WO2022155779A1 - Preparation process for epichlorohydrin - Google Patents
Preparation process for epichlorohydrin Download PDFInfo
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- WO2022155779A1 WO2022155779A1 PCT/CN2021/072661 CN2021072661W WO2022155779A1 WO 2022155779 A1 WO2022155779 A1 WO 2022155779A1 CN 2021072661 W CN2021072661 W CN 2021072661W WO 2022155779 A1 WO2022155779 A1 WO 2022155779A1
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- epichlorohydrin
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- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 45
- 239000007789 gas Substances 0.000 claims abstract description 41
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000007788 liquid Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 29
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 26
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 238000004821 distillation Methods 0.000 claims description 41
- XEPXTKKIWBPAEG-UHFFFAOYSA-N 1,1-dichloropropan-1-ol Chemical compound CCC(O)(Cl)Cl XEPXTKKIWBPAEG-UHFFFAOYSA-N 0.000 claims description 32
- 238000010992 reflux Methods 0.000 claims description 23
- 238000010521 absorption reaction Methods 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000010410 layer Substances 0.000 claims description 17
- 238000003860 storage Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 238000005516 engineering process Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 claims description 7
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 6
- 239000003518 caustics Substances 0.000 claims description 4
- 239000012044 organic layer Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000004065 wastewater treatment Methods 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- 235000011187 glycerol Nutrition 0.000 description 11
- 238000010586 diagram Methods 0.000 description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 4
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- HUXDTFZDCPYTCF-UHFFFAOYSA-N 1-chloropropane-1,1-diol Chemical compound CCC(O)(O)Cl HUXDTFZDCPYTCF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003225 biodiesel Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- MLHOXUWWKVQEJB-UHFFFAOYSA-N Propyleneglycol diacetate Chemical compound CC(=O)OC(C)COC(C)=O MLHOXUWWKVQEJB-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical group OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000013072 incoming material Substances 0.000 description 1
- 239000013461 intermediate chemical Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/24—Synthesis of the oxirane ring by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
- C07D301/26—Y being hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
Definitions
- the invention relates to the technical field of epichlorohydrin production, in particular to a preparation process of epichlorohydrin.
- Epichlorohydrin is an important organic chemical intermediate and fine chemical with a wide range of uses. The production capacity has exceeded 2.2 million t/a.
- epichlorohydrin preparation technology has the following two kinds:
- the technical problem to be solved by the present invention is: to overcome the deficiencies of the prior art, a preparation process of epichlorohydrin is provided, the chromaticity (platinum-cobalt number) of the epichlorohydrin produced is less than or equal to 20, and the moisture content is less than or equal to 0.060%. , Epichlorohydrin content ⁇ 99.80%.
- the preparation technology of epichlorohydrin comprises the following steps:
- chlorination reaction glycerol and hydrogen chloride gas are transported to the reactor to carry out chlorination reaction;
- step (2) the product obtained in step (1) and liquid caustic soda are first mixed in a pipeline mixer to carry out a preliminary cyclization reaction, and the product after the reaction is transported to a cyclization tower to complete the cyclization reaction, Generate epichlorohydrin.
- the product obtained in step (1) is subjected to the cyclization reaction, it is first transported to the first rectification tower for rectification, and the rectification temperature is 100-140° C.
- the cooler and the secondary cooler are condensed and transported to the crude dichloropropanol tank; a part of the material in the crude dichloropropanol tank is refluxed to the top of the first rectifying tower, and a part is transported to the crude dichloropropanol transfer tank;
- the heavy components at the bottom of a rectifying tower are returned to the reactor and continue to participate in the chlorination reaction.
- step (1) after the excess hydrogen chloride gas in the chlorination reaction and the water generated by the reaction are condensed by the initial evaporation condenser, gas-liquid separation is carried out through the chlorination gas-liquid separation tank, and the separated liquid is transported to the initial stage. In the steam storage tank, the separated hydrogen chloride gas is returned to the reactor to continue to participate in the chlorination reaction.
- the material in the primary steam storage tank is transported to the dichloropropanol separation tower, and after the hydrogen chloride gas is removed, the primary steam at the bottom of the tower is transported to the primary steam transfer tank.
- the materials in the crude dichloropropanol transfer tank and the primary steam transfer tank are transported to the dichloropropanol mixing tank for mixing, and then transported to the pipeline mixer to participate in the cyclization reaction.
- the tail gas of the reactor, the tail gas of the crude dichloropropanol tank and the tail gas of the primary steam storage tank are transported to the tail gas water absorption tower, and the concentrated hydrochloric acid produced after countercurrent contact with the dilute hydrochloric acid is transported to the water absorption circulation tank, and then from the water absorption circulation tank It is transported to the hydrochloric acid storage tank; the tail gas absorbed by the dilute hydrochloric acid in the tail gas water absorption tower is transported to the alkali absorption tower, and the solution generated after countercurrent contact with the dilute alkali is transported to the alkali absorption circulation tank, and then transported from the alkali absorption circulation tank to the circulation tank.
- Chemical wastewater treatment plant Chemical wastewater treatment plant.
- the chlorination reaction temperature is 90-120° C.
- the reaction pressure is 0.05-0.3 MPa.
- step (1) glycerol and hydrogen chloride gas are sequentially transported to the first reactor, the second reactor and the third reactor for chlorination reaction.
- step (2) before the liquid caustic soda is transported to the pipeline mixer, it is heated to 50-60° C. in a liquid caustic heater.
- step (2) the gas product generated at the top of the cyclization tower is transported to the cyclization tower condenser to be condensed to below 40 ° C, and then transported to the cyclization tower reflux tank; the water in the upper layer of the cyclization tower reflux tank The layer is returned to the top of the cyclization tower, and the oil layer in the lower layer is transported to the crude epichlorohydrin buffer tank.
- the material in the crude epichlorohydrin buffer tank is transported to the preliminary distillation tower, and the crude epichlorohydrin at the bottom of the preliminary distillation tower is cooled to 60-80°C by the preliminary distillation tower tower kettle liquid cooler;
- the low boilers at the top are cooled by the top cooler of the initial distillation column and then transported to the reflux tank of the preliminary distillation column.
- the organic layer was refluxed to the initial distillation column.
- the crude epichlorohydrin at the bottom of the preliminary distillation column is cooled and transported to the second distillation column, and the dichloropropanol at the bottom of the second distillation column is transported to the primary distillation medium-turning tank; the top of the second distillation column
- the epichlorohydrin is condensed to below 40 °C by the condenser at the top of the rectification tower, it is transported to the reflux tank of the rectification column.
- a part of the material in the reflux tank of the rectification column is refluxed to the top of the second rectification column, and part of it is transported to the reflux tank of the rectification column.
