热器，20为第一反应器，22为第一反应器底部入口，24为第一反应器顶部出口，50为第二换热器，30为第二反应器，32为第二反应器底部入口，34为第二反应器顶部，36为第二反应器顶部出口。Wherein, 10 is the material tank, 12 and 14 are the feeding lines, 40 is the first heat exchanger, 20 is the first reactor, 22 is the bottom inlet of the first reactor, 24 is the top outlet of the first reactor, and 50 is the first reactor. Two heat exchangers, 30 is the second reactor, 32 is the bottom inlet of the second reactor, 34 is the top of the second reactor, and 36 is the top outlet of the second reactor.
具体实施方式Detailed ways
本发明提供了一种工业化异戊烯醇的生产工艺，包括以下步骤：The invention provides a kind of production process of industrialized prenol, comprising the following steps:
A)多聚甲醛进行解聚生成游离的甲醛；A) depolymerization of paraformaldehyde generates free formaldehyde;
B)将所述游离的甲醛与碱性异丁烯接触，进行普林斯反应，得到异戊烯醇；B) contacting described free formaldehyde with basic isobutene, carries out Prince reaction, obtains prenol;
所述碱性异丁烯为包括异丁烯和碱性介质，所述碱性异丁烯的pH值为7.4～7.8。The basic isobutene includes isobutene and an alkaline medium, and the pH value of the basic isobutene is 7.4-7.8.
本发明中的生产工艺主要包括两个阶段：The production process in the present invention mainly includes two stages:
第一阶段：多聚甲醛解聚生成游离的甲醛；The first stage: depolymerization of paraformaldehyde to generate free formaldehyde;
第二阶段：异丁烯同甲醛反应生成异戊烯醇。The second stage: isobutene reacts with formaldehyde to generate prenol.
本发明包括上述两个阶段的生产工艺采用图1所示的生产装置进行。The production process of the present invention including the above two stages is carried out using the production device shown in FIG. 1 .
本发明优选将碱性异丁烯溶液和多聚甲醛分别经管线12和管线14将物料加入物料罐10内，在罐内搅拌器的搅拌作用下，碱性异丁烯-多聚甲醛悬浮液形成均匀相，同时物料罐10连接泵，增加储罐内压力，当压力达到一定值时，悬浮液加入解聚反应器。悬浮液中碱性异丁烯的量一定要远超多聚甲醛的量。碱性异丁烯除与甲醛反应外也是输送多聚甲醛到解聚反应器的载体，过量的碱性异丁烯也可以确保输送。同时碱性异丁烯对多聚甲醛起有效的分散作用。In the present invention, preferably, the alkaline isobutylene solution and the paraformaldehyde are added into the material tank 10 through the pipeline 12 and the pipeline 14, respectively. Under the stirring action of the stirrer in the tank, the alkaline isobutylene-paraformaldehyde suspension forms a uniform phase, At the same time, the material tank 10 is connected to the pump to increase the pressure in the storage tank. When the pressure reaches a certain value, the suspension is added to the depolymerization reactor. The amount of basic isobutene in the suspension must be far greater than the amount of paraformaldehyde. In addition to reacting with formaldehyde, basic isobutene is also a carrier for transporting paraformaldehyde to the depolymerization reactor, and excess basic isobutene can also ensure delivery. At the same time, basic isobutylene has an effective dispersing effect on paraformaldehyde.
在本发明中，所述碱性异丁烯是在异丁烯内加入碱性介质，形成pH值在7.4～7.8之间的碱性异丁烯溶液。In the present invention, the alkaline isobutene is added with an alkaline medium in isobutene to form an alkaline isobutene solution with a pH value between 7.4 and 7.8.
在本发明中，所述碱性介质优选为氢氧化钠和/或氢氧化钾。本发明对所述碱性介质的用量没有特殊的限制，能够将所述异丁烯溶液的pH值调节至7.4～7.8这一范围内即可。In the present invention, the alkaline medium is preferably sodium hydroxide and/or potassium hydroxide. The present invention has no particular limitation on the amount of the alkaline medium, and the pH value of the isobutene solution can be adjusted within the range of 7.4-7.8.
