阅读说明：本技术 一种无溶剂分段式环氧氯丙烷的生产方法 (Solvent-free sectional type epichlorohydrin production method ) 是由 吴迪 马东兴 张萌 刘�东 于 2019-10-14 设计创作，主要内容包括：本发明提供一种无溶剂分段式环氧氯丙烷的生产方法,包括以下步骤：向一段反应器内加入氯丙烯、H<Sub>2</Sub>O<Sub>2</Sub>水溶液、钛硅分子筛催化剂和<I>p</I>H调节剂,进行环氧化反应,所得反应液进入一段分离器中进行油水分离,得有机相和水相；所得有机相经脱氢、精制,得环氧氯丙烷成品；水相进入下一段反应器,与新加入的氯丙烯继续反应,所得反应液经油水分离,得有机相和水相,如此反复,直至H<Sub>2</Sub>O<Sub>2</Sub>全部转化后进行固液分离,回收催化剂。本发明以氯丙烯和双氧水为原料,在无第三方溶剂参与条件下,以钛硅分子筛为催化剂进行分段式反应,工艺简单,条件温和,催化剂易于分离和回收套用,产品选择性高,生产效率高,绿色安全环保,生产成本及能耗低,具有极大的工业应用前景。(The invention provides a solvent-free sectional type epichlorohydrin production method, which comprises the following steps: adding chloropropene and H into a first-stage reactor 2 O 2 Aqueous solution, titanium silicalite catalyst and p h regulator, carrying out epoxidation reaction, and feeding the obtained reaction liquid into a first-stage separator for oil-water separation to obtain an organic phase and a water phase; dehydrogenating and refining the obtained organic phase to obtain a finished product of epoxy chloropropane; the water phase enters the next stage reactor, continuously reacts with the chloropropene which is newly added, the obtained reaction liquid is subjected to oil-water separation to obtain an organic phase and a water phase, and the steps are repeated until H is reached 2 O 2 After all the conversion, solid-liquid separation is carried out to recover the catalyst. The invention takes chloropropene and hydrogen peroxide as raw materials, and takes titanium silicalite molecular sieve as a catalyst to carry out sectional reaction under the condition of no participation of a third party solventThe method has the advantages of simple process, mild conditions, easy separation, recovery and reuse of the catalyst, high product selectivity, high production efficiency, environmental protection, low production cost and energy consumption, and great industrial application prospect.)

1. The solvent-free sectional type epichlorohydrin production method is characterized by comprising the following steps:

(1) reaction and isolation

Adding chloropropene and H into the reactor₂O₂Aqueous solution, titanium silicalite catalyst andph regulator, epoxidation reaction is carried out, the obtained reaction liquid enters a separator for oil-water separation, and organic phase mainly containing chloropropylene and epichlorohydrin, and organic phase mainly containing water and H are obtained₂O₂And an aqueous phase of catalyst;

(2) chloropropene recovery and product refining

Carrying out lightness removal treatment on the organic phase obtained in the step (1), recovering chloropropene and a crude epoxy chloropropane product, and refining the crude epoxy chloropropane product to obtain a finished epoxy chloropropane product;

(3) catalyst separation

And (2) carrying out solid-liquid separation on the water phase obtained in the step (1) and recovering the catalyst.

2. The method for producing solvent-free segmented epichlorohydrin according to claim 1, wherein in the step (1), the water phase obtained by separation in the first-stage separator enters the next-stage reactor, chloropropene is added into the next-stage reactor to perform the next-stage reaction, the obtained reaction liquid enters the next-stage separator to perform oil-water separation, and an organic phase and a water phase are obtained, and so on; the reactors in each reactor are arranged in one or more series and/or parallel connection, and each separator is arranged in one or more series and/or parallel connection;

the organic phase obtained by the separation of each separator enters a lightness-removing tower for lightness-removing treatment; and (5) carrying out solid-liquid separation on the water phase obtained by the last stage separator, and recovering the catalyst.

3. The method for producing solvent-free segmented epichlorohydrin according to claim 1, wherein in the step (1), the reactor is one or more of a slurry bed reactor, a micro-reactor and a pipeline reactor.

