CN113831215A

CN113831215A - Multifunctional methane chloride production system

Info

Publication number: CN113831215A
Application number: CN202111116362.3A
Authority: CN
Inventors: 高永宝
Original assignee: Individual
Current assignee: Individual
Priority date: 2021-09-23
Filing date: 2021-09-23
Publication date: 2021-12-24

Abstract

The invention discloses a multifunctional methane chloride production system, which comprises a methane chloride production device by a methanol hydrochlorination method, a methane chloride production device by a methane chloride thermochlorination method, a dichloromethane refining device, a trichloromethane refining device, a carbon tetrachloride refining device, a methane chloride production device by carbon tetrachloride conversion and a hydrochloric acid depth analysis device, and realizes the ultra-large range free adjustment of the proportion of a full series of products; the byproduct hydrochloric acid is not generated, the whole process is coupled, energy is saved, the energy consumption is reduced, and the energy is effectively saved and the emission is reduced; the process can meet the modern engineering requirements of high quality, low consumption, long period, high load, multifunction, environmental protection and integration, realizes the limit utilization of chlorine atoms, and has the utilization rate of over 99 percent.

Description

Multifunctional methane chloride production system

Technical Field

The invention relates to the technical field of multifunctional methane chloride production systems and process methods, in particular to a multifunctional methane chloride production system for multifunctional full-series products and a multifunctional methane chloride production system for limiting utilization of chlorine atoms.

Background

The ratio of dichloromethane to trichloromethane of the product of the existing methane chloride device is basically 1:1, the adjusting range is small, one product cannot be produced independently, and only dichloromethane and trichloromethane can be produced in a balanced manner, or trichloromethane and carbon tetrachloride are produced mainly by using dichloromethane, or dichloromethane and carbon tetrachloride are produced mainly by using trichloromethane. The byproduct hydrochloric acid has large amount, which restricts the development of methane chloride. The utilization rate of the chlorine is low, calculated on the methane chloride, the utilization rate is only 85-87%, and a large amount of chlorine is converted into hydrochloric acid. The heat energy of the reaction heat generated by the chemical reaction of the device is not effectively utilized, and the energy consumption is relatively high.

In the prior art, CN 87103016B-methane thermal chlorination process discloses a process for producing methane chloride, dichloromethane, chloroform and carbon tetrachloride by methane thermal chlorination method, which returns cooled and purified gaseous products as small circulation to a reactor, and adjusts the relative proportion of four methane chlorides in the gaseous products, but the process can only produce one substance and the other three substances, the maximum proportion of the main product of dichloromethane is 60%, the maximum proportion of the main product of chloroform is 50%, and the maximum proportion of the main product of carbon tetrachloride is 80%. When the existing methane chloride is produced, on one hand, the obtained products are not high enough in purity, on the other hand, if only one product is required to be produced, redundant byproducts such as hydrochloric acid byproducts can be brought out, the obtained hydrochloric acid byproducts are more in impurities and cannot be directly applied to other fields, the waste of chlorine elements can be caused, and the production requirement of the existing methane chloride cannot be met.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention provides the multifunctional methane chloride production system which has the advantages of energy conservation, energy consumption reduction, effective energy conservation and emission reduction, can adjust the proportion of the produced methane chloride products in a wireless proportion, and can meet the requirements of high quality, low consumption, long period, high load, multiple functions, environmental protection.

The technical scheme adopted by the invention is as follows: a multifunctional methane chloride production system comprises a methane chloride production device by a methanol gas phase hydrochlorination method,

a methane chloride production device by a methanol gas phase hydrochlorination method, a methane chloride production device by a methane chloride thermochlorination method, a methylene chloride refining device, a trichloromethane refining device, a carbon tetrachloride refining device, a methane chloride production device by carbon tetrachloride conversion and a hydrochloric acid deep resolution device are sequentially connected, and methanol reacts with hydrogen chloride from the methane chloride production device by the methane chloride thermochlorination method and the hydrochloric acid deep resolution device to generate methane chloride;

