CN113582808B - Method for continuously producing chloroethane - Google Patents

Method for continuously producing chloroethane Download PDF

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Publication number
CN113582808B
CN113582808B CN202110981128.0A CN202110981128A CN113582808B CN 113582808 B CN113582808 B CN 113582808B CN 202110981128 A CN202110981128 A CN 202110981128A CN 113582808 B CN113582808 B CN 113582808B
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gas
chloroethane
hydrochloric acid
ethanol
chloride
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CN113582808A (en
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罗勇
唐智勇
周海斌
陈建峰
邹海魁
初广文
孙宝昌
张亮亮
徐斌
徐万福
朱庆阳
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Zhejiang Dibang Chemical Co ltd
Beijing University of Chemical Technology
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Zhejiang Dibang Chemical Co ltd
Beijing University of Chemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/16—Preparation of halogenated hydrocarbons by replacement by halogens of hydroxyl groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B01J19/0013—Controlling the temperature of the process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/008—Feed or outlet control devices
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2204/00—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices
    • B01J2204/005—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices the outlet side being of particular interest
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2204/00—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices
    • B01J2204/007—Aspects relating to the heat-exchange of the feed or outlet devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00103—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor in a heat exchanger separate from the reactor

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a method for continuously producing chloroethane, which comprises the steps of enabling ethanol gas and hydrogen chloride gas to contact with aluminum chloride-zinc chloride-hydrochloric acid composite catalyst solution in a hypergravity reactor for chlorination reaction; carrying out heat exchange on the crude chloroethane gas and liquid ethanol to obtain cooled crude chloroethane gas; wherein at least a portion of the ethanol gas is obtained by gasification of the liquid ethanol upon the heat exchange; and (3) washing the cooled crude chloroethane gas with water, removing water from the washed refined chloroethane gas by a demister and a renewable water absorbent, and compressing, cooling and liquefying to obtain finished chloroethane. The method has the advantages of higher production efficiency and yield, smaller volume of reaction equipment, less waste water and lower energy consumption, and can continuously produce the chloroethane.

Description

Method for continuously producing chloroethane
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a method for continuously producing chloroethane.
Background
At present, the ethylene hydrochlorination method is commonly adopted for industrially producing chloroethane, the ethane chlorination method is adopted for a small number of chloroethane, and the ethanol chlorination method is adopted for a small number of chloroethane; and a large amount of recovered ethanol and byproduct hydrochloric acid are produced in the industrial production of China, so that the recovered ethanol and byproduct hydrochloric acid become a chemical raw material with low added value, and the chloroethane produced by an ethanol chlorination method has remarkable economic benefit in China.
Industrially, the ethanol process for producing chloroethane is basically carried out in a kettle reactor, and two methods are mainly adopted. Concentrated hydrochloric acid and ethanol are put into a kettle-type reactor, and the reaction is heated to generate chloroethane under the action of a catalyst, so that continuous production is difficult to realize, and along with the reduction of the concentration of zinc chloride, the catalyst solution needs to be concentrated periodically, so that the production efficiency is lower. And the other is to utilize a resolving tower to resolve the concentrated hydrochloric acid, and the resolved hydrogen chloride and ethanol are continuously fed into a reaction kettle (reactor) filled with catalyst solution for reaction, so as to realize continuous production of chloroethane. However, to ensure the production of ethyl chloride, the reactor is often relatively bulky; in order to ensure the quality of the product, the post-reaction treatment often needs treatment equipment such as a rectifying tower, a sulfuric acid drying tower and the like.
Many efforts have been made in the art to devise a more cost effective process for producing ethyl chloride. For example, non-patent documents (research on new processes for synthesizing chloroethane and industrialization thereof, xu Mofu et al, modern chemical industry, volume 40, 2 nd, month 2020, pages 215 to 221) have studied factors such as the type of catalyst and the reaction scheme used in the process for synthesizing chloroethane. This document suggests that AlCl 3-ZnCl2 is an excellent catalyst for the catalytic synthesis of ethyl chloride, and that a higher ethyl chloride yield can be achieved by the application of distillate. However, the use of AlCl 3-ZnCl2 as a catalyst in this document only achieves yields of up to 78.8%, and the distillate-on-duty process achieves higher yields but requires a longer process flow and large reaction equipment.
Disclosure of Invention
Problems to be solved by the invention
The method for continuously producing chloroethane in the prior art still has the problems of low reaction efficiency, large equipment volume, more waste water, high energy consumption and the like. Thus, there remains a need for further reduction in reaction equipment volume, improvement in reaction efficiency and yield, reduction in wastewater production, and reduction in energy consumption.
Solution for solving the problem
In order to solve the technical problems, the invention provides a method for continuously producing chloroethane, which has higher production efficiency and yield, smaller reaction equipment volume, less waste water and lower energy consumption. Specifically, the present invention solves the technical problems of the present invention by the following means.
[1] A process for the continuous production of ethyl chloride comprising the steps of:
the ethanol gas and the hydrogen chloride gas are contacted with an aluminum chloride-zinc chloride-hydrochloric acid composite catalyst solution to carry out chlorination reaction, so as to obtain crude chloroethane gas; wherein the chlorination reaction is carried out in a hypergravity reactor;
carrying out heat exchange on the crude chloroethane gas and liquid ethanol to obtain cooled crude chloroethane gas, wherein at least part of the ethanol gas is obtained by gasifying the liquid ethanol during the heat exchange;
And (3) washing the cooled crude chloroethane gas with water, removing water from the washed refined chloroethane gas by a demister and a renewable water absorbent, and compressing, cooling and liquefying to obtain finished chloroethane.