在本发明中，所述多聚甲醛为固态多聚甲醛，所述多聚甲醛的聚合度优选为4～50，更优选为10～40，最优选为20～30，优选的，在本发明的实施例中，可以是30；所述多聚甲醛的粒径优选为300～900μm，更优选为400～800μm，最优选为500～700μm。In the present invention, the paraformaldehyde is solid paraformaldehyde, and the degree of polymerization of the paraformaldehyde is preferably 4-50, more preferably 10-40, most preferably 20-30, preferably, in the present invention In the embodiment of , it can be 30; the particle size of the paraformaldehyde is preferably 300-900 μm, more preferably 400-800 μm, and most preferably 500-700 μm.
本发明研究发现，多聚甲醛的聚合等级及颗粒度影响解聚反应。因高分子量聚合物解聚需要较高的反应器全部解聚多聚甲醛，因此不要选择太高分子量多聚甲醛。应该使多聚甲醛在解聚反应器内解聚达到90％以上，并留有少量未反应聚合物避免生成的甲醛与碱性异丁烯直接在解聚反应器内聚合。多聚甲醛的颗粒尺寸大小对多聚甲醛的浓度产生影响，进而影响异戊烯醇的平均收率。实验结果表明，多聚甲醛的浓度为91％时，异戊烯醇的平均收率最佳。According to the research of the present invention, it is found that the polymerization grade and particle size of paraformaldehyde affect the depolymerization reaction. Because high molecular weight polymer depolymerization requires a higher reactor to depolymerize all paraformaldehyde, do not choose too high molecular weight paraformaldehyde. The depolymerization of paraformaldehyde in the depolymerization reactor should reach more than 90%, and a small amount of unreacted polymer should be left to avoid the direct polymerization of formaldehyde and basic isobutylene in the depolymerization reactor. The particle size of paraformaldehyde has an effect on the concentration of paraformaldehyde, which in turn affects the average yield of prenol. The experimental results show that when the concentration of paraformaldehyde is 91%, the average yield of prenol is the best.
在本发明中，所述碱性异丁烯与多聚甲醛的摩尔比为(10～30)：1，优选为(12～25)：1，更优选为(15～20)：1，具体的，在本发明的实施例中，可以是12:1。In the present invention, the molar ratio of the basic isobutene to paraformaldehyde is (10-30):1, preferably (12-25):1, more preferably (15-20):1, specifically, In an embodiment of the present invention, it may be 12:1.
由于泵的压力推动碱性异丁烯和多聚甲醛悬浮液由悬浮液储罐10输送到第一个换热器40，在换热器40内碱性异丁烯和多聚甲醛悬浮液的温度升高， 使部分多聚甲醛解聚成游离甲醛。换热器40加热段的末端，悬浮液的温度在120～220℃。该温度下悬浮液由第一反应器底端22进入反应器，在第一反应器内多聚甲醛解聚成游离甲醛。As the pressure of the pump pushes the alkaline isobutylene and paraformaldehyde suspension from the suspension storage tank 10 to the first heat exchanger 40, the temperature of the alkaline isobutylene and paraformaldehyde suspension increases in the heat exchanger 40, Part of the paraformaldehyde is depolymerized into free formaldehyde. At the end of the heating section of the heat exchanger 40, the temperature of the suspension is 120-220°C. At this temperature, the suspension enters the reactor from the bottom end 22 of the first reactor, and paraformaldehyde is depolymerized into free formaldehyde in the first reactor.
所述第一反应器内压力在0.6×10 7～1.4×10 7帕时，在反应器的末端24形成碱性异丁烯、游离态甲醛和少量的低于10％的未解聚的多聚甲醛气相混合物。 When the pressure in the first reactor is 0.6×10 7 to 1.4×10 7 Pa, basic isobutylene, free formaldehyde and a small amount of undepolymerized paraformaldehyde gas phase less than 10% are formed at the end 24 of the reactor. mixture.
反应器20反应混合物出口温度在120～190℃之间。而进入反应器的碱性异丁烯-多聚甲醛悬浮液的温度对出口温度没有太大影响。The outlet temperature of the reaction mixture of the reactor 20 is between 120 and 190°C. The temperature of the alkaline isobutylene-paraformaldehyde suspension entering the reactor did not have much effect on the outlet temperature.