the methane chloride production device by using the methane chloride thermal chlorination method comprises the steps of reacting methane chloride with chlorine to obtain a methane chloride mixed solution, feeding the methane chloride mixed solution serving as a raw material to a dichloromethane refining device to prepare dichloromethane, and simultaneously using the thermal energy of a high-temperature reaction mixed gas for byproduct steam;

the method comprises the following steps of (1) producing methane chloride by a dichloromethane refining device, a trichloromethane refining device, a carbon tetrachloride refining device and a carbon tetrachloride conversion device, sequentially separating and refining the obtained methane chloride mixed solution, dichloromethane mixed solution, trichloromethane mixed solution and carbon tetrachloride mixed solution one by one to simultaneously, sectionally or intermittently obtain dichloromethane products, trichloromethane products and carbon tetrachloride products in required production proportions;

the hydrochloric acid deep analysis device carries out deep analysis on dilute hydrochloric acid generated by a methane chloride production device by a methanol gas phase hydrochlorination method and a methane chloride production device by carbon tetrachloride conversion to obtain hydrogen chloride, and then returns the hydrogen chloride to a production system for recycling.

Preferably, the hydrochloric acid deep analysis device comprises a mixer, a hydrochloric acid deep analysis tower and a vacuum concentration tower which are connected in sequence;

the mixer is used for obtaining calcium water from a feed pump of the mixer for spraying, so that hydrochloric acid sent by a methane chloride production device by a methanol gas phase hydrochlorination method and a methane chloride production device by carbon tetrachloride conversion are fully mixed;

the hydrochloric acid deep desorption tower is used for desorbing hydrogen chloride, and the obtained hydrogen chloride sequentially passes through a primary condenser, a primary separator, a secondary condenser, a secondary separator and a hydrochloric acid demister for defoaming and is then supplied to a methane chloride production device by a methanol gas phase hydrochlorination method and/or a methane chloride production device by carbon tetrachloride conversion for reaction; the bottom of the vacuum concentration tower is provided with concentrated raw materials into the vacuum concentration tower through a feed pump of the vacuum concentration tower;

the vacuum concentration tower is used for concentrating the calcium chloride aqueous solution in a vacuum environment.

Preferably, the bottom of the vacuum concentration tower is connected with a heater of the vacuum concentration tower for steam heating, and the heated calcium chloride solution is supplied to the mixer through a feed pump of the mixer, so that the steam vaporization deep analysis is realized, and the analysis efficiency of the hydrochloric acid deep analysis device on hydrochloric acid is improved.

Preferably, the bottom of the hydrochloric acid deep desorption tower is further connected with a hydrochloric acid desorption tower reboiler, and the hydrochloric acid deep desorption tower reboiler is arranged to heat and gasify the liquid at the lower part of the hydrochloric acid deep desorption tower by using steam.

Preferably, the top of the vacuum concentration tower is sequentially connected with a condenser at the top of the vacuum concentration tower, a separator at the top of the vacuum concentration tower, a vacuum jet pump, a waste water storage tank and a waste water delivery pump, so that the separated waste water is sent out for treatment.

Compared with the prior art, the invention has the beneficial effects that:

1. the product of dichloromethane and trichloromethane, carbon tetrachloride that this system production obtained obtains the proportion, can infinitely adjust according to the production demand, and the product proportion can be: 0-30% of methane chloride, 0-100% of dichloromethane, 0-100% of trichloromethane and 0-100% of carbon tetrachloride. The purity of dichloromethane, trichloromethane and carbon tetrachloride reaches ultra-high purity grade, and common grade and high-purity grade products can also be produced; the product variety is multifunctional, the product purity is also multifunctional, measures can be flexibly adopted according to market conditions, and the economic benefit is maximized.

2. The hydrogen chloride separated in the system is completely used for producing methane chloride, so that the chlorine is recycled. Because a large amount of hydrochloric acid is not produced as a byproduct, the production cannot be restricted, and the economic benefit cannot be tired, and the methane chloride is completely produced by the hydrogen chloride, the productivity of the device is improved, and the economic benefit of the device is greatly improved.