[2] The method according to [1], further comprising the steps of:
resolving the concentrated hydrochloric acid to generate the hydrogen chloride gas; and
And (3) using the water washing liquid generated by water washing and the diluted hydrochloric acid generated by concentrated hydrochloric acid analysis for absorbing hydrogen chloride gas in a chlorobenzene workshop to obtain concentrated hydrochloric acid, and optionally recycling the concentrated hydrochloric acid for the concentrated hydrochloric acid analysis.
[3] The process according to [1] or [2], further comprising discharging the reaction liquid in the hypergravity reactor and recirculating it back to the hypergravity reactor, optionally after passing through a heat exchanger.
[4] The method according to [3], further comprising mixing the ethanol gas with the hydrogen chloride gas, and then feeding the mixed gas into the hypergravity reactor in parallel with the composite catalyst solution or the circulating reaction liquid of the hypergravity reactor in a static tube mixer, and dispersing the mixed gas on a packing layer of the hypergravity reactor.
[5] The method according to [1] or [2], wherein the aluminum chloride in the aluminum chloride-zinc chloride-hydrochloric acid composite catalyst solution is: the mass ratio of the zinc chloride is 1:1-5, the hydrogen chloride content is 10-15%, and the total content of the aluminum chloride and the zinc chloride is 30-50%; the mol ratio of the ethanol gas to the hydrogen chloride gas is 1:1-1.15.
[6] The process according to [1] or [2], wherein the heat exchange of the crude chloroethane gas with liquid ethanol is performed in a plate heat exchanger.
[7] The method according to [1] or [2], wherein the regenerable water absorbent is one or more selected from the group consisting of calcium chloride, molecular sieves, alumina and silica gel.
[8] The method according to [4], wherein the static tube mixer is one selected from the group consisting of a venturi tube, an SV type static tube mixer and an SX type static tube mixer.
[9] The method according to [1] or [2], wherein the temperature of the chlorination reaction is 105 to 140 ℃; the temperature of the water washing is 30-35 ℃, and the chloroethane gas after water removal is compressed to the pressure of 0.1-0.4 MPa.
[10] The method according to [2], wherein the concentrated hydrochloric acid is at a desorption temperature of 110 to 150 ℃ and a desorption pressure of 0.1 to 0.3MPa.
ADVANTAGEOUS EFFECTS OF INVENTION
Compared with the prior art, the invention has the following beneficial technical effects.
1. The aluminum chloride-zinc chloride-hydrochloric acid composite catalytic system with stronger catalytic activity is adopted, so that the reaction speed is improved, the reaction temperature is reduced, and the use amount of the catalyst is reduced.
2. The liquid ethanol and the crude product chloroethane gas are subjected to heat exchange, so that on one hand, the heat load generated by heat absorption of a normal-temperature ethanol feeding reaction system can be reduced, and on the other hand, cooler equipment for cooling the crude product chloroethane gas to remove water vapor entrained in the crude product chloroethane gas can be reduced, and the use of a refrigerant is reduced.
3. The method strengthens mass transfer of chlorination reaction by using the hypergravity technology, improves reaction speed and ethanol conversion rate, and has small volume, simple post-treatment procedure and high efficiency compared with the common multi-stage spray tower equipment by using the hypergravity rotary packed bed as the water washing device.
4. The demister and the regenerable water absorbent are adopted to remove water in a combined way, so that the problem of post-treatment of waste sulfuric acid caused by the use of sulfuric acid is avoided.
5. The device used is small in size, small in number and small in occupied area, reduces the cost of production equipment and improves the production safety.
Drawings
FIG. 1 is a schematic flow diagram of one embodiment of the present invention.
Description of the reference numerals
A-circulating liquid heat exchanger; b-supergravity reactor; c-a circulating liquid receiving tank; d-static tube mixer; e-plate heat exchanger; f-a mother liquor receiving tank; g-super gravity rotating packed bed; h-refined liquid receiving tank; i-demister; j-desiccant packed column; a K-compressor; an L-cooler; m-chloroethane finished product tank; p-circulation pump.
Detailed Description
< Terms and definitions >
In the present specification, the numerical range indicated by the term "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, a numerical range indicated by "above" or "below" is a numerical range including the present number.
In the present specification, the meaning of "can" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
In this specification, the use of "optionally" or "optional" means that certain substances, components, steps of performing, conditions of applying, etc. may or may not be used.
In the present specification, unit names used are international standard unit names, and "%" used represent weight or mass% unless otherwise specified.
Reference in the specification to "a preferred embodiment," "an embodiment," and the like, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the elements may be combined in any suitable manner in the various embodiments.
One of the purposes of the invention is to provide a method for continuously producing chloroethane, which comprises the following steps:
the ethanol gas and the hydrogen chloride gas are contacted with an aluminum chloride-zinc chloride-hydrochloric acid composite catalyst solution to carry out chlorination reaction, so as to obtain crude chloroethane gas; wherein the chlorination reaction is carried out in a hypergravity reactor;
carrying out heat exchange on the crude chloroethane gas and liquid ethanol to obtain cooled crude chloroethane gas, wherein at least part of the ethanol gas is obtained by gasifying the liquid ethanol during the heat exchange;
And (3) washing the cooled crude chloroethane gas with water, removing water from the washed refined chloroethane gas by a demister and a renewable water absorbent, and compressing, cooling and liquefying to obtain finished chloroethane.