- the epichlorohydrin intermediate tank is transported to the epichlorohydrin storage tank after passing the sampling test.
- the present invention has the following beneficial effects:
- the invention adopts the glycerol method to produce epichlorohydrin, gets rid of dependence on petroleum resources as raw materials, not only saves a lot of petroleum resources, but also reduces environmental pollution.
- the generation of three wastes is greatly reduced, and the amount of wastewater produced is only 1/5-6/1 of the propylene method.
- the annual COD emission reduction is about 13kg/t epichlorohydrin, and the annual standard coal saving is about 256kg/t. tEpichlorohydrin.
- the high oil price has driven the price of downstream propylene, and glycerol is a by-product of biodiesel production.
- the process of the invention makes full use of the biological resources of crops, which facilitates the recycling of resources and the sustainable development of economy.
- the chromaticity (platinum-cobalt number) of epichlorohydrin produced by the process of the invention is less than or equal to 20, the moisture content is less than or equal to 0.060%, and the content of epichlorohydrin is greater than or equal to 99.80%.
- Fig. 1 is the process flow diagram of the chlorination reaction unit of the present invention.
- Fig. 2 is the process flow diagram of the primary distillation unit of the present invention.
- Figure 3 is a process flow diagram of the primary vapor degassing unit of the present invention.
- Fig. 4 is the process flow diagram of the dichloropropanol mixing unit of the present invention.
- Figure 5 is a process flow diagram of the tail gas absorption unit of the present invention.
- Figure 6 is a process flow diagram of the cyclization reaction unit of the present invention.
- Figure 7 is a process flow diagram of the fore distillation unit of the present invention.
- Figure 8 is a process flow diagram of the secondary rectification unit of the present invention.
- the present invention provides a preparation process of epichlorohydrin, comprising the following steps:
- the glycerin enters the first reaction kettle, is pumped into the second reaction kettle, and then is pumped into the third reaction kettle; the hydrogen chloride gas is distributed through the HCl distribution table and then introduced into the three reaction kettles for further chlorination reaction.
- the temperature is 90-120°C, and the reaction pressure is 0.05-0.3MPa.
- Excessive HCl gas in the chlorination reaction and the water generated by the reaction are condensed by the primary evaporation condenser, and then gas-liquid separation is carried out in the chlorination gas-liquid separation tank.
- the separated liquid mainly water, HCl, dichloropropanol and a small amount of monochloropropanediol
- the separated HCl gas enters the second reaction kettle, and the glycerin in the second reaction kettle is used to absorb excess HCl gas to continue participating in the chlorination reaction, and the absorbed HCl tail gas enters the tail gas absorption unit.
- the fully reacted material in the third reaction kettle is pumped into the first rectification tower, the first rectification tower is evacuated by a vacuum pump, the bottom of the first rectification tower is heated by the reboiler of the first rectification tower, and the temperature is controlled at 100-140°C.
- the incoming materials are subjected to negative pressure rectification, and light components such as HCl, water, and dichloropropanol (DCH) enter the primary cooler and the secondary cooler for condensation.
- the condensed materials enter the crude dichloropropanol tank, and a part of Backflow to the top of the first rectifying tower, and a part is pumped to the thick dichloropropanol transfer tank; the heavy components such as catalyst, tar, unreacted glycerin at the bottom of the first rectifying tower are pumped to the reactor to continue Involved in the chlorination reaction.
- step (1) the first steam in the first steam material storage tank (mainly water, HCl, DCH and a trace amount of monochloropropanediol) enters the dichlorohydrin separation tower from the upper part of the tower, and is heated by the circulation of the reboiler.
- the HCl is removed by the method, and the primary steam after removing HCl is controlled at the liquid level at the bottom of the column, and is transported to the primary steam transfer tank by a pump.
- step (3) the first distillation thing of the transfer tank in the first distillation is transported to the thick dichlorohydrin transfer tank of step (2) with pump flow control, and the thick DCH in the thick dichlorohydrin transfer tank is transferred with thick dichlorohydrin Pump flow control to the dichloropropanol mixing tank.
- the primary distillation product after rectification and crude DCH are mixed to a specified concentration in a dichloropropanol mixing tank and then transported to a pipeline mixer by a dichloropropanol feed pump to participate in the cyclization reaction.
- the flow rate of the primary steam and crude DCH entering the dichloropropanol mixing tank is adjusted to ensure the concentration of the two mixed.
- the HCl tail gas enters the tail gas water absorption tower from the bottom of the tower, and is in countercurrent contact with the dilute hydrochloric acid sprayed at the top of the tower, After HCl and dilute hydrochloric acid form concentrated hydrochloric acid, the liquid level control at the bottom of the tower enters the water absorption circulation tank; the concentrated hydrochloric acid in the water absorption circulation tank is pumped to the hydrochloric acid storage tank.
- the absorbed tail gas enters the alkali absorption tower from the lower part of the tower, and is in countercurrent contact with the dilute liquid alkali sprayed at the top of the tower. HCl and the dilute liquid alkali generate sodium chloride aqueous solution at the bottom of the tower. After reaching a certain concentration, it is pumped to the cyclization wastewater treatment device.
- the liquid caustic soda is transported to the liquid caustic heater by the liquid caustic pump flow control for heat exchange.
- the liquid alkali solution is preheated to 50-60° C. and then enters the pipeline mixer through flow control, and is mixed with the mixed solution from the dichloropropanol mixing tank in step (4). Most of the reactions are carried out during mixing, and the mixed reaction enters the cyclization tower, where the reaction of remaining DCH and liquid alkali to generate epichlorohydrin (ECH) is completed in the cyclization tower.
- ECH epichlorohydrin
- the ECH generated by the cyclization tower is steamed from the top of the tower, condensed to below 40°C with circulating water through the cyclization tower condenser, and the condensate enters the cyclization tower reflux tank.
- the condensate is divided into a water layer and an oil layer in the reflux tank of the cyclization tower.
- the upper water layer is returned to the top of the cyclization tower after being controlled by the pump liquid level. Propane buffer tank.
- the ring tower is evacuated by a vacuum pump.
- the generated ECH must be quickly rectified from the top of the ring tower with steam, and the steam enters directly from the bottom of the tower.
- the cyclization wastewater is sent from the bottom of the cyclization tower to the bottom of the cyclization tower with a pump to adjust the liquid level at the bottom of the tower, and then sent to the flash tank. It is sent to the cyclization wastewater storage tank.
- a certain amount of tail gas waste acid is added through the regulating valve, and it is adjusted and processed by an online pH meter, and the specified pH value is adjusted and sent to the sewage workshop.
- the crude ECH in the crude epichlorohydrin buffer tank is sent to the preliminary distillation column to separate low boiler water through the flow control of the preliminary distillation column feed pump.