4. The method for producing solvent-free segmented epichlorohydrin according to claim 1, wherein in the step (1), the reaction temperature is 20 ~ 85 ℃, the reaction pressure is ~ 0.6.6 mPa under normal pressure, and the reaction system ispH is 3 ~ 11, the mass fraction of the catalyst is 1 percent ~ 15 percent, and H is₂O₂5 percent of water solution ~ 70 percent of chloropropene and H₂O₂The molar ratio of (A) to (B) is 1 ~ 20: 20, and the reaction residence time is 30 ~ 500 min.

5. The process for producing solvent-free segmented epichlorohydrin according to claim 1, wherein in the step (1),pthe H regulator is one or more of sodium hydroxide, ammonia water, ammonia gas, sulfuric acid, phosphoric acid, butyric acid and triethanolamine.

6. The production method of the solvent-free segmented epichlorohydrin according to claim 1, wherein in the step (1), the separation mode is one or more of centrifugal separation, plate-frame filtration/pressure filtration, membrane filtration, natural sedimentation, hydrocyclone separation and cloth bag filtration.

7. The method for producing solvent-free segmented epichlorohydrin according to claim 1, wherein the catalyst slurry is subjected to solvent removal and then is utilized in one of three ways: all the components are used in epoxidation reaction; all the catalyst is regenerated; one part is used for epoxidation reaction, and the rest is used for catalyst regeneration.

Technical Field

The invention relates to a production method of epichlorohydrin, in particular to a production method of solvent-free sectional epichlorohydrin.

Background

Epichlorohydrin (ECH) is an important organic chemical raw material and a fine chemical product, and has wide application. The epoxy resin prepared by using the epoxy resin as a raw material has the characteristics of strong cohesiveness, chemical medium corrosion resistance, low shrinkage, good chemical stability, high impact strength, excellent dielectric property and the like, and has wide application in the industries of coatings, adhesives, reinforcing materials, casting materials, electronic laminated products and the like. In addition, epichlorohydrin can also be used for synthesizing glycerol, nitroglycerin explosive, glass fiber reinforced plastic, electrical insulation products, surfactants, medicines, pesticides, coatings, sizing materials, ion exchange resins, plasticizers, (condensed) glycerin derivatives, chlorohydrin rubber and other products, and can be used as solvents of cellulose ester, resin and cellulose ether, and used for producing chemical stabilizers, chemical dyes, water treatment agents and the like.

At present, the method for producing epichlorohydrin mainly comprises a propylene high-temperature chlorination method, an acetate propylene-propylene alcohol method, an acrolein method, a glycerol chlorination method and a chloropropene direct epoxidation method.

The epoxy chloropropane is produced by performing chloropropene epoxidation reaction by adopting the traditional process, a large amount of saponification wastewater is generated, the environment is polluted, and the national environmental protection policy is not met; in the chloropropene direct epoxidation process, when other third-party solvents are used, the problems of low product yield, overlarge circulation amount in a system, high separation difficulty, high system energy consumption and the like are caused. Therefore, there is a need to develop a new epichlorohydrin production process.

Disclosure of Invention

The invention aims to provide a solvent-free sectional type epichlorohydrin production method, which aims to solve the problems of low reaction efficiency, high energy consumption, large pollution and the like in the existing method.

The purpose of the invention is realized as follows:

a solvent-free sectional type epichlorohydrin production method comprises the following steps:

(1) reaction and isolation

Adding chloropropene and H into the reactor₂O₂Aqueous solution, titanium silicalite catalyst andph regulator, epoxidation reaction is carried out, the obtained reaction liquid enters a separator for oil-water separation, and organic phase mainly containing chloropropylene and epichlorohydrin, and organic phase mainly containing water and H are obtained₂O₂And an aqueous phase of catalyst;

(2) chloropropene recovery and product refining

Carrying out lightness removal treatment on the organic phase obtained in the step (1), recovering chloropropene and a crude epoxy chloropropane product, and refining the crude epoxy chloropropane product to obtain a finished epoxy chloropropane product;

(3) catalyst separation

And (2) carrying out solid-liquid separation on the water phase obtained in the step (1) and recovering the catalyst.