The individual steps of the process according to the invention are described in detail below.
Chlorination reaction step
In the invention, ethanol gas and hydrogen chloride gas are contacted with aluminum chloride-zinc chloride-hydrochloric acid composite catalyst solution to carry out chlorination reaction, thus obtaining crude chloroethane gas; wherein the chlorination reaction is carried out in a hypergravity reactor.
In a specific embodiment, the method further comprises circulating the reaction liquid in the hypergravity reactor. In particular, the reaction liquid in the hypergravity reactor may be discharged and optionally recycled back to the hypergravity reactor after passing through a heat exchanger. More specifically, the reaction liquid in the hypergravity reactor may be discharged to a receiving container, such as a receiving tank or a receiving tank, and then the reaction liquid in the receiving container is transferred to a heat exchanger for heat exchange to control the temperature of the reaction liquid to a desired chlorination reaction temperature, and then the heat exchanged reaction liquid is transferred back to the hypergravity reactor. Wherein the heat exchanger is preferably a graphite heat exchanger.
In a specific embodiment, ethanol gas and hydrogen chloride gas are mixed, and then the obtained mixed gas is contacted with a composite catalyst solution or a circulating reaction liquid of a hypergravity reactor in a static tubular mixer in parallel to be fed into the hypergravity reactor, and is dispersed on a packing layer of the hypergravity reactor.
Wherein the static tube mixer may be any suitable mixer known in the art including, but not limited to, venturi, SV-type static tube mixer, and SX-type static tube mixer. By pre-mixing in a static tube mixer, better dispersion contact of the hydrogen chloride-ethanol mixed gas and the catalyst solution can be promoted, thereby being beneficial to improving the yield of the reaction efficiency.
The packing layer of the hypergravity reactor is of a conventional structure such as porous corrugated plate cross-flow packing, multi-stage cross-flow rotary packing, split packing and the like, and because the hypergravity rotary bed rotates at a high speed to generate huge shearing force, liquid exists in the packing in the forms of liquid film, liquid yarn, liquid drops and the like, so that the contact probability of hydrogen chloride, ethanol and a catalyst is greatly improved, and the reaction is accelerated.
In the method, the aluminum chloride-zinc chloride-hydrochloric acid composite catalyst solution is used for catalyzing the reaction of ethanol and hydrogen chloride, and the catalyst has higher catalytic efficiency. Wherein aluminum chloride: the mass ratio of the zinc chloride is 1:1-5, preferably 1:2-3; the hydrogen chloride content of the catalyst solution is 10-15%; the total content of aluminum chloride and zinc chloride is 30 to 50%, preferably 30 to 40%. Because aluminum chloride belongs to strong Lewis acid, compared with zinc chloride, the catalytic activity is higher, and the hydroxyl group in ethanol is easier to leave, so that the reaction speed is increased. Therefore, the aluminum chloride-zinc chloride-hydrochloric acid composite catalytic system is adopted, so that the reaction temperature can be reduced, the production of byproducts such as diethyl ether and the like is reduced, and the reaction efficiency and the yield are improved.
In a specific embodiment, the molar ratio of ethanol gas to hydrogen chloride gas is 1:1 to 1.15, preferably 1:1.02 to 1.12. The temperature of the chlorination reaction is 105 to 140 ℃, preferably 110 to 135 ℃.
Heat exchange step
In the invention, the crude chloroethane gas obtained by the chlorination reaction is subjected to heat exchange with liquid ethanol, the crude chloroethane gas is cooled, and the liquid ethanol is heated and gasified. Through the heat exchange step, water vapor and hydrogen chloride entrained in the crude chloroethane gas are condensed into liquid so as to be separated from the chloroethane gas, and cooled to obtain cooled crude chloroethane gas. In the present invention, at least part of the ethanol gas involved in the chlorination reaction is obtained by gasifying the liquid ethanol when the heat exchange is performed. The temperature of the ethanol gas after heat exchange is controlled between 60 and 80 ℃. Preferably, during the reaction run, all ethanol gas involved in the chlorination reaction is obtained by gasification of liquid ethanol as it undergoes said heat exchange.
In a specific embodiment, the heat exchange of the crude chloroethane gas obtained from the chlorination reaction with liquid ethanol may be carried out in any suitable heat exchanger known in the art, preferably in a plate heat exchanger, more preferably in a double effect plate heat exchanger. The process design of heat exchange between the crude chloroethane gas obtained by the chlorination reaction and the liquid ethanol can make the liquid ethanol converted into ethanol gas while maximally utilizing the heat in the reaction system, so that the conversion rate of the ethanol is improved; on the other hand, the cooling of crude chloroethane gas is not needed, the process flow is simplified, the use of refrigerants is reduced, and the reaction energy consumption is reduced.
It should be noted that, although the heat exchange step is described in the present specification after the chlorination reaction step, it will be understood by those skilled in the art that as a continuous production process, the heat exchange step is performed simultaneously with the chlorination reaction step during the normal operation phase to supply the raw ethanol gas for the chlorination reaction. Furthermore, one skilled in the art will appreciate that at the beginning of the reaction or at the start-up of the reaction unit, since there is not enough crude chloroethane gas produced, an additional small amount of heat input may be required to heat the liquid ethanol, thereby beginning the reaction and gradually reaching the normal operating stage.