- the crude ECH obtained from the bottom of the preliminary distillation tower is transported by the bottom pump of the preliminary distillation tower, and cooled to 60-80 °C by circulating water through the liquid cooler of the preliminary distillation tower tower. After metering, it enters the rectification tower.
- the low boiler obtained at the top of the preliminary distillation tower is condensed to below 40°C with circulating water through the top of the preliminary distillation tower cooler, and enters the preliminary distillation tower reflux tank, where the water layer and the organic layer are separated.
- the upper layer is the water layer, overflows into the vacuum sealing tank, and is pumped to the loop tower reflux tank of step (6) with ECH; the organic layer of the lower layer is controlled by the preliminary distillation column reflux tank liquid level through the preliminary distillation column reflux pump and After the flow detection, it is returned to the initial distillation column as the reflux of the initial distillation column.
- the ECH obtained at the bottom of the preliminary distillation column enters the second distillation column, and the high boilers therein are separated.
- the DCH separated from the column bottom is transported by a pump, and is sent to the initial distillation transfer tank of step (3) after adjusting the liquid level at the column bottom and detecting the flow rate.
- the rectified ECH obtained at the top of the second rectification tower is cooled to below 40°C by circulating water through the rectification tower overhead condenser, and enters the rectification tower reflux tank. A part of the rectified ECH in the rectification tower reflux tank is passed through the rectification reflux pump.
- the flow is adjusted and returned to the top of the second rectifying tower; the other part is adjusted by the liquid level of the rectifying tower, and the flow is measured into the epichlorohydrin intermediate tank.
- the chloropropane feed pump is transported to the epichlorohydrin storage tank.
- the chromaticity (platinum-cobalt number) of epichlorohydrin produced by the process of the invention is less than or equal to 20, the moisture content is less than or equal to 0.060%, and the content of epichlorohydrin is greater than or equal to 99.80%.
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Abstract
A preparation process for epichlorohydrin. The process involves the following steps: (1) a chlorination reaction, wherein glycerol and hydrogen chloride gas are transported to a reaction kettle for a chlorination reaction; and (2) a cyclization reaction, wherein the product obtained from step (1) and a liquid alkali are mixed in a tube mixer for a preliminary cyclization reaction, and then delivered to a cyclization tower to complete the cyclization reaction and to obtain the product. The chromaticity (Pt-Co number) of epichlorohydrin produced by the present method is less than or equal to 20, the water content is less than or equal to 0.060%, and the epichlorohydrin content is greater than or equal to 99.80%.
Description
本发明涉及环氧氯丙烷生产技术领域,具体涉及一种环氧氯丙烷的制备工艺。The invention relates to the technical field of epichlorohydrin production, in particular to a preparation process of epichlorohydrin.
环氧氯丙烷是一种重要的有机化工中间体和精细化学品,用途非常广泛,主要用于生产环氧树脂、氯醇橡胶、表面活性剂、甘油缩水衍生物和阻燃材料等,全球的生产能力已经超过220万t/a。Epichlorohydrin is an important organic chemical intermediate and fine chemical with a wide range of uses. The production capacity has exceeded 2.2 million t/a.
目前,常用的环氧氯丙烷制备工艺有以下两种:At present, the commonly used epichlorohydrin preparation technology has the following two kinds:
一、丙烯高温氯化法1. High temperature chlorination of propylene
存在的问题是:(1)反应副产物较多,原材料转化率低,消耗定额较高;The existing problems are: (1) there are many reaction by-products, the conversion rate of raw materials is low, and the consumption quota is high;
(2)设备腐蚀严重,能耗较高、污水排放量较大。(2) The equipment is seriously corroded, the energy consumption is high, and the sewage discharge is large.
二、醋酸丙烯酯法Second, the propylene acetate method
存在的问题是:(1)反应步骤多,工艺路线长而复杂;(2)系统中有醋酸,要用不锈钢设备;(3)氧化反应器体积大,不易检修,催化剂昂贵不能再生;(4)反应中加入氯气,循环气压缩,必须重视丙烯醇单元防混合气爆炸的安全可靠性。The existing problems are: (1) there are many reaction steps, and the process route is long and complicated; (2) there is acetic acid in the system, and stainless steel equipment is used; (3) the oxidation reactor is large in size, difficult to overhaul, and the catalyst is expensive and cannot be regenerated; (4) ) In the reaction, chlorine gas is added, and the circulating gas is compressed, and attention must be paid to the safety and reliability of the propenyl alcohol unit against the explosion of the mixed gas.
发明内容SUMMARY OF THE INVENTION
本发明要解决的技术问题是:克服现有技术的不足,提供一种环氧氯丙烷的制备工艺,所生产的环氧氯丙烷色度(铂-钴号)≤20,水份≤0.060%,环氧氯丙烷含量≥99.80%。The technical problem to be solved by the present invention is: to overcome the deficiencies of the prior art, a preparation process of epichlorohydrin is provided, the chromaticity (platinum-cobalt number) of the epichlorohydrin produced is less than or equal to 20, and the moisture content is less than or equal to 0.060%. , Epichlorohydrin content ≥ 99.80%.
本发明的技术方案为:The technical scheme of the present invention is:
环氧氯丙烷的制备工艺,包括以下步骤:The preparation technology of epichlorohydrin, comprises the following steps:
(1)氯化反应:甘油与氯化氢气体输送至反应釜进行氯化反应;(1) chlorination reaction: glycerol and hydrogen chloride gas are transported to the reactor to carry out chlorination reaction;
(2)环化反应:将步骤(1)制得的产物与液碱先在管道混合器中混合,进行初步环化反应,反应完后的产物再输送至环化塔中完成环化反应,生成环氧氯丙烷。(2) cyclization reaction: the product obtained in step (1) and liquid caustic soda are first mixed in a pipeline mixer to carry out a preliminary cyclization reaction, and the product after the reaction is transported to a cyclization tower to complete the cyclization reaction, Generate epichlorohydrin.
优选地,步骤(1)制得的产物进行环化反应前,先输送至第一精馏塔中进行精馏,精馏温度为100-140℃,精馏出的轻组分先后经一级冷却器和二级冷却器冷凝后输送至粗二氯丙醇罐;粗二氯丙醇罐中的物料一部分回流至第一精馏塔塔顶,一部分输送至粗二氯丙醇中转罐;第一精馏塔塔底的重组分则返回至反应釜中继续参与氯化反应。Preferably, before the product obtained in step (1) is subjected to the cyclization reaction, it is first transported to the first rectification tower for rectification, and the rectification temperature is 100-140° C. The cooler and the secondary cooler are condensed and transported to the crude dichloropropanol tank; a part of the material in the crude dichloropropanol tank is refluxed to the top of the first rectifying tower, and a part is transported to the crude dichloropropanol transfer tank; The heavy components at the bottom of a rectifying tower are returned to the reactor and continue to participate in the chlorination reaction.