在本发明中，所述第一个反应器20优选为柱塞流反应器，设计解聚反应器考虑到解聚动力及较高的产率，对年产3000到5000吨异戊烯醇产能解聚反应器设计的长度在3米到9米之间，优选为4～8米之间，更优选为5～7米之间，具体的，在本发明的实施例中，可以是5.5米；相应直径在1米到2米之间，优选为1.5米。按上述产率的解聚反应器长度和高度应在此范围内选择，解聚反应可向正确方向进行。In the present invention, the first reactor 20 is preferably a plug flow reactor, and the design of the depolymerization reactor takes into account the depolymerization power and higher productivity, and the annual production capacity of 3,000 to 5,000 tons of prenyl alcohol The designed length of the depolymerization reactor is between 3 meters and 9 meters, preferably between 4 and 8 meters, and more preferably between 5 and 7 meters. Specifically, in the embodiment of the present invention, it can be 5.5 meters. ; the corresponding diameter is between 1 m and 2 m, preferably 1.5 m. The length and height of the depolymerization reactor at the above-mentioned yield should be selected within this range, and the depolymerization reaction can proceed in the correct direction.
在本发明中，所述第一反应器中使用气动鼓泡结合机械搅拌的方式促进物料的混合与接触。In the present invention, the first reactor uses pneumatic bubbling combined with mechanical stirring to promote the mixing and contact of materials.
在本发明中，所述解聚的温度优选为120～220℃，更优选为150～200℃，最优选为160～190℃；所述解聚的压力优选为0.6×10 7～1.4×10 7Pa，更优选为0.8×10 7～1.2×10 7Pa，最优选为0.9×10 7～1.0×10 7Pa，具体的，在本发明的实施例中，可以是0.7×10 7Pa；所述解聚的时间优选为30～80min，更优选为40～70min，最优选为50～60min，具体的，在本发明的实施例中，可以是50min。 In the present invention, the depolymerization temperature is preferably 120-220°C, more preferably 150-200°C, and most preferably 160-190°C; the depolymerization pressure is preferably 0.6×10 7 ～1.4×10 7 Pa, more preferably 0.8×10 7 to 1.2×10 7 Pa, most preferably 0.9×10 7 to 1.0×10 7 Pa, specifically, in the embodiment of the present invention, it can be 0.7×10 7 Pa; The depolymerization time is preferably 30 to 80 minutes, more preferably 40 to 70 minutes, and most preferably 50 to 60 minutes. Specifically, in the embodiment of the present invention, it may be 50 minutes.
在第二阶段，温度在120-190℃的碱性异丁烯和甲醛混合物(低于该温度不发生烯烃和醛类的普林斯反应)进入第二个换热器50进一步提升温度至200～290℃，压力1.0×10 7～1.5×10 7帕时，碱性异丁烯-甲醛混合物进入第二个反应器30进行异丁烯和甲醛加成反应，生成异戊烯醇。 In the second stage, the basic isobutylene and formaldehyde mixture at a temperature of 120-190°C (below this temperature, no Prince reaction of olefins and aldehydes occurs) enters the second heat exchanger 50 to further increase the temperature to 200-290°C ℃, when the pressure is 1.0×10 7 to 1.5×10 7 Pa, the basic isobutene-formaldehyde mixture enters the second reactor 30 for the addition reaction of isobutene and formaldehyde to generate prenol.
本发明中，混合物由反应器底部32进入反应器30内。该条件下有利于异戊烯醇生成，最大限度减少副产物的生成。In the present invention, the mixture enters the reactor 30 from the bottom 32 of the reactor. This condition is favorable for the formation of prenol and minimizes the formation of by-products.
在本发明中，所述第二个反应器30优选为柱塞流反应器。反应器长度15～20米，直径1～2米，优选为1.3～1.5米。类似多聚甲醛解聚的绝热过程， 在绝热条件下发生加成反应。加成反应为放热过程，在反应末端温度稍有增加有利异戊烯醇进一步生成。In the present invention, the second reactor 30 is preferably a plug flow reactor. The length of the reactor is 15-20 meters, and the diameter is 1-2 meters, preferably 1.3-1.5 meters. Similar to the adiabatic process of paraformaldehyde depolymerization, the addition reaction occurs under adiabatic conditions. The addition reaction is an exothermic process, and a slight increase in the temperature at the end of the reaction facilitates the further formation of prenol.