Therefore, in the method of the present invention, the order of execution of the steps is not limited by the order in which the description is made.
Refining step
In the invention, the crude chloroethane gas obtained by the chlorination reaction is refined, and impurities such as water, hydrogen chloride, ethanol and the like in the chloroethane gas are removed to obtain the finished chloroethane product. In one embodiment, the refining step includes water washing, water removal, compression, and liquefaction. In a specific embodiment, the cooled crude chloroethane gas is subjected to water washing, and the refined chloroethane gas obtained after water washing is subjected to water removal by a demister and a renewable water absorbent, and is compressed, cooled and liquefied to obtain the finished chloroethane.
In one embodiment, the water wash is carried out in a super gravity rotating packed bed by countercurrent contact of crude chloroethane gas with water to wash out as much hydrogen chloride as possible. The temperature of the water washing is controlled to be 30-35 ℃, if the temperature is too low, the chloroethane is easy to be liquefied, and if the temperature is too high, the washing absorption efficiency of the hydrogen chloride is reduced. The water washing is preferably performed using pure water, so that the influence of salt or organic matters in water on the subsequent recovery and thickening of the water washing liquid is reduced as much as possible.
In one embodiment, the moisture in the fine chloroethane gas is removed by combining a demister and a regenerable water absorbent, thereby avoiding the post-treatment problems of the prior art that result from the use of sulfuric acid in the removal of water.
In this embodiment, the fine chloroethane gas after washing with water is first passed through a demister to remove fine droplets thereof, i.e., water and hydrogen chloride dissolved therein. The present invention is not particularly limited to the mist eliminator used and any suitable mist eliminator known in the art may be used, including but not limited to baffle mist eliminators, swirl vane mist eliminators, tube bundle mist eliminators and circular wire mesh mist eliminators. By using the demister, water and hydrogen chloride carried in the chloroethane gas can be removed as much as possible, and the acidity of the chloroethane gas is reduced, so that the load of dewatering of a subsequent drying agent can be reduced, the service cycle of the drying agent is prolonged, and the product quality is improved.
The fine chloroethane gas after passing through the demister is then contacted with a regenerable water absorbent to further remove moisture therefrom. In a specific embodiment, the fine chloroethane gas after passing through the mist eliminator is sent to an absorption tower packed with a regenerable water absorbent to remove moisture therefrom. Herein, "regenerable water absorbent" refers to a water absorbent that is capable of regenerating after absorbing water, releasing the absorbed water and recovering the water absorbing capacity, for example, by absorbing water by means of chemical reaction or physical adsorption, and releasing water by reverse chemical reaction or physical desorption at an elevated temperature, while recovering the absorbing capacity. Examples of the regenerable water absorbent include calcium chloride, molecular sieves, alumina, silica gel, and the like.
In the method of the present invention, the dehydrated chloroethane gas is liquefied by compression and cooling. In a specific embodiment, the dehydrated fine chloroethane gas is compressed to a pressure of 0.1-0.4 Mpa, preferably 0.2-0.3 Mpa, and then cooled and liquefied to obtain the finished chloroethane liquid. Wherein the compression may be performed using any gas compressor known in the art. If the compression pressure is too low, the dew point of the chloroethane is also lowered, and it is difficult to cool and liquefy the chloroethane gas, and if the compression pressure is too high, the energy consumption of the compressor is increased. The cooling may be performed by any medium in any suitable cooling device known in the art. For economic reasons of the process according to the invention, it is preferred to cool the compressed chloroethane gas using normal temperature water.
In one embodiment, the method of the present invention further comprises the steps of: the concentrated hydrochloric acid is resolved to produce the hydrogen chloride gas. In this embodiment, the raw material hydrogen chloride gas is obtained by resolving concentrated hydrochloric acid. In a specific embodiment, concentrated hydrochloric acid is analyzed in an analysis device to produce hydrogen chloride gas, and the dilute hydrochloric acid produced by the analysis is collected. The resolving device may be any resolving device known in the art suitable for concentrated hydrochloric acid, such as a resolving tower. The dilute hydrochloric acid produced by the resolution may be collected, for example, in a dilute acid tank. The desorption temperature of the concentrated hydrochloric acid is 110 to 150 ℃, preferably 120 to 140 ℃, more preferably 125 to 140 ℃. If the analysis temperature is too low, the analysis efficiency is low, and if the analysis temperature is too high, the temperature is increased due to the azeotropic point of water and hydrogen chloride, so that the quality of the analyzed hydrogen chloride is not increased, but the energy consumption is increased. The analysis pressure is controlled to be 0.1-0.3 MPa.
In one embodiment, the method of the present invention further comprises the steps of: the dilute hydrochloric acid generated by the water washing and/or the concentrated hydrochloric acid analysis is used for absorbing the hydrogen chloride gas in the chlorobenzene workshop, so that the concentrated hydrochloric acid is obtained, and the concentrated hydrochloric acid is optionally recycled for the concentrated hydrochloric acid analysis.
Through the process design, the method solves the treatment problem of dilute hydrochloric acid generated by water washing liquid and concentrated hydrochloric acid analysis and the treatment problem of hydrogen chloride gas in a chlorobenzene workshop, and further improves the economy of the method.
One embodiment of the method of the present invention will be described in detail below with reference to the accompanying drawings.