优选地,步骤(1)中,氯化反应中过量的氯化氢气体及反应生成的水经初蒸冷凝器 冷凝后,再经氯化气液分离罐进行气液分离,分离出的液体输送至初蒸物储罐中,分离出的氯化氢气体则返回至反应釜中继续参与氯化反应。Preferably, in step (1), after the excess hydrogen chloride gas in the chlorination reaction and the water generated by the reaction are condensed by the initial evaporation condenser, gas-liquid separation is carried out through the chlorination gas-liquid separation tank, and the separated liquid is transported to the initial stage. In the steam storage tank, the separated hydrogen chloride gas is returned to the reactor to continue to participate in the chlorination reaction.
优选地,初蒸物储罐中的物料输送至二氯丙醇脱析塔,脱除掉其中的氯化氢气体后,塔底的初蒸物则输送至初蒸物中转罐。Preferably, the material in the primary steam storage tank is transported to the dichloropropanol separation tower, and after the hydrogen chloride gas is removed, the primary steam at the bottom of the tower is transported to the primary steam transfer tank.
优选地,粗二氯丙醇中转罐和初蒸物中转罐中的物料输送至二氯丙醇混合罐混合后,再输送至管道混合器参与环化反应。Preferably, the materials in the crude dichloropropanol transfer tank and the primary steam transfer tank are transported to the dichloropropanol mixing tank for mixing, and then transported to the pipeline mixer to participate in the cyclization reaction.
优选地,反应釜尾气、粗二氯丙醇罐尾气和初蒸物储罐尾气输送至尾气水吸收塔,与稀盐酸逆流接触后产生的浓盐酸输送至水吸收循环罐,再从水吸收循环罐输送至盐酸储罐;尾气水吸收塔中被稀盐酸吸收后的尾气输送至碱吸收塔,与稀液碱逆流接触后产生的溶液输送至碱吸收循环罐,再从碱吸收循环罐输送至环化废水处理装置。Preferably, the tail gas of the reactor, the tail gas of the crude dichloropropanol tank and the tail gas of the primary steam storage tank are transported to the tail gas water absorption tower, and the concentrated hydrochloric acid produced after countercurrent contact with the dilute hydrochloric acid is transported to the water absorption circulation tank, and then from the water absorption circulation tank It is transported to the hydrochloric acid storage tank; the tail gas absorbed by the dilute hydrochloric acid in the tail gas water absorption tower is transported to the alkali absorption tower, and the solution generated after countercurrent contact with the dilute alkali is transported to the alkali absorption circulation tank, and then transported from the alkali absorption circulation tank to the circulation tank. Chemical wastewater treatment plant.
优选地,步骤(1)中,氯化反应温度为90-120℃,反应压力为0.05-0.3MPa。Preferably, in step (1), the chlorination reaction temperature is 90-120° C., and the reaction pressure is 0.05-0.3 MPa.
优选地,步骤(1)中,甘油与氯化氢气体依次输送至第一反应釜、第二反应釜和第三反应釜中进行氯化反应。Preferably, in step (1), glycerol and hydrogen chloride gas are sequentially transported to the first reactor, the second reactor and the third reactor for chlorination reaction.
优选地,步骤(2)中,液碱输送至管道混合器之前,先在液碱加热器中加热至50-60℃。Preferably, in step (2), before the liquid caustic soda is transported to the pipeline mixer, it is heated to 50-60° C. in a liquid caustic heater.
优选地,步骤(2)中,环化塔塔顶产生的气体产物输送至环化塔冷凝器中冷凝至40℃以下,再输送至环化塔回流罐中;环化塔回流罐上层的水层返回至环化塔塔顶,下层的油层输送至粗环氧氯丙烷缓冲罐。Preferably, in step (2), the gas product generated at the top of the cyclization tower is transported to the cyclization tower condenser to be condensed to below 40 ° C, and then transported to the cyclization tower reflux tank; the water in the upper layer of the cyclization tower reflux tank The layer is returned to the top of the cyclization tower, and the oil layer in the lower layer is transported to the crude epichlorohydrin buffer tank.
优选地,粗环氧氯丙烷缓冲罐中的物料输送至初馏塔,初馏塔塔底的粗环氧氯丙烷经初馏塔塔釜液冷却器冷却至60-80℃;初馏塔塔顶的低沸物经初馏塔塔顶冷却器冷却后输送至初馏塔回流罐,初馏塔回流罐中上层的水输送至真空密封槽后,再输送至环化塔回流罐,下层的有机层回流至初馏塔。Preferably, the material in the crude epichlorohydrin buffer tank is transported to the preliminary distillation tower, and the crude epichlorohydrin at the bottom of the preliminary distillation tower is cooled to 60-80°C by the preliminary distillation tower tower kettle liquid cooler; The low boilers at the top are cooled by the top cooler of the initial distillation column and then transported to the reflux tank of the preliminary distillation column. The organic layer was refluxed to the initial distillation column.
优选地,初馏塔塔底的粗环氧氯丙烷冷却后输送至第二精馏塔,第二精馏塔塔底的二氯丙醇输送至初蒸物中转罐;第二精馏塔塔顶的环氧氯丙烷经精馏塔塔顶冷凝器冷凝至40℃以下后,再输送至精馏塔回流罐,精馏塔回流罐的物料一部分回流至第二精馏塔塔顶,一部分输送至环氧氯丙烷中间槽,经取样化验合格后输送至环氧氯丙烷储罐。Preferably, the crude epichlorohydrin at the bottom of the preliminary distillation column is cooled and transported to the second distillation column, and the dichloropropanol at the bottom of the second distillation column is transported to the primary distillation medium-turning tank; the top of the second distillation column After the epichlorohydrin is condensed to below 40 ℃ by the condenser at the top of the rectification tower, it is transported to the reflux tank of the rectification column. A part of the material in the reflux tank of the rectification column is refluxed to the top of the second rectification column, and part of it is transported to the reflux tank of the rectification column. The epichlorohydrin intermediate tank is transported to the epichlorohydrin storage tank after passing the sampling test.