3. The methane chloride thermal chlorination reaction system adopts a high-power double-injection jet mixing technology to fully mix the raw material gas and the chlorine; the high-power explosion-proof electric heating technology is adopted, so that the temperature of the thermal chlorination reactor can be raised, and the temperature of the reactor can be stabilized; the reaction capacity is doubled, the production capacity of a single set of chloromethane thermal chlorination reactor provided with a high-power explosion-proof electric heater and a high-power double-injection jet mixer can reach 12 ten thousand tons per year, and the reaction capacity is doubled.

4. The intermediate liquid material of the methane chloride heat chlorination device and the product separation device is circularly dried by adopting a drying agent, so that the moisture of the material reaches the standard, the device is prevented from being corroded, and the device can be produced for a long period.

5. Coupling energy conservation and ultra-low energy consumption. Steam condensate water collected in the methane chloride production is used for preheating methanol; the heat released by the reaction of methanol and hydrogen chloride is totally used for vaporizing the methanol and heating the reaction raw materials; the produced methane chloride gas is pressurized by a compressor and then directly sent to a methane chloride thermal chlorination device without condensation liquefaction and then vaporization; the heat byproduct steam of the methane chloride heat chlorination reaction is used for the process system; the cold energy of condensate of the deep condenser is utilized; the tower kettle discharge of the light component separation tower exchanges heat with the tower feed; the tower bottom discharge of the dichloromethane rectification tower exchanges heat with the tower feed, the tower bottom discharge of the trichloromethane rectification tower exchanges heat with the tower feed, and the reaction heat of methane chloride produced by the conversion of carbon tetrachloride is fully utilized to heat the raw material; the steam condensate water of the device is completely collected and is firstly used for preheating raw materials and then sent to a deionized water device to be used as raw materials; the effect of reducing carbon emission is very obvious.

6. The method has the advantages that no water washing and alkali washing are carried out, the three wastes are less, deep condensation sulfuric acid series drying is directly carried out after cooling, and the water content of the methane chloride is ultra-low.

7. After the dry methane chloride gas (containing a small amount of hydrogen chloride) is pressurized by a compressor, the hot crude methane chloride gas is directly sent to a methane chloride thermal chlorination reaction device instead of being cooled, liquefied and stored and then vaporized to be sent to the methane chloride thermal chlorination reaction device, so the process is short, and the energy-saving effect is good. And performing dry separation on the redundant crude chloromethane and the light component to obtain the commercial chloromethane.

In conclusion, the multifunctional methane chloride production system of the invention enables the whole methane chloride system to achieve infinite flexibility, and can produce only dichloromethane, only trichloromethane, only carbon tetrachloride and two products except methane chloride, thereby meeting various requirements. The purity of the products of the monochloro methane, the methylene dichloride, the trichloromethane and the carbon tetrachloride reaches an ultra-high purity level, and common pure and high-grade pure products can be produced, so that the multifunctionality of the device is fully embodied; the residual hydrogen chloride and the low-concentration hydrochloric acid are deeply analyzed to obtain the hydrogen chloride which is all used for producing the methane chloride, so that the factors restricting the production are reduced, and the economic benefit is improved.

The utilization rate of chlorine is increased to more than 99.5 percent according to the methane chloride. The whole process is coupled to save energy, reduce energy consumption, effectively save energy and reduce emission; the single-set capacity of the methane chloride produced by the dry-method hydrochlorination of the methanol is improved by 3 times, and the annual capacity of a single set of device can reach more than 10 ten thousand tons. The single-set capacity of methane chloride production by a methane chloride gas phase thermal chlorination method is improved by 1 time.

The multifunctional methane chloride production system of the invention enables the utilization of chlorine atoms to reach the limit, and the utilization rate far exceeds that of the existing methane chloride production device. And various new coupling energy-saving technologies are adopted, so that energy conservation, consumption reduction and emission reduction are greatly realized. The single set of capacity reaches 12 ten thousand tons per year, and is the device with the largest single set of production capacity in China. And by adopting a comprehensive dewatering technology, the moisture in the material is greatly reduced, and the service life of the system is effectively prolonged. The multifunctional methane chloride production system and the process requirements of multifunction, low consumption, large capacity, high quality, long period, environmental protection and integration modern engineering requirements are completely met.