As shown in fig. 1, the liquid ethanol exchanges heat with the crude chloroethane gas from the hypergravity reactor B generated by the chlorination reaction in the plate heat exchanger E, and is converted into ethanol gas, which enters the static tube mixer D simultaneously with the hydrogen chloride gas from the desorption device (not shown). The reaction liquid in the hypergravity reactor B is discharged into a circulating liquid receiving tank C, then is conveyed into a circulating liquid heat exchanger A through a circulating pump P for heat exchange, and the reaction liquid after heat exchange is conveyed into a static tube type mixer D, mixed with ethanol gas and hydrogen chloride gas and then enters the hypergravity reactor B for chlorination reaction. The crude chloroethane gas generated in the hypergravity reactor B is conveyed to a plate heat exchanger E to exchange heat with liquid ethanol, the cooled crude chloroethane gas is conveyed to a hypergravity rotating packed bed G to be washed, the washed refined chloroethane gas sequentially passes through a demister I and a desiccant packing tower J and then enters a compressor K to be compressed, the compressed chloroethane gas is conveyed to a cooler L, and the cooled and liquefied chloroethane gas enters a chloroethane finished product tank M.
The invention is further illustrated below in connection with specific examples. The devices used in the present invention are all conventional devices unless otherwise specified.
Numerous specific details are set forth in the following description in order to provide a better understanding of the invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In other instances, well known methods, procedures, means, equipment and steps have not been described in detail so as not to obscure the present invention.
Example 1
Preparing an aluminum chloride-zinc chloride-hydrochloric acid solution in a 5-side circulating liquid receiving tank, wherein the aluminum chloride is as follows: the mass ratio of zinc chloride is 1:2; the content of hydrogen chloride in the solution is 10%; the total content of aluminum chloride-zinc chloride was 30%. The hypergravity reactor and hypergravity refining equipment are started, and the rotating speed is controlled at 500r/min. And (3) starting a circulating pump P to circulate the solution of the composite catalyst system, and heating to 115-120 ℃ through a circulating liquid heat exchanger A. Starting a concentrated hydrochloric acid analysis device, feeding 31% concentrated hydrochloric acid, controlling the flow to 7600kg/h, controlling the analysis temperature to 125-130 ℃, and monitoring the generated hydrogen chloride gas by using a flowmeter, wherein the feeding amount is 1070kg/h. The liquid ethanol is heated in a plate heat exchanger, is converted into ethanol gas and starts to be fed, wherein the molar ratio of the ethanol to the hydrogen chloride is controlled to be 1:1.05, namely the feeding amount of the ethanol is 1284kg/h, and the ethanol and the hydrogen chloride are mixed and then are contacted with a circulating catalyst solution in a static tubular mixer again to be fed into a hypergravity reactor for chlorination reaction. The crude chloroethane gas generated by the reaction is subjected to heat exchange with liquid ethanol through a plate heat exchanger, wherein water and hydrogen chloride are cooled to liquid and flow to a mother liquor water receiving tank; the cooled crude chloroethane gas is fed from the bottom of the hypergravity refining equipment and is in countercurrent contact with water, a small amount of hydrogen chloride entrained in the crude chloroethane gas is further washed and removed, and the refining temperature is controlled to be 30-35 ℃. Collecting refined liquid and pumping the refined liquid and the diluted hydrochloric acid generated by analysis to a chlorobenzene workshop for thickening to obtain concentrated hydrochloric acid. The refined chloroethane gas is fed into a demister and a drying agent calcium chloride packing tower for dewatering, and then is fed into a compressor. The chloroethane gas is compressed to the pressure of 0.2MPa by a compressor, cooled to liquid chloroethane by a cooler at normal temperature, and stored in a chloroethane finished product tank. The finished product chloroethane has the water content of 60ppm, the purity of 99.97 percent and the acidity of 6ppm after detection. The yield of ethyl chloride produced for 24 hours by calculation based on the ethanol feed amount was 96.05%.
Comparative example 1
And preparing zinc chloride-hydrochloric acid solution in a 5-side circulating liquid receiving tank, wherein the content of hydrogen chloride in the solution is 10%, and the total content of zinc chloride is 30%. The hypergravity reactor and hypergravity refining equipment are started, and the rotating speed is controlled at 500r/min. And (3) starting a circulating pump P to circulate the solution of the composite catalyst system, and heating to 115-120 ℃ through a circulating liquid heat exchanger A. Starting a concentrated hydrochloric acid analysis device, feeding 31% concentrated hydrochloric acid, controlling the flow to 7600kg/h, controlling the analysis temperature to 125-130 ℃, and monitoring the generated hydrogen chloride gas by using a flowmeter, wherein the feeding amount is 1070kg/h. The liquid ethanol is heated in a plate heat exchanger, is converted into ethanol gas and starts to be fed, wherein the molar ratio of the ethanol to the hydrogen chloride is controlled to be 1:1.05, namely the ethanol feeding amount is 1284kg/h, and the ethanol and the hydrogen chloride are mixed and then are contacted with the circulating catalytic solution in a static tube type mixer D again to be fed into a hypergravity reactor for chlorination reaction. And carrying out heat exchange on crude chloroethane gas generated by the reaction and ethanol through a plate heat exchanger, wherein water and hydrogen chloride are cooled to liquid and flow to a mother liquor water receiving tank. The cooled crude chloroethane gas is fed from the bottom of the hypergravity refining device G and is in countercurrent contact with water, a small amount of hydrogen chloride entrained in the crude chloroethane gas is further washed and removed, and the refining temperature is controlled to be 30-35 ℃. Collecting refined liquid and pumping the refined liquid and the diluted hydrochloric acid generated by analysis to a chlorobenzene workshop for thickening to obtain concentrated hydrochloric acid. The refined chloroethane gas is fed into a demister and a drying agent calcium chloride packing tower for dewatering, and then is fed into a compressor. The chloroethane gas is compressed to the pressure of 0.2MPa by a compressor, cooled to liquid chloroethane by a cooler at normal temperature, and stored in a chloroethane finished product tank. The finished product chloroethane has the water content of 60ppm, the purity of 99.90 percent and the acidity of 6ppm after detection. The yield of ethyl chloride produced for 24 hours by calculation based on the ethanol feed amount was 90.3%.