本发明与现有技术相比,具有以下有益效果:Compared with the prior art, the present invention has the following beneficial effects:
本发明采用甘油法生产环氧氯丙烷,摆脱了以石油资源为原料的依附,既节约了大量的石油资源,还减少了环境污染。三废的产生较丙烯法大大减少,废水的产生量仅为 丙烯法的1/5-6/1,较丙烯法相比年减排COD约13kg/t环氧氯丙烷,年节约标准煤约256kg/t环氧氯丙烷。近年来石油价格居高不下,带动了下游丙烯的价格,而甘油是生物柴油生产的副产物,随着全球生物柴油的兴起,甘油的价格逐年下降,在生产成本上甘油法较丙烯法有着明显优势。另外在设备投资上,甘油法生产环氧氯丙烷仅为丙烯法的三分之一。本发明的工艺充分利用了农作物生物资源,便于资源的循环利用与经济的可持续发展。且本发明工艺所生产的环氧氯丙烷色度(铂-钴号)≤20,水份≤0.060%,环氧氯丙烷含量≥99.80%。The invention adopts the glycerol method to produce epichlorohydrin, gets rid of dependence on petroleum resources as raw materials, not only saves a lot of petroleum resources, but also reduces environmental pollution. Compared with the propylene method, the generation of three wastes is greatly reduced, and the amount of wastewater produced is only 1/5-6/1 of the propylene method. Compared with the propylene method, the annual COD emission reduction is about 13kg/t epichlorohydrin, and the annual standard coal saving is about 256kg/t. tEpichlorohydrin. In recent years, the high oil price has driven the price of downstream propylene, and glycerol is a by-product of biodiesel production. With the rise of global biodiesel, the price of glycerol has dropped year by year, and the glycerol method has obvious advantages over the propylene method in terms of production cost. Advantage. In addition, in terms of equipment investment, the production of epichlorohydrin by the glycerol method is only one-third of the propylene method. The process of the invention makes full use of the biological resources of crops, which facilitates the recycling of resources and the sustainable development of economy. And the chromaticity (platinum-cobalt number) of epichlorohydrin produced by the process of the invention is less than or equal to 20, the moisture content is less than or equal to 0.060%, and the content of epichlorohydrin is greater than or equal to 99.80%.
图1是本发明的氯化反应单元的工艺流程图。Fig. 1 is the process flow diagram of the chlorination reaction unit of the present invention.
图2是本发明的一次精馏单元的工艺流程图。Fig. 2 is the process flow diagram of the primary distillation unit of the present invention.
图3是本发明的初蒸物脱气单元的工艺流程图。Figure 3 is a process flow diagram of the primary vapor degassing unit of the present invention.
图4是本发明的二氯丙醇混合单元的工艺流程图。Fig. 4 is the process flow diagram of the dichloropropanol mixing unit of the present invention.
图5是本发明的尾气吸收单元的工艺流程图。Figure 5 is a process flow diagram of the tail gas absorption unit of the present invention.
图6是本发明的环化反应单元的工艺流程图。Figure 6 is a process flow diagram of the cyclization reaction unit of the present invention.
图7是本发明的初馏单元的工艺流程图。Figure 7 is a process flow diagram of the fore distillation unit of the present invention.
图8是本发明的二次精馏单元的工艺流程图。Figure 8 is a process flow diagram of the secondary rectification unit of the present invention.
如图1-8所示,本发明提供了一种环氧氯丙烷的制备工艺,包括以下步骤:As shown in Figures 1-8, the present invention provides a preparation process of epichlorohydrin, comprising the following steps:
(1)氯化反应单元(1) Chlorination reaction unit
甘油进入第一反应釜,通过泵打入第二反应釜,再通过泵打入第三反应釜;氯化氢气体经HCl分配台分配后分别通入三个反应釜中进行进一步的氯化反应,反应温度90-120℃,反应压力为0.05-0.3MPa。The glycerin enters the first reaction kettle, is pumped into the second reaction kettle, and then is pumped into the third reaction kettle; the hydrogen chloride gas is distributed through the HCl distribution table and then introduced into the three reaction kettles for further chlorination reaction. The temperature is 90-120°C, and the reaction pressure is 0.05-0.3MPa.
氯化反应方程式如下:The chlorination reaction equation is as follows:
CH
2CHCH
2(OH)
3+HCl=CH
2CHCH
2(OH)
2Cl+H
2O
CH2CHCH2 (OH )3 + HCl = CH2CHCH2 (OH)2Cl + H2O
CH
2CHCH
2(OH)
2Cl+HCl=CH
2CHCH
2OHCl
2+H
2O。
CH2CHCH2 ( OH) 2Cl + HCl= CH2CHCH2OHCl2 + H2O .
氯化反应中过量的HCl气体及反应生成的水经初蒸冷凝器冷凝后,在氯化气液分离罐 中进行气液分离。分离出的液体(主要是水、HCl、二氯丙醇和微量的一氯丙二醇)经初蒸物受器液位控制,初蒸物输送泵输送至初蒸物储罐中,并进入初蒸物脱气单元;分离出的HCl气体进入第二反应釜,用第二反应釜中的甘油吸收过量的HCl气体继续参与氯化反应,吸收后的HCl尾气进入尾气吸收单元。Excessive HCl gas in the chlorination reaction and the water generated by the reaction are condensed by the primary evaporation condenser, and then gas-liquid separation is carried out in the chlorination gas-liquid separation tank. The separated liquid (mainly water, HCl, dichloropropanol and a small amount of monochloropropanediol) is controlled by the liquid level of the primary steam receiver, and the primary steam delivery pump is transported to the primary steam storage tank, and enters the primary steam degassing unit; The separated HCl gas enters the second reaction kettle, and the glycerin in the second reaction kettle is used to absorb excess HCl gas to continue participating in the chlorination reaction, and the absorbed HCl tail gas enters the tail gas absorption unit.
(2)一次精馏单元(2) Primary rectification unit
第三反应釜内反应完全的物料通过泵打入第一精馏塔,第一精馏塔通过真空泵抽真空,第一精馏塔塔底通过第一精馏塔再沸器加热,温度控制在100-140℃。进入的物料经过负压精馏,HCl、水、二氯丙醇(DCH)等轻组分进入一级冷却器及二级冷却器进行冷凝,冷凝后的物料进入粗二氯丙醇罐,一部分回流至第一精馏塔塔顶,一部分泵送至粗二氯丙醇中转罐;第一精馏塔塔底的催化剂、焦油、未反应完全的甘油等重组分通过泵输送至反应釜内继续参与氯化反应。The fully reacted material in the third reaction kettle is pumped into the first rectification tower, the first rectification tower is evacuated by a vacuum pump, the bottom of the first rectification tower is heated by the reboiler of the first rectification tower, and the temperature is controlled at 100-140℃. The incoming materials are subjected to negative pressure rectification, and light components such as HCl, water, and dichloropropanol (DCH) enter the primary cooler and the secondary cooler for condensation. The condensed materials enter the crude dichloropropanol tank, and a part of Backflow to the top of the first rectifying tower, and a part is pumped to the thick dichloropropanol transfer tank; the heavy components such as catalyst, tar, unreacted glycerin at the bottom of the first rectifying tower are pumped to the reactor to continue Involved in the chlorination reaction.