Drawings

FIG. 1 is a block diagram of a multi-functional methane chloride production system;

FIG. 2 is a process flow diagram of the methanol hydrochlorination process for producing methyl chloride;

FIG. 3 is a process flow diagram of methane chloride production by a methane chloride gas phase thermal chlorination process;

FIG. 4 is a process flow diagram of a dichloromethane refining apparatus;

FIG. 5 is a process flow diagram of a chloroform refining apparatus;

FIG. 6 is a process flow diagram of a carbon tetrachloride refining apparatus;

FIG. 7 is a flow chart of a process for producing methane chloride by the conversion of carbon tetrachloride;

FIG. 8 is a process flow diagram of a hydrochloric acid deep desorption apparatus.

Detailed Description

Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.

In the description of the present invention, it is to be understood that the terms "center", "upper", "lower", "front", "rear", "left", "right", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience in describing the present invention and simplifying the description, but do not indicate or imply that the combination or element referred to must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, are not to be construed as limiting the present invention. In addition, in the description process of the embodiment of the present invention, the positional relationships of the devices such as "upper", "lower", "front", "rear", "left", "right", and the like in all the drawings are based on fig. 1.

As shown in fig. 1, a multifunctional methane chloride production system, wherein a methane chloride production device 100 by a methanol gas phase hydrochlorination method is sequentially connected with a methane chloride production device 200 by a methane chloride thermochlorination method, a dichloromethane refining device 300, a trichloromethane refining device 400, a carbon tetrachloride refining device 500, a methane chloride production device 600 by carbon tetrachloride conversion and a hydrochloric acid deep resolution device 700, and methanol reacts with hydrogen chloride from the methane chloride production device 200 by the methane chloride thermochlorination method and the hydrochloric acid deep resolution device 700 to produce methane chloride;

the methane chloride production device 200 by a methane chloride thermal chlorination method comprises the steps of reacting methane chloride with chlorine to obtain a methane chloride mixed solution, supplying the methane chloride mixed solution serving as a raw material to a dichloromethane refining device 300 to prepare dichloromethane, and simultaneously thermally producing steam as a byproduct from high-temperature reaction mixed gas;

the dichloromethane refining device 300 is used for separating and refining the obtained methane chloride mixed solution to obtain a dichloromethane product, and providing a dichloromethane mixed solution raw material for the trichloromethane refining device 400 according to requirements;

the chloroform refining device 400 is used for obtaining dichloromethane mixed liquid raw materials, performing separation and refining to obtain chloroform products, and providing the chloroform mixed liquid raw materials for the carbon tetrachloride refining device 500 according to requirements;

a carbon tetrachloride refining device 500 for obtaining the chloroform mixed solution to separate and refine the carbon tetrachloride product and providing the raw material for the carbon tetrachloride conversion methane chloride production device 600 according to the requirement;

a methane chloride production device 600 for converting carbon tetrachloride, wherein the carbon tetrachloride is subjected to conversion reaction in the environment of methanol and hydrogen chloride to generate methane chloride, and a methane chloride product is obtained;

the hydrochloric acid deep analysis device 700 deeply analyzes dilute hydrochloric acid generated by the methane chloride production device 100 by a methanol gas phase hydrochlorination method and the methane chloride production device 600 by carbon tetrachloride conversion to obtain hydrogen chloride, and then returns the hydrogen chloride to the system for recycling, namely, the multifunctional methane chloride production system can realize the adjustment of the proportion of a dichloromethane product by 0-100, the adjustment of the proportion of a trichloromethane product by 0-100 and the adjustment of the proportion of a carbon tetrachloride product by 0-100, can not by-produce hydrochloric acid, can improve the utilization rate of chlorine to more than 99%, can fully utilize all chlorides, saves chlorine elements, and returns the hydrogen chloride obtained by analysis to the methane chloride production device 100 by the methanol gas phase hydrochlorination method and the methane chloride production device 600 by carbon tetrachloride conversion as raw materials, thereby further improving the utilization rate of the chlorine elements.