Comparative example 2
And preparing zinc chloride-hydrochloric acid solution in a 5-side circulating liquid receiving tank, wherein the content of hydrogen chloride in the solution is 10%, and the total content of zinc chloride is 30%. The hypergravity reactor and hypergravity refining equipment are started, and the rotating speed is controlled at 500r/min. And (3) starting a circulating pump P to circulate the solution of the composite catalyst system, and heating to 135-140 ℃ through a circulating liquid heat exchanger A. Starting a concentrated hydrochloric acid analysis device, feeding 31% concentrated hydrochloric acid, controlling the flow to 7600kg/h, controlling the analysis temperature to 125-130 ℃, and monitoring the generated hydrogen chloride gas by using a flowmeter, wherein the feeding amount is 1070kg/h. The liquid ethanol is heated in a plate heat exchanger, is converted into ethanol gas and starts to be fed, wherein the molar ratio of the ethanol to the hydrogen chloride is controlled to be 1:1.05, namely the ethanol feeding amount is 1284kg/h, and the ethanol and the hydrogen chloride are mixed and then are contacted with the circulating catalytic solution in a static tube type mixer D again to be fed into a hypergravity reactor for chlorination reaction. And carrying out heat exchange on crude chloroethane gas generated by the reaction and ethanol through a plate heat exchanger, wherein water and hydrogen chloride are cooled to liquid and flow to a mother liquor water receiving tank. The cooled crude chloroethane gas is fed from the bottom of the hypergravity refining equipment and is in countercurrent contact with water, a small amount of hydrogen chloride entrained in the crude chloroethane gas is further washed and removed, and the refining temperature is controlled to be 30-35 ℃. Collecting refined liquid and pumping the refined liquid and the diluted hydrochloric acid generated by analysis to a chlorobenzene workshop for thickening to obtain concentrated hydrochloric acid. The refined chloroethane gas is fed into a demister and a drying agent calcium chloride packing tower for dewatering, and then is fed into a compressor. The chloroethane gas is compressed to the pressure of 0.2MPa by a compressor, cooled to liquid chloroethane by a cooler at normal temperature, and stored in a chloroethane finished product tank. The finished product chloroethane has the water content of 60ppm, the purity of 99.90 percent and the acidity of 6ppm after detection. The yield of ethyl chloride produced for 24 hours by calculation based on the ethanol feed amount was 95.3%.
Comparative example 3
Preparing an aluminum chloride-zinc chloride-hydrochloric acid solution in a 5-side circulating liquid receiving tank, wherein the aluminum chloride is as follows: the mass ratio of zinc chloride is 1:2; the content of hydrogen chloride in the solution is 10%; the total content of aluminum chloride-zinc chloride was 30%. The hypergravity reactor and hypergravity refining equipment are started, and the rotating speed is controlled at 500r/min. And (3) starting a circulating pump P to circulate the solution of the composite catalyst system, and heating to 115-120 ℃ through a circulating liquid heat exchanger A. Starting a concentrated hydrochloric acid analysis device, feeding 31% concentrated hydrochloric acid, controlling the flow to 7600kg/h, controlling the analysis temperature to 125-130 ℃, and monitoring the generated hydrogen chloride gas by using a flowmeter, wherein the feeding amount is 1070kg/h. The liquid ethanol is heated in a plate heat exchanger, is converted into ethanol gas and starts to be fed, wherein the molar ratio of the ethanol to the hydrogen chloride is controlled to be 1:1.05, namely the ethanol feeding amount is 1284kg/h, and the ethanol is directly mixed with the hydrogen chloride without heat exchange and then is contacted with a circulating catalytic solution in a static tubular mixer again to be fed into a hypergravity reactor for chlorination reaction. And carrying out heat exchange on crude chloroethane gas generated by the reaction and cooling water through a plate heat exchanger, wherein the water and hydrogen chloride are cooled to liquid and flow to a mother liquor water receiving tank. The cooled crude chloroethane gas is fed from the bottom of the hypergravity refining equipment and is in countercurrent contact with water, a small amount of hydrogen chloride entrained in the crude chloroethane gas is further washed and removed, and the refining temperature is controlled to be 30-35 ℃. Collecting refined liquid and pumping the refined liquid and the diluted hydrochloric acid generated by analysis to a chlorobenzene workshop for thickening to obtain concentrated hydrochloric acid. The refined chloroethane gas is fed into a demister and a drying agent calcium chloride packing tower for dewatering, and then is fed into a compressor. The chloroethane gas is compressed to the pressure of 0.2MPa by a compressor, cooled to liquid chloroethane by a cooler at normal temperature, and stored in a chloroethane finished product tank. The finished product chloroethane has the water content of 60ppm, the purity of 99.97 percent and the acidity of 6ppm after detection. The yield of ethyl chloride produced for 24 hours by taking the ethanol feed amount as a reference is 91.02 percent.