(3)初蒸物脱气单元(3) Primary steam degassing unit
步骤(1)中,初蒸物料储罐中的初蒸物(主要是水、HCl、DCH和微量的一氯丙二醇)从塔上部进入二氯丙醇脱析塔,通过再沸器的循环加热的方式脱除HCl,脱除HCl后的初蒸物在塔底液位控制,用泵输送至初蒸物中转罐。In step (1), the first steam in the first steam material storage tank (mainly water, HCl, DCH and a trace amount of monochloropropanediol) enters the dichlorohydrin separation tower from the upper part of the tower, and is heated by the circulation of the reboiler. The HCl is removed by the method, and the primary steam after removing HCl is controlled at the liquid level at the bottom of the column, and is transported to the primary steam transfer tank by a pump.
(4)二氯丙醇混合单元(4) Dichloropropanol mixing unit
步骤(3)中初蒸物中转罐的初蒸物用泵流量控制输送至步骤(2)的粗二氯丙醇中转罐中,粗二氯丙醇中转罐中的粗DCH用粗二氯丙醇中转泵流量控制输送至二氯丙醇混合罐中。精馏后的初蒸物与粗DCH在二氯丙醇混合罐混合至规定浓度后用二氯丙醇输料泵输送至管道混合器中参与环化反应。进入二氯丙醇混合罐的初蒸物与粗DCH的流量实行比例调节以确保二者混合的浓度。In the step (3), the first distillation thing of the transfer tank in the first distillation is transported to the thick dichlorohydrin transfer tank of step (2) with pump flow control, and the thick DCH in the thick dichlorohydrin transfer tank is transferred with thick dichlorohydrin Pump flow control to the dichloropropanol mixing tank. The primary distillation product after rectification and crude DCH are mixed to a specified concentration in a dichloropropanol mixing tank and then transported to a pipeline mixer by a dichloropropanol feed pump to participate in the cyclization reaction. The flow rate of the primary steam and crude DCH entering the dichloropropanol mixing tank is adjusted to ensure the concentration of the two mixed.
(5)尾气吸收单元(5) Exhaust gas absorption unit
来自步骤(1)的反应釜尾气、初蒸物储罐尾气和步骤(2)的粗二氯丙醇罐含HCl尾气从塔下部进入尾气水吸收塔,与塔顶喷淋的稀盐酸逆流接触,HCl与稀盐酸行成浓盐酸后在塔底液位控制进入水吸收循环罐;水吸收循环罐中的浓盐酸用泵输送至盐酸储罐。吸收后的尾气从塔下部进入碱吸收塔,与塔顶喷淋的稀液碱逆流接触,HCl与稀液碱生成氯化钠水溶液在塔底液位控制进入碱吸收循环罐,稀液碱循环至一定浓度后用泵输送至环化废水处理装置。From the reactor tail gas of step (1), the first steam storage tank tail gas and the thick dichloropropanol tank of step (2), the HCl tail gas enters the tail gas water absorption tower from the bottom of the tower, and is in countercurrent contact with the dilute hydrochloric acid sprayed at the top of the tower, After HCl and dilute hydrochloric acid form concentrated hydrochloric acid, the liquid level control at the bottom of the tower enters the water absorption circulation tank; the concentrated hydrochloric acid in the water absorption circulation tank is pumped to the hydrochloric acid storage tank. The absorbed tail gas enters the alkali absorption tower from the lower part of the tower, and is in countercurrent contact with the dilute liquid alkali sprayed at the top of the tower. HCl and the dilute liquid alkali generate sodium chloride aqueous solution at the bottom of the tower. After reaching a certain concentration, it is pumped to the cyclization wastewater treatment device.
(6)环化反应单元(6) Cyclization reaction unit
液碱经液碱泵流量控制输送至液碱加热器进行换热。液碱溶液被预热至50-60℃后经流量控制进入管道混合器,与来自步骤(4)的二氯丙醇混合罐的混合溶液混合。混合时 进行了大部分反应,混合反应后进入环化塔,在环化塔内完成剩余的DCH与液碱生成环氧氯丙烷(ECH)的反应。液碱与DCH溶液采用流量比例控制。The liquid caustic soda is transported to the liquid caustic heater by the liquid caustic pump flow control for heat exchange. The liquid alkali solution is preheated to 50-60° C. and then enters the pipeline mixer through flow control, and is mixed with the mixed solution from the dichloropropanol mixing tank in step (4). Most of the reactions are carried out during mixing, and the mixed reaction enters the cyclization tower, where the reaction of remaining DCH and liquid alkali to generate epichlorohydrin (ECH) is completed in the cyclization tower. Liquid caustic soda and DCH solution adopt flow proportional control.
环化反应方程式如下:The cyclization reaction equation is as follows:
环化塔生成的ECH从塔顶蒸出,经环化塔冷凝器用循环水冷凝至40℃以下,冷凝液进入环化塔回流罐。在环化塔回流罐内冷凝液分成水层和油层,上层的水层经泵液位控制后返回环化塔塔顶,下层的油层为粗ECH,通过泵液位控制输送至粗环氧氯丙烷缓冲罐。The ECH generated by the cyclization tower is steamed from the top of the tower, condensed to below 40°C with circulating water through the cyclization tower condenser, and the condensate enters the cyclization tower reflux tank. The condensate is divided into a water layer and an oil layer in the reflux tank of the cyclization tower. The upper water layer is returned to the top of the cyclization tower after being controlled by the pump liquid level. Propane buffer tank.
环化塔由真空泵抽真空,为抑制甘油的产生,必须快速用蒸汽从环化塔塔顶将生成的ECH精馏出,蒸汽从塔底直接进入。环化废水从环化塔塔底用泵变频调节塔底液位后,送入闪蒸罐中,回收废热蒸汽后,环化废水被冷却,在液碱换热器中与液碱换热后送往环化废水储罐,在环化废水储罐之前通过调节阀加入一定量的尾气废酸,通过在线pH计调节处理,调节出规定的pH值送到污水车间。The ring tower is evacuated by a vacuum pump. In order to suppress the production of glycerol, the generated ECH must be quickly rectified from the top of the ring tower with steam, and the steam enters directly from the bottom of the tower. The cyclization wastewater is sent from the bottom of the cyclization tower to the bottom of the cyclization tower with a pump to adjust the liquid level at the bottom of the tower, and then sent to the flash tank. It is sent to the cyclization wastewater storage tank. Before the cyclization wastewater storage tank, a certain amount of tail gas waste acid is added through the regulating valve, and it is adjusted and processed by an online pH meter, and the specified pH value is adjusted and sent to the sewage workshop.