As shown in fig. 2, the apparatus 100 for producing methane chloride by the methanol hydrochlorination method of the present invention includes:

the device 100 for producing the methane chloride by the methanol hydrochlorination method comprises a hydrochlorination reactor 106, a quench tower 107, a quench tank 108 and the like, wherein the hydrochlorination reactor 106 is mixed with three gas streams to carry out gas-phase fixed-bed catalytic hydrochlorination to generate the methane chloride, and the three gas streams are respectively:

the first air flow: the methanol is superheated by a methanol preheater I101, a methanol vaporizer I102, a methanol heater I103 and a methanol superheater I104 which are connected in sequence to obtain superheated methanol;

and (2) airflow II: hydrogen chloride separated by the methane chloride production device 200 by a methane chloride hot chlorination method is superheated by a hydrogen chloride superheater I105 to obtain superheated hydrogen chloride;

airflow III: the hydrogen chloride separated by the hydrochloric acid deep analysis device 700 is mixed with the hydrogen chloride separated by the methane chloride production device 200 by a methane chloride gas phase thermal chlorination method, and superheated hydrogen chloride is obtained after the mixture is superheated by a hydrogen chloride superheater I105;

the first chilling tower 107 is also sequentially connected with a first acid condenser 109, a first separator 110, a first chilling tank 108, a first demister 111, a sulfuric acid drying tower I112, a sulfuric acid drying tower II 113, a sulfuric acid drying tower III 114, a sulfuric acid demister 115 and a first compressor 116; the connection is that the reaction mixed gas from the hydrochlorination reactor 106 firstly enters a quench tower I107 to be quenched, then is condensed by an acid condenser I109 and is separated by a separator I110 to obtain hydrochloric acid condensate, and the separated hydrochloric acid condensate is used as a quench liquid to quench the reaction mixed gas in the quench tower I107;

the hydrochloric acid discharged from the first chilling tank 108 enters the hydrochloric acid deep analysis device 700, the mixed gas discharged from the first chilling tank is cooled and separated to obtain condensate, the condensate is cooled and separated to be removed from the first chilling tower 107, the obtained uncondensed gas sequentially enters the sulfuric acid drying tower I, the sulfuric acid drying tower II, the sulfuric acid drying tower III, the sulfuric acid drying tower I112, the sulfuric acid drying tower II 113 and the sulfuric acid drying tower III 114 to be subjected to deep condensation sulfuric acid drying, and then the condensate enters the compressor I116.

The crude methane chloride gas compressed by the compressor I116 can be sent to a methane chloride production device 200 by methane chloride thermal chlorination as a raw material, and a part of the crude methane chloride is liquefied by a condensate to obtain liquid crude methane chloride which is stored in a crude methane chloride storage tank 117 to be supplied to the methane chloride production device 200 by methane chloride thermal chlorination.

Specifically, the first methanol preheater 101 is arranged to preheat methanol by using heat of steam condensate collected by the device; the first methanol vaporizer 102 is arranged to vaporize methanol by using a heating medium of the hydrochlorination reactor; the first methanol heater 103 is arranged to further heat the vaporized methanol with steam; the first methanol superheater 104 is configured to heat the methanol gas to the feed temperature required by the hydrochlorination reactor using the heating medium of the hydrochlorination reactor. The hydrogen chloride superheater one 105 is arranged to heat the hydrogen chloride gas to the feed temperature required by the hydrochlorination reactor by using the heating medium of the hydrochlorination reactor. The hydrochlorination reactor 106 is configured to produce methyl chloride by a gas phase fixed bed catalytic reaction of superheated hydrogen chloride and methanol at a temperature and pressure. The quench tower one 107 is configured to quench the reaction mixture with liquid acid. The quench tank one 108 is configured to separate acid from the gas. The first acid condenser 109 is arranged to fractionate the gas exiting the quench tank. The first separator 110 is configured to separate gas and liquid from the material sent from the first acid condenser 109. The first demister 111 is arranged to intercept mist in the gas sent by the first separator 110. Sulfuric acid drying I tower the sulfuric acid drying I tower 112 is configured to perform a first drying of the reaction gas. Sulfuric acid drying II tower the sulfuric acid drying II tower 113 is configured to perform a second drying of the reaction gas. The sulfuric acid drying III tower 114 is configured to dry the reaction gas a third time. The sulfuric acid demister 115 is configured to intercept entrainment in the gas. Compressor one 116 is configured to boost the pressure of the crude methyl chloride gas. The crude methane chloride storage tank 117 is configured to store qualified methane chloride liquid.