Example 2
Preparing an aluminum chloride-zinc chloride-hydrochloric acid solution in a 5-side circulating liquid receiving tank, wherein the aluminum chloride is as follows: the mass ratio of zinc chloride is 1:2.5; the content of hydrogen chloride in the solution is 10%; the total content of aluminum chloride-zinc chloride was 40%. The hypergravity reactor and hypergravity refining equipment are started, and the rotating speed is controlled at 500r/min. And (3) starting a circulating pump P to circulate the solution of the composite catalyst system, and heating to 120-125 ℃ through a circulating liquid heat exchanger A. Starting a concentrated hydrochloric acid analysis device, feeding 31% concentrated hydrochloric acid, controlling the flow to 6600kg/h, controlling the analysis temperature to 130-135 ℃, and monitoring the generated hydrogen chloride gas by using a flowmeter, wherein the feeding amount is 1070kg/h. The liquid ethanol is heated in a plate heat exchanger, is converted into ethanol gas and starts to be fed, wherein the mol ratio of the ethanol to the hydrogen chloride is controlled to be 1:1.08, the feeding amount of the ethanol is 1248kg/h, and the ethanol and the hydrogen chloride are mixed and then are contacted with a circulating catalytic solution in a static tube type mixer again to be fed into a hypergravity reactor for chlorine substitution reaction. And carrying out heat exchange on crude chloroethane gas generated by the reaction and ethanol through a plate heat exchanger, wherein water and hydrogen chloride are cooled to liquid and flow to a mother liquor water receiving tank. The cooled crude chloroethane gas is fed from the bottom of the hypergravity refining equipment and is in countercurrent contact with water, a small amount of hydrogen chloride entrained in the crude chloroethane gas is further washed and removed, and the refining temperature is controlled to be 30-35 ℃. Collecting refined liquid and pumping the refined liquid and the diluted hydrochloric acid generated by analysis to a chlorobenzene workshop for thickening to obtain concentrated hydrochloric acid. The refined chloroethane gas is fed into a demister and a desiccant molecular sieve packing tower for dewatering, and then is fed into a compressor. The chloroethane gas is compressed to the pressure of 0.25MPa by a compressor, cooled to liquid chloroethane by a cooler at normal temperature, and stored in a chloroethane finished product tank. The finished product chloroethane has the water content of 65ppm, the purity of 99.95 percent and the acidity of 8ppm after detection. The yield of chloroethane produced for 24 hours by calculation based on the ethanol feeding amount is 97.05 percent.
Example 3
Preparing an aluminum chloride-zinc chloride-hydrochloric acid solution in a 5-side circulating liquid receiving tank, wherein the aluminum chloride is as follows: the mass ratio of zinc chloride is 1:3; the content of hydrogen chloride in the solution is 15%; the total content of aluminum chloride-zinc chloride was 50%. The hypergravity reactor and hypergravity refining equipment are started, and the rotating speed is controlled at 500r/min. And (3) starting a circulating pump P to circulate the solution of the composite catalyst system, and heating to 125-130 ℃ through a circulating liquid heat exchanger A. Starting a concentrated hydrochloric acid analysis device, feeding 31% concentrated hydrochloric acid, controlling the flow to 6500kg/h, controlling the analysis temperature to 135-140 ℃, and monitoring the generated hydrogen chloride gas by using a flowmeter, wherein the feeding amount is 1070kg/h. The liquid ethanol is heated in a plate heat exchanger, is converted into ethanol gas and starts to be fed, wherein the molar ratio of the ethanol to the hydrogen chloride is controlled to be 1:1.1, namely the ethanol feeding amount is 1225kg/h, and the ethanol and the hydrogen chloride are mixed and then are contacted with a circulating catalytic solution in a static tubular mixer again to be fed into a hypergravity reactor for chlorine substitution reaction. And carrying out heat exchange on crude chloroethane gas generated by the reaction and ethanol through a plate heat exchanger, wherein water and hydrogen chloride are cooled to liquid and flow to a mother liquor water receiving tank. The cooled crude chloroethane gas is fed from the bottom of the hypergravity refining equipment and is in countercurrent contact with water, a small amount of hydrogen chloride entrained in the crude chloroethane gas is further washed and removed, and the refining temperature is controlled to be 30-35 ℃. Collecting the generated refined solution, and pumping the refined solution and the diluted hydrochloric acid generated by analysis into a chlorobenzene workshop for thickening to obtain concentrated hydrochloric acid. The refined chloroethane gas is fed into a demister and a desiccant molecular sieve packing tower for dewatering, and then is fed into a compressor. The chloroethane gas is compressed to the pressure of 0.3MPa by a compressor, cooled to liquid chloroethane by a cooler at normal temperature, and stored in a chloroethane finished product tank. The finished product chloroethane has the water content of 70ppm, the purity of 99.98 percent and the acidity of 9ppm after detection. The yield of chloroethane produced for 24 hours by calculation based on the ethanol feeding amount is 97.35 percent.
As can be seen from the above examples 1 to 3 and comparative examples 1 to 3, the yields of ethyl chloride in examples 1 to 3 in which the method of the present invention was used were high, and the use of a cooling medium was reduced and the reaction energy consumption was reduced due to the heat exchange between the crude ethyl chloride gas and liquid ethanol. The yields of ethyl chloride were lower in comparative examples 1-2, in which the catalyst in the method of the present invention was not used, and the yields were not ideal even if the reaction temperature was increased in comparative example 2. The yield of ethyl chloride was also lower in comparative example 3, in which the crude ethyl chloride gas was not heat-exchanged with liquid ethanol, and cooling of the crude ethyl chloride with additional cooling water was required.
