阅读说明：本技术 一种以二氯异丙醚为原料的水泥助磨剂助磨成分的合成方法 (Synthesis method of cement grinding aid component using dichloroisopropyl ether as raw material ) 是由 张瑞涛 江元华 潘玉杰 王书华 邹君 索喜梅 于 2019-09-18 设计创作，主要内容包括：本发明公开了一种以二氯异丙醚为原料的水泥助磨剂助磨成分的合成方法,包括如下步骤：(1)水解反应：并向反应器中一次性加入一定摩尔比例的固体碱、水、催化剂,加热到150～250℃,以10g/min的速度加入二氯异丙醚,使二氯异丙醚在固体碱的存在下充分水解至完全转化；(2)蒸馏除水：将蒸馏釜中的真空度控制在-0.07Mpa,温度控制在100℃～110℃之间,减压蒸馏除去其中的水分,得到有机液体及盐的残液；(3)过滤除盐：通过压滤设备或者离心设备除去反应过程中生成的盐分,得到以二丙二醇为主要有效成分的水溶性有机液体。本发明能够进一步降低以二乙醇单异丙醇胺或三异丙醇胺为主要成分的水泥助磨剂的成本。(The invention discloses a method for synthesizing a grinding aid component by using dichloroisopropyl ether as a raw material, which comprises the following steps: (1) and (3) hydrolysis reaction: adding solid alkali, water and a catalyst into a reactor at a certain molar ratio at one time, heating to 150-250 ℃, and adding dichloroisopropyl ether at the speed of 10g/min to fully hydrolyze the dichloroisopropyl ether in the presence of the solid alkali until the dichloroisopropyl ether is completely converted; (2) and (3) distillation and water removal: controlling the vacuum degree in the distillation kettle at-0.07 Mpa and the temperature between 100 ℃ and 110 ℃, and removing water in the distillation kettle by reduced pressure distillation to obtain organic liquid and salt residual liquid; (3) filtering and desalting: removing salt generated in the reaction process by using filter pressing equipment or centrifugal equipment to obtain the water-soluble organic liquid taking the dipropylene glycol as a main effective component. The invention can further reduce the cost of the cement grinding aid taking diethanol monoisopropanolamine or triisopropanolamine as the main component.)

1. A method for synthesizing a grinding aid component by using dichloroisopropyl ether as a raw material is characterized by comprising the following steps:

(1) and (3) hydrolysis reaction: selecting a reactor, adding solid alkali, water and a catalyst into the reactor at a certain molar ratio at one time, heating to 150-250 ℃, adding dichloroisopropyl ether at the speed of 10g/min, and increasing the pressure to 1.0-6.5 MPa to show CO₂And (3) generating, namely fully hydrolyzing the dichloroisopropyl ether in the presence of solid alkali until the dichloroisopropyl ether is completely converted, wherein the specific chemical reaction principle is as follows:

(2) and (3) distillation and water removal: controlling the vacuum degree in the distillation kettle at-0.07 Mpa and the temperature between 100 ℃ and 110 ℃, and removing water in the distillation kettle by reduced pressure distillation to obtain organic liquid and salt residual liquid;

(3) filtering and desalting: removing salt generated in the reaction process by using filter pressing equipment or centrifugal equipment to obtain the water-soluble organic liquid taking the dipropylene glycol as a main effective component.

2. The method for synthesizing the grinding aid ingredient by using the dichloroisopropyl ether as the raw material according to claim 1, which is characterized by comprising the following steps of: the dichloroisopropyl ether is derived from a byproduct in the chlorohydrin method propylene oxide industry.

3. The method for synthesizing the grinding aid ingredient by using the dichloroisopropyl ether as the raw material according to claim 1, which is characterized by comprising the following steps of: the reactor is a high-pressure reaction kettle or a slurry bed three-phase reactor suitable for a solid-liquid-gas three-phase reactor, and the material of the reactor can be a 316 stainless steel reaction kettle or a hastelloy reaction kettle.

4. The method for synthesizing the grinding aid ingredient by using the dichloroisopropyl ether as the raw material according to claim 1, which is characterized by comprising the following steps of: the solid base may be sodium carbonate, sodium bicarbonate or potassium carbonate.

5. The method for synthesizing the grinding aid ingredient by using the dichloroisopropyl ether as the raw material according to claim 1, which is characterized by comprising the following steps of: the catalyst is mainly hexadecyl tributyl phosphonium bromide or tetrabutyl ammonium bromide quaternary ammonium salt phase transfer catalyst.