As shown in fig. 3, the device 200 for producing methane chloride by a methane chloride thermochlorination method comprises a methane chloride vaporizer 201, a methylene dichloride vaporizer 202, a chloroform vaporizer 203, a mixed gas heating 204, a double-injection jet mixer 205, a methane chloride thermochlorination reactor 206, a waste heat boiler 207, a steam pocket 208 and a second quench tower 209 which are sequentially connected, wherein the second quench tower 209 is sequentially connected with a first-stage condenser 210, a first-stage separator 211, a gas inlet heat exchanger 213, a second-stage separator 214, a deep condenser 215 and a deep condensation separator 216, wherein:

the first-stage separator 211 is used for inputting the separated gas into a heat exchanger 213 to exchange heat with cold materials and then entering a second-stage separator 214, and the separated liquid enters a primary material storage tank 212;

the raw material storage tank 212 is connected with a tower bottom heat exchanger 219 of a primary separation tower 218 and a tower bottom cooler 220 of the primary separation tower in sequence, so that methane chloride discharged from the raw material storage tank 212 is subjected to light component removal and cooling, and then is conveyed to a dichloromethane refining device 300 of a multifunctional methane chloride production system;

the deep condensation separator 216 is used for separating and exchanging heat and is connected with the heat exchanger feed chute 217, so that the heat exchanger feed chute provides cold materials for the heat exchanger, and the gas separated by the deep condensation separator provides hydrogen chloride gas as a raw material for the methane chloride production device 200 by a methane chloride gas phase thermal chlorination method;

the waste heat boiler 207 is connected with the steam drum 208 to obtain steam, and the steam produced by utilizing the heat energy of the reaction mixed gas enters the steam pipe network of the device as heat energy, so that the steam consumption of the device is reduced, and the purposes of energy conservation and emission reduction are achieved.

More preferably, the top of the primary tower 218 is connected with a primary tower top condenser 221 and a light component storage tank 222, and light components are provided for the methane chloride production device 200 by a methane chloride thermal chlorination method.

A methane chloride vaporizer 201, a methylene dichloride vaporizer 202, and a mixed gas heater 204 configured to vaporize methane chloride, methylene dichloride, and chloroform into gases, respectively, using steam. The mixed gas heater 204 is configured to mix methane chloride and the light component gas and heat the mixture to a predetermined temperature. The high-power double-injection jet mixer 205 is set to be high in capacity because the first-stage injection utilizes chlorine under certain pressure to inject and mix methane chloride and light components, and the second-stage injection utilizes the raw material gas to inject and mix high-temperature reaction gas. The methane chloride thermal chlorination reactor 206 is configured to perform a thermal chlorination reaction of methane chloride and light components with chlorine gas at a certain temperature and under a certain pressure to generate methane chloride. The exhaust-heat boiler 207 is a heat energy transfer device for exchanging heat between the high-temperature reaction gas mixture and the hot water, the reaction gas mixture can be rapidly cooled, and the hot water can be rapidly heated. The steam drum 208 is provided as a container for flowing hot water into the waste heat boiler 207, receiving high-temperature hot water sent by the waste heat boiler and then flashing to form steam, and is provided with a water heating device. The second quench tower 209 is a reaction gas quench tower for further rapidly cooling the cooled reaction mixture gas to a temperature below a predetermined temperature by using liquid methane chloride. The primary condenser 210 is provided as a water-cooled condenser that partially condenses the methane chloride mixed gas into a liquid phase. The first-stage separator 211 is provided to separate the gas and liquid of the coolant supplied from the front. The coarse material storage tank 212 is configured to collect liquid materials from the first stage separator 211 and the second stage separator 214. The heat exchanger 213 is arranged to further cool the noncondensable gas from the onward supply by means of the refrigeration content of the after-system material. The second separator 214 is provided to separate the cooled material sent from the heat exchanger 213 into gas and liquid. The deep condenser 215 is provided to cryogenically cool the noncondensable gas supplied from the front side by a refrigerant. The deep condensate separator 216 is configured to separate the cryogenic feed from the deep condenser 215 into a vapor and a liquid. The low level sump 217 is configured to collect liquid material separated by the deep condensate separator 216. The primary separation tower 218 is configured to separate the light components from the heavy components of the chloride mixed liquor. The preliminary separation tower bottom heat exchanger 219 is configured to exchange heat between the tower bottom discharge and the tower feed of the preliminary separation tower 218. The preliminary separation column bottoms cooler 220 is configured to further cool the crude methane chloride from the preliminary separation column bottoms heat exchanger 219. The condenser 221 at the top of the primary tower is arranged to partially condense the material coming out of the top of the primary tower 218. The light component tank 222 is provided to separate the gas and liquid of the material sent from the condenser 221 at the top of the preliminary separation column and store the liquid as a reflux liquid.