(7)初馏单元(7) Preliminary distillation unit
粗环氧氯丙烷缓冲罐中的粗ECH通过初馏塔进料泵流量控制送入初馏塔中分离低沸物水。初馏塔塔底得到的粗ECH由初馏塔塔底泵输送,经过初馏塔塔釜液冷却器用循环水冷却至60-80℃,塔底泵出口流量由塔底液位控制并经计量器计量后进入精馏塔。初馏塔塔顶得到的低沸物,经过初馏塔塔顶冷却器用循环水冷凝到40℃以下,进入初馏塔回流罐中,在初馏塔回流罐中分离出水层及有机层。上层为水层,溢流到真空密封槽中,用ECH返回泵送至步骤(6)的环化塔回流罐;下层的有机层经初馏塔回流泵通过初馏塔回流罐液位控制并流量检测后返回初馏塔,作为初馏塔的回流。The crude ECH in the crude epichlorohydrin buffer tank is sent to the preliminary distillation column to separate low boiler water through the flow control of the preliminary distillation column feed pump. The crude ECH obtained from the bottom of the preliminary distillation tower is transported by the bottom pump of the preliminary distillation tower, and cooled to 60-80 ℃ by circulating water through the liquid cooler of the preliminary distillation tower tower. After metering, it enters the rectification tower. The low boiler obtained at the top of the preliminary distillation tower is condensed to below 40°C with circulating water through the top of the preliminary distillation tower cooler, and enters the preliminary distillation tower reflux tank, where the water layer and the organic layer are separated. The upper layer is the water layer, overflows into the vacuum sealing tank, and is pumped to the loop tower reflux tank of step (6) with ECH; the organic layer of the lower layer is controlled by the preliminary distillation column reflux tank liquid level through the preliminary distillation column reflux pump and After the flow detection, it is returned to the initial distillation column as the reflux of the initial distillation column.
(8)二次精馏单元(8) Secondary rectification unit
初馏塔塔底得到的ECH进入第二精馏塔,分离其中的高沸物。在第二精馏塔中,从塔底分离出的DCH由经泵输送,通过塔底液位调节、检测流量后送至步骤(3)的初蒸物中转罐。第二精馏塔塔顶得到的精ECH经精馏塔塔顶冷凝器用循环水冷却到40℃以下,进入精馏塔回流罐,精馏塔回流罐中的精ECH,一部分经精馏回流泵由流量调节回流到第二精馏塔塔顶;另一部分由精馏塔液位调节、流量计量后进入环氧氯丙烷中间槽,在环氧氯丙烷中间槽中当班取样化验合格后用环氧氯丙烷输料泵输送至环氧氯丙烷储罐。The ECH obtained at the bottom of the preliminary distillation column enters the second distillation column, and the high boilers therein are separated. In the second rectifying column, the DCH separated from the column bottom is transported by a pump, and is sent to the initial distillation transfer tank of step (3) after adjusting the liquid level at the column bottom and detecting the flow rate. The rectified ECH obtained at the top of the second rectification tower is cooled to below 40°C by circulating water through the rectification tower overhead condenser, and enters the rectification tower reflux tank. A part of the rectified ECH in the rectification tower reflux tank is passed through the rectification reflux pump. The flow is adjusted and returned to the top of the second rectifying tower; the other part is adjusted by the liquid level of the rectifying tower, and the flow is measured into the epichlorohydrin intermediate tank. The chloropropane feed pump is transported to the epichlorohydrin storage tank.
本发明工艺所生产的环氧氯丙烷色度(铂-钴号)≤20,水份≤0.060%,环氧氯丙烷含量≥99.80%。The chromaticity (platinum-cobalt number) of epichlorohydrin produced by the process of the invention is less than or equal to 20, the moisture content is less than or equal to 0.060%, and the content of epichlorohydrin is greater than or equal to 99.80%.
Claims (12)
- 环氧氯丙烷的制备工艺,其特征在于,包括以下步骤:The preparation technology of epichlorohydrin, is characterized in that, comprises the following steps:(1)氯化反应:甘油与氯化氢气体输送至反应釜进行氯化反应;(1) chlorination reaction: glycerol and hydrogen chloride gas are transported to the reactor to carry out chlorination reaction;(2)环化反应:将步骤(1)制得的产物与液碱先在管道混合器中混合,进行初步环化反应,反应完后的产物再输送至环化塔中完成环化反应,生成环氧氯丙烷。(2) cyclization reaction: the product obtained in step (1) and liquid caustic soda are first mixed in a pipeline mixer to carry out a preliminary cyclization reaction, and the product after the reaction is transported to a cyclization tower to complete the cyclization reaction, Generate epichlorohydrin.
- 如权利要求1所述的环氧氯丙烷的制备工艺,其特征在于,步骤(1)制得的产物进行环化反应前,先输送至第一精馏塔中进行精馏,精馏温度为100-140℃,精馏出的轻组分先后经一级冷却器和二级冷却器冷凝后输送至粗二氯丙醇罐;粗二氯丙醇罐中的物料一部分回流至第一精馏塔塔顶,一部分输送至粗二氯丙醇中转罐;第一精馏塔塔底的重组分则返回至反应釜中继续参与氯化反应。The preparation technique of epichlorohydrin as claimed in claim 1, is characterized in that, before the product obtained in step (1) is carried out cyclization reaction, it is first transported to the first rectifying tower for rectification, and the rectification temperature is 100-140℃, the light components from the rectification are condensed by the primary cooler and the secondary cooler successively and then transported to the crude dichloropropanol tank; a part of the material in the crude dichloropropanol tank is refluxed to the first rectification At the top of the tower, a part is transported to the crude dichloropropanol transfer tank; the heavy components at the bottom of the first rectification tower are returned to the reactor to continue to participate in the chlorination reaction.
- 如权利要求2所述的环氧氯丙烷的制备工艺,其特征在于,步骤(1)中,氯化反应中过量的氯化氢气体及反应生成的水经初蒸冷凝器冷凝后,再经氯化气液分离罐进行气液分离,分离出的液体输送至初蒸物储罐中,分离出的氯化氢气体则返回至反应釜中继续参与氯化反应。The preparation technique of epichlorohydrin as claimed in claim 2, it is characterized in that, in step (1), after the excessive hydrogen chloride gas in the chlorination reaction and the water that the reaction generates are condensed by the initial evaporation condenser, then chlorinated The gas-liquid separation tank conducts gas-liquid separation, the separated liquid is transported to the primary steam storage tank, and the separated hydrogen chloride gas is returned to the reactor to continue participating in the chlorination reaction.