6. The method for synthesizing the grinding aid ingredient by using the dichloroisopropyl ether as the raw material according to claim 1, which is characterized by comprising the following steps of: the filtering equipment in the filtering and desalting process can be an intermittent pressure filter or a tubular filter; the centrifuge device may be a tube centrifuge.

7. The method for synthesizing the grinding aid ingredient by using the dichloroisopropyl ether as the raw material according to claim 1, which is characterized by comprising the following steps of: the main component of the finally obtained water-soluble organic liquid comprises more than 93 percent of dipropylene glycol, and a small amount of 2-chloropropyl-allyl ether and 2-hydroxypropyl-allyl ether are byproducts, and the organic liquid belongs to a polyhydroxy strong polar compound and can be used as a grinding aid component in a cement grinding aid.

8. The method for synthesizing the grinding aid ingredient by using the dichloroisopropyl ether as the raw material according to claim 1, which is characterized by comprising the following steps of: the molar ratio of the dichloroisopropyl ether to water is 1: 2.1-1: 10, and the excessive water in a reaction system must be ensured so as to completely convert the dichloroisopropyl ether.

9. The method for synthesizing the grinding aid ingredient by using the dichloroisopropyl ether as the raw material according to claim 1, which is characterized by comprising the following steps of: the molar ratio of the dichloroisopropyl ether to the solid base is 2: 1-2.2: 1.

10. The method for synthesizing the grinding aid ingredient by using the dichloroisopropyl ether as the raw material according to claim 1, which is characterized by comprising the following steps of: the dosage of the catalyst is 0.5-2%.

Technical Field

The invention relates to the technical field of chemistry, in particular to a water-soluble organic substance which takes dipropylene glycol as a main component and is prepared by hydrolyzing a byproduct of dichloroisopropyl ether in the industrial production process of propylene oxide by a chlorohydrin method as a raw material. The organic matter can be used as a grinding aid component in a cement grinding aid.

Background

The chemical name of dichloroisopropyl ether is 1, 1' -oxyethylene (1-methyl-2-chloroethane), which is a by-product from a process for producing propylene oxide using chlorohydrin as a starting material. Most of the existing propylene oxide production processes in China are chlorohydrin methods, so that the dichloroisopropyl ether has the characteristics of wide sources and low cost. Which is known to those skilled in the art as a significant fraction of the bottoms stream from the rectification of Propylene Dichloride (PDC) in propylene oxide production. The PDC still bottoms stream is generally of no commercial value and is typically combusted in a CatoxidTM unit to recover hydrogen chloride (HCl) and heat. Thus, there is a need to recover at least a portion of the heavy distillate compounds from the PDC still bottoms stream in order to reduce the loss of carbon value and the load on the Catoxid unit.

Isopropyl dichloride is used in industry for recovery of hydrogen chloride and heat, but for a very small part as an agricultural nematicide. The dichloroisopropyl ether contains two chlorine atoms, has certain reaction activity, and can be subjected to nucleophilic substitution reaction with water under an alkaline condition to obtain the dipropylene glycol. The dipropylene glycol belongs to water-soluble strong-polarity micromolecules and can be used as a grinding aid component of a cement grinding aid in the cement grinding aid.

The grinding aid is an additive used in the cement clinker grinding process, and can obviously improve the grinding efficiency or reduce the energy consumption. The cement grinding aid mainly comprises alcohol amine substances, usually comprises Triethanolamine (TEA), Triisopropanolamine (TIPA), Methyldiethanolamine (MEA), Tetrahydroxyethylethylenediamine (THEED), Diethanolisopropanolamine (DEIPA), diisopropanolamine (EDIPA) and the like, and particularly has excellent grinding and reinforcing properties of DEIPA and EDIPA. In addition, the conventional cement grinding aid uses polyhydroxy surface active substances including ethanolamine, diethanolamine, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycerol, etc. as grinding aid ingredients to reduce the cost of the cement grinding aid.

US4298758 provides a process for the preparation of propylene glycol and dipropylene glycol by reacting dichloroisopropyl ether with a carboxylic acid salt, such as sodium acetate, and its corresponding carboxylic acid, such as acetic acid. The ester compounds can be hydrolyzed to obtain corresponding diol compounds, namely dipropylene glycol. However, the process is divided into two steps, wherein in the first step, carboxylic acid and corresponding sodium carboxylate react with dichloroisopropyl ether under the anhydrous condition under pressure, and then the salt is removed by filtration to obtain dipropylene glycol carboxylate; the second step is the further hydrolysis of dipropylene glycol carboxylate in an acidic aqueous solution to give dipropylene glycol. The sodium carboxylate and sodium chloride produced by this process are not well separated and the two-step reaction process is cumbersome.