在本发明中，第二反应器30顶端34生成含有异戊烯醇、未反应的异丁烯、少量的未反应甲醛及极少部分的副反应物混合物。第二反应器30出口36送出生成的异戊烯醇和上述未反应的原料混合物，其混合物的分离较容易，因原料混合物中主要成分为碱性异丁烯和甲醛，不含催化剂或溶剂；未反应的原料混合物返回系统可以优化工艺原料的使用。反应器30出口的混合物中分离异戊烯醇，主要是将混合物的温度降低到异戊烯醇沸点以下。混合物的温度降低到<130℃使异戊烯醇液化，分离出异戊烯醇后，其他反应物仍显气相，分离气相组分后，含有重组分的异戊烯醇送去蒸馏净化提纯。In the present invention, the top 34 of the second reactor 30 produces a mixture containing prenol, unreacted isobutene, a small amount of unreacted formaldehyde, and a very small amount of side reactants. The generated prenyl alcohol and the above-mentioned unreacted raw material mixture are sent out from the outlet 36 of the second reactor 30, and the separation of the mixture is easier, because the main components in the raw material mixture are basic isobutene and formaldehyde, without catalyst or solvent; The feed mixture return system can optimize the use of process feedstocks. The prenol is separated from the mixture at the outlet of the reactor 30, mainly by reducing the temperature of the mixture to below the boiling point of the prenol. The temperature of the mixture is lowered to <130°C to liquefy the prenol. After the prenol is separated, the other reactants are still in the gas phase. After the gas phase components are separated, the prenol containing the heavy components is sent to distillation and purification.
在本发明中，所述普林斯反应的温度优选为200～295℃，更优选为230～280℃，最优选为250～270℃，具体的，在本发明的实施例中，可以是270℃；所述普林斯反应的压力为1.0×10 7～1.5×10 7Pa，更优选为1.1×10 7～1.4×10 7Pa，最优选为1.2×10 7～1.3×10 7Pa，具体的，在本发明的实施例中，可以是1.15×10 7Pa；所述普林斯反应的时间为50～100min，更优选为60～90min，最优选为70～80min，具体的，在本发明的实施例中，可以是75min。 In the present invention, the temperature of the Prince reaction is preferably 200-295°C, more preferably 230-280°C, most preferably 250-270°C, specifically, in the embodiment of the present invention, it can be 270°C ℃; the pressure of the Prince reaction is 1.0×10 7 to 1.5×10 7 Pa, more preferably 1.1×10 7 to 1.4×10 7 Pa, most preferably 1.2×10 7 to 1.3×10 7 Pa, Specifically, in the embodiment of the present invention, it can be 1.15×10 7 Pa; the time of the Prince reaction is 50-100 min, more preferably 60-90 min, and most preferably 70-80 min. In the embodiment of the present invention, it may be 75min.
本发明提供了一种工业化异戊烯醇的生产工艺，包括以下步骤：A)多聚甲醛进行解聚生成游离的甲醛；B)将所述游离的甲醛与碱性异丁烯接触，进行普林斯反应，得到异戊烯醇；所述碱性异丁烯为包括异丁烯和碱性介质，所述碱性异丁烯的pH值为7.4～7.8。本发明的原料为碱性异丁烯，碱性异丁烯中的碱可以中和加成反应中甲醛歧化生成的甲酸，并且有效阻止异丁烯二聚生成二甲基己烯和三甲基环戊烷的副反应；从而提高异戊烯醇产品的色度，得到无色透明的异戊烯醇。The invention provides an industrialized production process for prenol, comprising the following steps: A) depolymerizing paraformaldehyde to generate free formaldehyde; B) contacting the free formaldehyde with alkaline isobutylene to carry out Prince The reaction is carried out to obtain prenol; the basic isobutene includes isobutene and an alkaline medium, and the pH value of the basic isobutene is 7.4-7.8. The raw material of the present invention is basic isobutene, and the alkali in the basic isobutene can neutralize the formic acid generated by the disproportionation of formaldehyde in the addition reaction, and effectively prevent the side reaction of isobutene dimerization to generate dimethylhexene and trimethylcyclopentane ; thereby improving the chromaticity of the prenol product to obtain colorless and transparent prenol.
另外，本发明中的生产工艺还具有以下优点：In addition, the production technique in the present invention also has the following advantages:
1.本发明中的工艺具有高选择性、高收率，没有污染物。1. The process in the present invention has high selectivity, high yield and no pollutants.
2.本发明提供的异戊烯醇生产工艺没有溶剂、没有有机物及水溶液。这样的工艺避免异戊烯醇分离操作即可获得高纯度及无污染的产品。2. The prenol production process provided by the present invention has no solvent, no organic matter and no aqueous solution. Such a process can obtain a high-purity and pollution-free product by avoiding the separation of prenol.