- 如权利要求3所述的环氧氯丙烷的制备工艺,其特征在于,初蒸物储罐中的物料输送至二氯丙醇脱析塔,脱除掉其中的氯化氢气体后,塔底的初蒸物则输送至初蒸物中转罐。The preparation technology of epichlorohydrin as claimed in claim 3, it is characterized in that, the material in the primary steam storage tank is transported to the dichlorohydrin separation tower, after removing the hydrogen chloride gas therein, the primary steam at the bottom of the tower Then it is transported to the primary steam transfer tank.
- 如权利要求4所述的环氧氯丙烷的制备工艺,其特征在于,粗二氯丙醇中转罐和初蒸物中转罐中的物料输送至二氯丙醇混合罐混合后,再输送至管道混合器参与环化反应。The preparation technology of epichlorohydrin as claimed in claim 4, it is characterized in that, after the material in the thick dichlorohydrin transfer tank and the initial steaming medium transfer tank is transported to the dichlorohydrin mixing tank for mixing, and then transported to the pipeline for mixing Participate in the cyclization reaction.
- 如权利要求3-5任一项所述的环氧氯丙烷的制备工艺,其特征在于,反应釜尾气、粗二氯丙醇罐尾气和初蒸物储罐尾气输送至尾气水吸收塔,与稀盐酸逆流接触后产生的浓盐酸输送至水吸收循环罐,再从水吸收循环罐输送至盐酸储罐;尾气水吸收塔中被稀盐酸吸收后的尾气输送至碱吸收塔,与稀液碱逆流接触后产生的溶液输送至碱吸收循环罐,再从碱吸收循环罐输送至环化废水处理装置。The preparation technology of epichlorohydrin according to any one of claims 3-5, it is characterised in that the tail gas of the reactor, the tail gas of the thick dichloropropanol tank and the tail gas of the primary steam storage tank are transported to the tail gas water absorption tower, and the The concentrated hydrochloric acid produced after the countercurrent contact with hydrochloric acid is transported to the water absorption circulation tank, and then transported from the water absorption circulation tank to the hydrochloric acid storage tank; the tail gas absorbed by the dilute hydrochloric acid in the tail gas water absorption tower is transported to the alkali absorption tower, and countercurrent with the dilute liquid alkali The solution generated after the contact is transported to the alkali absorption circulation tank, and then transported from the alkali absorption circulation tank to the cyclization wastewater treatment device.
- 如权利要求1-5任一项所述的环氧氯丙烷的制备工艺,其特征在于,步骤(1)中,氯化反应温度为90-120℃,反应压力为0.05-0.3MPa。The preparation process of epichlorohydrin according to any one of claims 1-5, characterized in that, in step (1), the chlorination reaction temperature is 90-120° C., and the reaction pressure is 0.05-0.3 MPa.
- 如权利要求1-5任一项所述的环氧氯丙烷的制备工艺,其特征在于,步骤(1)中,甘油与氯化氢气体依次输送至第一反应釜、第二反应釜和第三反应釜中进行氯化反应。The preparation technique of epichlorohydrin according to any one of claims 1-5, wherein in step (1), glycerol and hydrogen chloride gas are sequentially transported to the first reaction kettle, the second reaction kettle and the third reaction kettle The chlorination reaction is carried out in the kettle.
- 如权利要求1-5任一项所述的环氧氯丙烷的制备工艺,其特征在于,步骤(2)中,液碱输送至管道混合器之前,先在液碱加热器中加热至50-60℃。The preparation technology of epichlorohydrin according to any one of claims 1-5, it is characterized in that, in step (2), before the liquid caustic soda is transported to the pipeline mixer, it is first heated to 50-50 in the liquid caustic heater 60°C.
- 如权利要求1-5任一项所述的环氧氯丙烷的制备工艺,其特征在于,步骤(2)中,环化塔塔顶产生的气体产物输送至环化塔冷凝器中冷凝至40℃以下,再输送至环化塔回流罐中;环化塔回流罐上层的水层返回至环化塔塔顶,下层的油层输送至粗环氧氯丙烷缓冲罐。The preparation technology of epichlorohydrin according to any one of claims 1-5, it is characterized in that, in step (2), the gas product that the cyclization tower tower top produces is transported to the cyclization tower condenser to be condensed to 40 Below ℃, it is transported to the reflux tank of the cyclization tower; the water layer of the upper layer of the reflux tank of the cyclization tower is returned to the top of the cyclization tower, and the oil layer of the lower layer is transported to the crude epichlorohydrin buffer tank.
- 如权利要求10所述的环氧氯丙烷的制备工艺,其特征在于,粗环氧氯丙烷缓冲罐中的物料输送至初馏塔,初馏塔塔底的粗环氧氯丙烷经初馏塔塔釜液冷却器冷却至60-80℃;初馏塔塔顶的低沸物经初馏塔塔顶冷却器冷却后输送至初馏塔回流罐,初馏塔回流罐中上层的水输送至真空密封槽后,再输送至环化塔回流罐,下层的有机层回流至初馏塔。The preparation technology of epichlorohydrin as claimed in claim 10, is characterized in that, the material in the crude epichlorohydrin buffer tank is transported to the preliminary distillation column, and the crude epichlorohydrin at the bottom of the preliminary distillation column is passed through the preliminary distillation column. The tower kettle liquid cooler is cooled to 60-80 °C; the low boilers at the top of the preliminary distillation tower are cooled by the preliminary distillation tower top cooler and then sent to the preliminary distillation tower reflux tank, and the water in the upper and middle layers of the preliminary distillation tower reflux tank is sent to After vacuum sealing the tank, it is transported to the reflux tank of the cyclization tower, and the organic layer of the lower layer is refluxed to the initial distillation tower.
- 如权利要求11所述的环氧氯丙烷的制备工艺,其特征在于,初馏塔塔底的粗环氧氯丙烷冷却后输送至第二精馏塔,第二精馏塔塔底的二氯丙醇输送至初蒸物中转罐;第二精馏塔塔顶的环氧氯丙烷经精馏塔塔顶冷凝器冷凝至40℃以下后,再输送至精馏塔回流罐,精馏塔回流罐的物料一部分回流至第二精馏塔塔顶,一部分输送至环氧氯丙烷中间槽,经取样化验合格后输送至环氧氯丙烷储罐。The preparation technique of epichlorohydrin as claimed in claim 11, is characterized in that, the thick epichlorohydrin at the bottom of the first distillation tower is cooled and transported to the second rectifying tower, and the dichloride at the bottom of the second rectifying tower is cooled. The propanol is transported to the primary steam transfer tank; the epichlorohydrin at the top of the second rectification tower is condensed to below 40°C by the condenser at the top of the rectification tower, and then transported to the reflux tank of the rectification tower and the reflux tank of the rectification tower A part of the material is refluxed to the top of the second rectification tower, and a part is transported to the middle tank of epichlorohydrin, which is transported to the epichlorohydrin storage tank after passing the sampling test.
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