Other applications of dichloroisopropyl ethers are rare, and limited patent literature reports also include a process for hydrogenating dichloroisopropyl ethers as reported in US3723544, by contacting dichloroisopropyl ether with a hydrogen source and a selected heterogeneous hydrogenation catalyst to convert the dichloroisopropyl ether to a halogenated derivative at a temperature in the range of 50 to 350 ℃ and a pressure in the range of 0.1MPa to 6.9MPa, with a ratio of liquid feed volume flow to catalyst mass in the range of 0.5L/Kg h to 10L/Kg h and a hydrogen volume/liquid volume ratio in the range of 100 ml gas/ml liquid to 5000 ml gas/ml liquid. The halogenated derivative is at least one of 1-chloro-2-propanol and 1, 2-dichloropropane and glycerol mono-chlorohydrin.

In order to solve the problem of complicated reaction process of the dichloroisopropyl ether, the sodium carboxylate and the carboxylic acid and further reduce the production cost, the invention provides a novel synthesis process of the dipropylene glycol, which is further applied to a cement grinding aid to be used as a grinding aid component so as to reduce the cost of the grinding aid.

Disclosure of Invention

The invention provides a method for synthesizing a grinding aid component by using dichloroisopropyl ether as a raw material, which aims to solve the problems in the background technology.

The invention provides a method for synthesizing a grinding aid component by using dichloroisopropyl ether as a raw material, which comprises the following steps:

(1) and (3) hydrolysis reaction: selecting a reactor, adding solid alkali, water and a catalyst into the reactor at a certain molar ratio at one time, heating to 150-250 ℃, adding dichloroisopropyl ether at the speed of 10g/min, and increasing the pressure to 1.0-6.5 MPa to show CO₂And (3) generating, namely fully hydrolyzing the dichloroisopropyl ether in the presence of solid alkali until the dichloroisopropyl ether is completely converted, wherein the specific chemical reaction principle is as follows:

(2) and (3) distillation and water removal: controlling the vacuum degree in the distillation kettle at-0.07 Mpa and the temperature between 100 ℃ and 110 ℃, and removing water in the distillation kettle by reduced pressure distillation to obtain organic liquid and salt residual liquid;

(3) filtering and desalting: removing salt generated in the reaction process by using filter pressing equipment or centrifugal equipment to obtain the water-soluble organic liquid taking the dipropylene glycol as a main effective component.

Preferably, the dichloroisopropyl ether is derived from a by-product of the chlorohydrin process propylene oxide industry, and the by-product is mainly derived from a significant fraction in a kettle bottom material flow in the rectification process of Propylene Dichloride (PDC) in the production of propylene oxide.

Preferably, the reactor is a high-pressure reactor or a slurry bed three-phase reactor, is suitable for a reactor with solid-liquid-gas three phases, and can be a 316 stainless steel reactor or a hastelloy reactor.

Preferably, the solid base may be sodium carbonate, sodium bicarbonate or potassium carbonate.

Preferably, the catalyst is mainly hexadecyl tributyl phosphonium bromide or tetrabutyl ammonium bromide quaternary ammonium salt phase transfer catalyst.

Preferably, the filtering equipment in the filtering and desalting process can be a batch type pressure filter or a tubular filter; the centrifuge device may be a tube centrifuge.

Preferably, the main component of the finally obtained water-soluble organic liquid comprises more than 93% of dipropylene glycol, and a small amount of 2-chloropropyl-allyl ether and 2-hydroxypropyl-allyl ether are byproducts, and the organic liquid belongs to a polyhydroxy strong polar compound and can be used as a grinding aid component in a cement grinding aid.

Preferably, the molar ratio of the dichloroisopropyl ether to the water is 1: 2.1-1: 10, and the excessive water in the reaction system must be ensured so as to completely convert the dichloroisopropyl ether.

Preferably, the molar ratio of the dichloroisopropyl ether to the solid base is 2: 1-2.2: 1.

Preferably, the amount of catalyst is 0.5% to 2%.

The invention provides a method for synthesizing a grinding aid component by using dichloroisopropyl ether as a raw material, which has the beneficial effects that: the water-soluble organic mixture which is prepared by the dichloroisopropyl ether and takes the dipropylene glycol as the main component is used as the grinding aid component of the grinding aid, has the advantages of low cost and changing waste into valuable, can further reduce the cost of the cement grinding aid taking the diethanol monoisopropanolamine or triisopropanolamine as the main component, and is suitable for being used by various enterprises producing the cement grinding aid.

Detailed Description

The invention is further illustrated by the following examples.