Industrial applicability
The method of the invention can be widely used for the industrialized production of chloroethane.

Claims (11)

1. A process for the continuous production of ethyl chloride comprising the steps of:
the ethanol gas and the hydrogen chloride gas are contacted with an aluminum chloride-zinc chloride-hydrochloric acid composite catalyst solution to carry out chlorination reaction, so as to obtain crude chloroethane gas; wherein the chlorination reaction is carried out in a hypergravity reactor;
carrying out heat exchange on the crude chloroethane gas and liquid ethanol to obtain cooled crude chloroethane gas, wherein at least part of the ethanol gas is obtained by gasifying the liquid ethanol during the heat exchange;
Washing the cooled crude chloroethane gas with water, removing water from the washed refined chloroethane gas by a demister and a regenerable water absorbent, and then compressing, cooling and liquefying to obtain finished chloroethane;
Wherein, aluminum chloride in the aluminum chloride-zinc chloride-hydrochloric acid composite catalyst solution: the mass ratio of the zinc chloride is 1:1-5, the hydrogen chloride content is 10-15 mass percent, and the total content of the aluminum chloride and the zinc chloride is 30-50 mass percent;
the method for continuously producing chloroethane further comprises the following steps:
resolving the concentrated hydrochloric acid to generate the hydrogen chloride gas; and
And (3) using the water washing liquid generated by water washing and the diluted hydrochloric acid generated by concentrated hydrochloric acid analysis to absorb hydrogen chloride gas in a chlorobenzene workshop, thereby obtaining concentrated hydrochloric acid.
2. The method of claim 1, further comprising discharging and recycling the reaction liquid in the hypergravity reactor back to the hypergravity reactor.
3. The method according to claim 2, further comprising mixing the ethanol gas with the hydrogen chloride gas and then feeding the mixed gas into the hypergravity reactor in parallel with the composite catalyst solution or the circulating reaction liquid of the hypergravity reactor in a static tube mixer and dispersing on a packing layer of the hypergravity reactor.
4. The method according to claim 1 or 2, wherein the molar ratio of the ethanol gas to the hydrogen chloride gas is 1:1-1.15.
5. A process according to claim 1 or 2, characterized in that the heat exchange of the crude chloroethane gas with liquid ethanol is carried out in a plate heat exchanger.
6. The method according to claim 1 or 2, wherein the regenerable water absorbent is one or more selected from the group consisting of calcium chloride, molecular sieves, alumina, silica gel.
7. A method according to claim 3, wherein the static tube mixer is one selected from the group consisting of venturi, SV-type static tube mixer and SX-type static tube mixer.
8. The process according to claim 1 or 2, wherein the temperature of the chlorination reaction is 105-140 ℃; the temperature of the water washing is 30-35 ℃, and the chloroethane gas after water removal is compressed to the pressure of 0.1-0.4 MPa.
9. The method according to claim 1, wherein the concentrated hydrochloric acid has a desorption temperature of 110 to 150 ℃ and a desorption pressure of 0.1 to 0.3MPa.
10. The method according to claim 1, wherein the aqueous washing liquid produced by the aqueous washing and the diluted hydrochloric acid produced by the concentrated hydrochloric acid analysis are used for absorption of hydrogen chloride gas in a chlorobenzene plant to obtain concentrated hydrochloric acid, and the obtained concentrated hydrochloric acid is recycled for the concentrated hydrochloric acid analysis.
11. The method of claim 1, further comprising discharging the reaction liquid in the hypergravity reactor and recirculating back to the hypergravity reactor after passing through a heat exchanger.
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Publication number Priority date Publication date Assignee Title
CN106336341A (en) * 2016-08-22 2017-01-18 中南林业科技大学 Process for synthesizing ethyl chloride
CN106397081A (en) * 2015-07-14 2017-02-15 北京化工大学苏州（相城）研究院 Halogenation reaction method
CN106748633A (en) * 2017-01-10 2017-05-31 连云港瑞威化工有限公司 A kind of chloroethanes vapor phase method synthesis technique
CN106831315A (en) * 2017-01-18 2017-06-13 浙江迪邦化工有限公司 A kind of continuous production method of chloroethanes
CN107043318A (en) * 2017-05-12 2017-08-15 中南林业科技大学 It is a kind of to reclaim catalyst and its method for catalyzing and synthesizing chloroethanes from synthesis N, N dicyanoethyl arylamine mother liquors

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106397081A (en) * 2015-07-14 2017-02-15 北京化工大学苏州（相城）研究院 Halogenation reaction method
CN106336341A (en) * 2016-08-22 2017-01-18 中南林业科技大学 Process for synthesizing ethyl chloride
CN106748633A (en) * 2017-01-10 2017-05-31 连云港瑞威化工有限公司 A kind of chloroethanes vapor phase method synthesis technique
CN106831315A (en) * 2017-01-18 2017-06-13 浙江迪邦化工有限公司 A kind of continuous production method of chloroethanes
CN107043318A (en) * 2017-05-12 2017-08-15 中南林业科技大学 It is a kind of to reclaim catalyst and its method for catalyzing and synthesizing chloroethanes from synthesis N, N dicyanoethyl arylamine mother liquors

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