3.本发明异戊烯醇生产工艺没有反应催化剂。避免了异戊烯醇与催化剂混合物中分离催化剂的操作，也避免使用昂贵催化剂，极大降低生产成本。3. The prenol production process of the present invention has no reaction catalyst. The operation of separating the catalyst from the mixture of the prenol and the catalyst is avoided, and the use of an expensive catalyst is also avoided, which greatly reduces the production cost.
4.本发明是在简单的装置中生产异戊烯醇。操作参数(仅温度和压力)容易控制及修改。在反应器中连续回收未反应物，优化物料消耗。4. The present invention is the production of prenol in a simple apparatus. Operating parameters (temperature and pressure only) are easy to control and modify. Continuous recovery of unreacted material in the reactor optimizes material consumption.
5.本发明中异丁烯加碱，使生成的异戊烯醇无色透明。5. In the present invention, alkali is added to isobutene to make the generated prenol colorless and transparent.
6.本发明下生产工艺可以使生产连续化，使装置简单易于操作和维修管理。6. The production process of the present invention can make the production continuous, and make the device simple and easy to operate and maintain.
为了进一步说明本发明，以下结合实施例对本发明提供的一种工业化异戊烯醇的生产工艺进行详细描述，但不能将其理解为对本发明保护范围的限定。In order to further illustrate the present invention, a production process of an industrialized prenol provided by the present invention is described in detail below with reference to the examples, but it should not be construed as a limitation on the protection scope of the present invention.
以下实施例均采用图1所示装置进行。The following examples were all carried out using the device shown in FIG. 1 .
实施例1Example 1
碱性异丁烯和多聚甲醛混合物进入储罐，其中多聚甲醛为中等聚合度30，粒度为400-800微米。碱性异丁烯和多聚甲醛摩尔比为12:1。The basic isobutylene and paraformaldehyde mixture enters the storage tank, wherein the paraformaldehyde has a medium degree of polymerization of 30 and a particle size of 400-800 microns. The molar ratio of basic isobutylene and paraformaldehyde was 12:1.
碱性异丁烯和多聚甲醛混合悬浮液在罐中保持搅拌状态，通过泵，将混合物送入换热器中使其混合物的温度达到190℃，被加热的悬浮液送入高度5.5米，直径1.5米第一个柱塞流反应器，在第一个反应器内多聚甲醛被解聚，该反应条件为压力7MPa，50分钟。解聚反应终点是在反应器顶部获得温度170℃的碱性异丁烯、游离甲醛和未解聚的多聚甲醛混合物。The mixed suspension of basic isobutylene and paraformaldehyde is kept in a stirred state in the tank, and the mixture is sent to a heat exchanger by a pump to make the temperature of the mixture reach 190 ℃, and the heated suspension is sent to a height of 5.5 meters and a diameter of 1.5 meters. The first plug flow reactor, in which paraformaldehyde is depolymerized, the reaction conditions are pressure 7MPa, 50 minutes. The end point of the depolymerization reaction was to obtain a mixture of basic isobutene, free formaldehyde and undepolymerized paraformaldehyde at a temperature of 170°C at the top of the reactor.
该混合物进入第二个换热器被加热温度达到270℃时送入高度为20米，直径为1.3米的第二个柱塞流反应器，该反应器内异丁烯和甲醛普林斯反应生成异戊烯醇，碱中和甲酸、降低异丁烯二聚的副反应。When the mixture enters the second heat exchanger and is heated to 270°C, it is sent to the second plug flow reactor with a height of 20 meters and a diameter of 1.3 meters, in which isobutene and formaldehyde Prince react to form isobutene. Pentenol, alkali neutralizes formic acid and reduces the side reaction of isobutene dimerization.
普林斯反应是在压力115bar，75分钟条件下进行的。普林斯反应终点是在反应器顶端获得温度为270℃的碱性异丁烯和异戊烯醇重组分混合物The Prince reaction was carried out at a pressure of 115 bar for 75 minutes. The end point of the Prince reaction is to obtain a basic isobutene and prenol heavy component mixture at a temperature of 270°C at the top of the reactor.