The step (1) of the invention is specifically as follows: adding chloropropene and H into a first-stage reactor₂O₂Aqueous solution, titanium silicalite catalyst andph regulator, epoxidation reaction is carried out, the obtained reaction liquid enters a first-stage separator for oil-water separation, and organic phase mainly containing chloropropylene and epichlorohydrin and organic phase mainly containing water and H are obtained₂O₂And an aqueous phase of catalyst;

the obtained product mainly contains water and H₂O₂The water phase of the catalyst and the water phase enter the next stage reactor to continuously react with the chloropropene which is newly added, and the obtained reaction liquid is subjected to oil-water separation by a second stage separator to obtain an organic phase mainly containing chloropropene and epichlorohydrin and an organic phase mainly containing water and H₂O₂And the aqueous phase of the catalyst, and so on, up to H₂O₂Carrying out complete conversion, carrying out solid-liquid separation on the finally obtained water phase, and recovering the catalyst; and (4) dehydrogenating and refining the organic phase obtained in each section to obtain a finished product of the epoxy chloropropane.

In the step (1) of the invention, one or more reactors are arranged in series and/or in parallel for each reactor section, and one or more separators are arranged in series and/or in parallel for each separator section.

The reactor used in the step (1) of the invention is one or the combination of a plurality of reactors of a slurry bed reactor, a micro-reactor and a channel reactor.

In the step (1) of the present invention, the reaction temperature is 20 ~ 85 deg.C, preferably 30 ~ 60 deg.C, more preferably 40 ~ 60 deg.C, the reaction pressure is ~ 0.6.6 mPa under normal pressure, preferably normal pressure, and the reaction systempH is 3 ~ 11, the mass of the silicon catalyst accounts for 1 percent of ~ 15 percent of the total mass of the reaction raw materials, the mass of the silicon catalyst is preferably 1 percent of ~ 10 percent, and H is 3 ~₂O₂The mass fraction of the aqueous solution is 5 percent ~ 70 percent, preferably 27.5 percent ~ 50 percent, chloropropene and H₂O₂The molar ratio of (A) to (B) is 1 ~ 20: 1, preferably 2 ~ 10: 1, and the reaction residence time is 30 ~ 500min, preferably 30 ~ 300 min;

in the step (1) of the present invention,pthe H regulator is one or more of sodium hydroxide, ammonia water, ammonia gas, sulfuric acid, phosphoric acid, butyric acid and triethanolamine.

In the step (1), the separation mode is one or a combination of several of centrifugal separation, plate-frame filtration/filter pressing, membrane filtration, natural sedimentation, hydrocyclone separation and cloth bag filtration.

In the step (3), after the solvent of the catalyst slurry is removed, the catalyst slurry is utilized by one of the following three ways: all the components are used in epoxidation reaction; all the catalyst is regenerated; one part is used for epoxidation reaction, and the rest is used for catalyst regeneration.

The method takes chloropropene and hydrogen peroxide as raw materials, and takes the titanium silicalite molecular sieve as the catalyst to carry out sectional reaction under the condition of no participation of other third-party solvents, the process is simple, the condition is mild, the catalyst is easy to separate and recycle, the conversion rate of the hydrogen peroxide can reach 98 percent at most, the product selectivity is high, the production efficiency is high, the method is green, safe and environment-friendly, the production cost and the energy consumption are low, and the method has great industrial application prospect and good economic and social benefits.

The method adopts a multi-stage reaction separation process, not only greatly improves the production efficiency, but also greatly reduces the ineffective decomposition rate of the hydrogen peroxide, has no oxygen in the gas phase at the upper part of each stage of reactor, does not need complicated gas phase deoxidation procedures and equipment, and reduces the equipment investment cost. The method has the advantages of no third-party solvent, small system circulation amount, few side reactions and byproduct types, high target product yield, low equipment investment and operating cost, wide application range of reaction equipment, less waste water, waste gas and waste residue, low investment and operating cost of environment-friendly treatment facilities and low comprehensive energy consumption in the whole process.

Drawings

FIG. 1 is a schematic process flow diagram of the present invention.

Detailed Description

The present invention is further illustrated by the following examples in which the procedures and methods not described in detail are conventional and well known in the art, and the starting materials or reagents used in the examples are commercially available, unless otherwise specified, and are commercially available.

The process flow diagram of the present invention is shown in figure 1.