混合物中含有未反应的碱性异丁烯、异戊烯醇和未反应的甲醛。依异丁烯计异戊烯醇的产率等于89％，混合物中未反应的剩余甲醛为11％(以异丁烯为基准)含有异戊烯醇的混合物冷却温度到25℃时，可以由混合物中分离出异戊烯醇。The mixture contains unreacted basic isobutene, prenol and unreacted formaldehyde. The yield of prenol based on isobutene is equal to 89%, the unreacted residual formaldehyde in the mixture is 11% (based on isobutene) The mixture containing prenol can be separated from the mixture when the temperature is cooled to 25°C Prenol.
反应后的物料中异戊烯醇的纯度为98.5～99％，含有1.5～1％的杂质，颜色透明。The purity of the prenol in the reacted material is 98.5-99 percent, contains 1.5-1 percent of impurities, and is transparent in color.
实施例2～4Examples 2 to 4
按照实施例1中的方法制备得到异戊烯醇，不同的是，解聚的温度和压力 按照表1进行。Prenyl alcohol was prepared according to the method in Example 1, except that the temperature and pressure of depolymerization were carried out according to Table 1.
表1实施例2～4中解聚的温度和压力Temperature and pressure of depolymerization in Table 1 Examples 2-4
Figure PCTCN2022071497-appb-000001
Figure PCTCN2022071497-appb-000001
由表1可知，多聚甲醛和碱性异丁烯的悬浮液在温度120～220℃的解聚过程中，反应参数温度、压力与多聚甲醛解聚率存在正向相关关系。It can be seen from Table 1 that during the depolymerization process of the suspension of paraformaldehyde and basic isobutylene at a temperature of 120-220 °C, there is a positive correlation between the reaction parameters temperature and pressure and the depolymerization rate of paraformaldehyde.
实施例5～8Examples 5 to 8
按照实施例1中的方法制备得到异戊烯醇，不同的是，实施例5～8中的多聚甲醛的颗粒尺寸与浓度按照表2中进行。Prenyl alcohol was prepared according to the method in Example 1, except that the particle size and concentration of paraformaldehyde in Examples 5-8 were carried out according to Table 2.
表2实施例5～8中多聚甲醛的尺寸与浓度The size and concentration of paraformaldehyde in Table 2 Examples 5-8
实施例Example 多聚甲醛尺寸(μm)Paraformaldehyde size (μm) 多聚甲醛浓度(％)Paraformaldehyde concentration (%) 异戊烯醇平均收率(％)Average yield of prenol (%)
55 ＞1500＞1500 9797 ＜80<80
66 900～1500900～1500 94.294.2 8383
77 300～900300～900 9191 9090
88 ＜300<300 ＜91<91 ****
注：“**”表示实施例8中，使用粒径小于300μm多聚甲醛，极易在溶液中结成大的团粒，实验证明异丁烯无能力扩散这种大的团粒以形成解聚要求的均匀相。因此，如满足解聚所需的均匀相，就要注入水分，其结果导致能量消耗比增加，对解聚工艺产生不良影响。另外因水分存在难于确保最终产品中水含量低于0.1％。Note: "**" means that in Example 8, using paraformaldehyde with a particle size of less than 300 μm, it is easy to form large agglomerates in the solution. Experiments have shown that isobutylene has no ability to diffuse such large agglomerates to form the uniformity required for depolymerization. Mutually. Therefore, if the homogeneous phase required for depolymerization is satisfied, water must be injected, resulting in an increase in the energy consumption ratio, which adversely affects the depolymerization process. In addition, it is difficult to ensure that the water content in the final product is less than 0.1% due to the presence of moisture.
颗粒尺寸大于900微米的多聚甲醛其浓度过高，低于300微米的多聚甲醛其浓度偏低。颗粒尺寸范围在300-900微米条件下，多聚甲醛浓度为91.0％；多聚甲醛颗粒尺寸大小对多聚甲醛浓度产生影响；多聚甲醛浓度对异戊烯醇平均收率产生影响。The concentration of paraformaldehyde with particle size larger than 900 microns is too high, and the concentration of paraformaldehyde below 300 microns is low. When the particle size range is 300-900 microns, the concentration of paraformaldehyde is 91.0%; the particle size of paraformaldehyde has an effect on the concentration of paraformaldehyde; the concentration of paraformaldehyde has an effect on the average yield of prenol.
比较例1Comparative Example 1
按照实施例1中的方法制备异戊烯醇，不同的是，比较例1中的原料为不加碱的异丁烯。Prenyl alcohol was prepared according to the method in Example 1, except that the raw material in Comparative Example 1 was isobutene without alkali.
反应后的物料中异戊烯醇纯度为98％，含有2％的杂质，颜色发黄。The purity of prenol in the reacted material was 98%, containing 2% impurities, and the color was yellow.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the principles of the present invention, several improvements and modifications can be made. It should be regarded as the protection scope of the present invention.

Claims (9)

  1. 一种工业化异戊烯醇的生产工艺，包括以下步骤：A production technique of industrialized prenol, comprising the following steps:
    A)多聚甲醛进行解聚生成游离的甲醛；A) depolymerization of paraformaldehyde generates free formaldehyde;
    B)将所述游离的甲醛与碱性异丁烯接触，进行普林斯反应，得到异戊烯醇；B) contacting described free formaldehyde with basic isobutene, carries out Prince reaction, obtains prenol;
    所述碱性异丁烯为包括异丁烯和碱性介质，所述碱性异丁烯的pH值为7.4～7.8。The basic isobutene includes isobutene and an alkaline medium, and the pH value of the basic isobutene is 7.4-7.8.
  2. 根据权利要求1所述的工业化异戊烯醇的生产工艺，其特征在于，所述多聚甲醛的聚合度为5～40，所述多聚甲醛的粒径为300～900μm。The production process of industrialized prenyl alcohol according to claim 1, wherein the degree of polymerization of the paraformaldehyde is 5-40, and the particle size of the paraformaldehyde is 300-900 μm.
  3. 根据权利要求1所述的工业化异戊烯醇的生产工艺，其特征在于，所述步骤A)中解聚的温度为120～220℃；所述解聚的压力为0.6×10 7～1.4×10 7Pa；所述解聚的时间为30～80min。 The production process of industrialized isoprenol according to claim 1, wherein the temperature of depolymerization in the step A) is 120～220°C; the pressure of the depolymerization is 0.6×10 7 ～1.4× 10 7 Pa; the depolymerization time is 30-80 min.
  4. 根据权利要求1所述的工业化异戊烯醇的生产工艺，其特征在于，所述碱性异丁烯与多聚甲醛的摩尔比为(10～30)：1。The production process of industrialized isoprenol according to claim 1, wherein the molar ratio of the basic isobutene to the paraformaldehyde is (10-30):1.
  5. 根据权利要求1所述的工业化异戊烯醇的生产工艺，其特征在于，所述普林斯反应的温度为200～295℃，所述普林斯反应的压力为1.0×10 7～1.5×10 7Pa；所述普林斯反应的时间为50～100min。 The production process of industrialized isoprenol according to claim 1, wherein the temperature of the Prince reaction is 200～295°C, and the pressure of the Prince reaction is 1.0×10 7 ～1.5× 10 7 Pa; the time of the Prince reaction is 50-100 min.
  6. 根据权利要求1所述的工业化异戊烯醇的生产工艺，其特征在于，所述碱性介质为氢氧化钠和/或氢氧化钾。The production technique of industrialized prenol according to claim 1, is characterized in that, described alkaline medium is sodium hydroxide and/or potassium hydroxide.
  7. 根据权利要求1～6任意一项所述的工业化异戊烯醇的生产工艺，其特征在于，在液态的碱性异丁烯中形成多聚甲醛颗粒的悬浮液，再进行解聚和普林斯反应。The production process of industrialized prenyl alcohol according to any one of claims 1 to 6, wherein a suspension of paraformaldehyde particles is formed in liquid alkaline isobutene, and then depolymerization and Prince reaction are carried out. .
  8. 根据权利要求1所述的工业化异戊烯醇的生产工艺，其特征在于，所述解聚在第一柱塞流反应器内进行，所述普林斯反应在第二柱塞流反应器内进行。The production process of industrialized isoprenol according to claim 1, wherein the depolymerization is carried out in the first plug flow reactor, and the Prince reaction is carried out in the second plug flow reactor conduct.
  9. 根据权利要求8所述的工业化异戊烯醇的生产工艺，其特征在于，所述第一柱塞流反应器的高度为3～9米，直径为1～2米；The production process of industrialized prenyl alcohol according to claim 8, wherein the height of the first plug flow reactor is 3 to 9 meters, and the diameter is 1 to 2 meters;
    所述第二柱塞流反应器的高度为15～20米，直径为1～2米。The height of the second plug flow reactor is 15-20 meters, and the diameter is 1-2 meters.
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