Preferably, the heat exchanger 213 is further connected with a mixed gas heater 204 of a methane chloride production device by a methane chloride thermochlorination method, and the hydrogen chloride obtained by the deep condensation separator 216 is supplied to the methane chloride production device 100 by a methanol hydrochlorination method and the methane chloride production device 600 by carbon tetrachloride conversion for recycling, so that the energy consumption is further saved.

As shown in fig. 4, the dichloromethane purification apparatus 300 of the present invention comprises a dichloromethane purification tower feeding and discharging heat exchanger 301, a dichloromethane purification tower 302, a dichloromethane purification tower reboiler 303, a dichloromethane purification tower overhead condenser 304, a dichloromethane purification tower reflux tank 305, a dichloromethane purification tower reflux pump 306, a dichloromethane alkaline washing pump 307, a dichloromethane alkaline washing tank 308, a dichloromethane azeotropic tower feeding pump 309, a dichloromethane azeotropic tower overhead condenser 310, a dichloromethane azeotropic tower 311, a dichloromethane azeotropic tower reboiler 312, a dichloromethane azeotropic tower bottom cooler 313, and a dichloromethane purification tower bottoms conveying pump 314, which are connected in sequence. The bottom of the dichloromethane refining tower 302 is connected with a dichloromethane refining tower feeding and discharging heat exchanger 301, so that heat exchange is realized.

A dichloromethane refining apparatus 300 for obtaining dichloromethane products and providing raw materials for the chloroform refining apparatus 400;

the dichloromethane refining tower feeding and discharging heat exchanger 301 is arranged to exchange heat between the chloride mixed solution from the methane chloride production device 200 by a monochloromethane thermal chlorination method and the crude trichloromethane mixed solution from the tower bottom of the dichloromethane refining tower 302; the dichloromethane refining column 302 is configured to separate dichloromethane from the chloride mixture; the dichloromethane refining tower reboiler 303 is set to heat the materials in the tower kettle of the dichloromethane refining tower 302 by using steam; the dichloromethane refining tower top condenser 304 is used for condensing dichloromethane from the top of the dichloromethane refining tower 302; the dichloromethane refining tower reflux tank 305 is arranged to store the condensate sent by the dichloromethane refining tower overhead condenser 304 and supply the condensate to the dichloromethane refining tower reflux pump 306; the dichloromethane refining tower reflux pump 306 is arranged to pump the condensate into the dichloromethane refining tower 302 as reflux, and send a part of the condensate into the dichloromethane alkaline washing pump 307; the dichloromethane alkali washing pump 307 is used for mixing and circulating the condensate and caustic soda to remove acid; a dichloromethane caustic wash tank 308 is configured to mix and separate the material with caustic soda while feeding a dichloromethane azeotrope column feed pump 309; a methylene chloride azeotropic column feed pump 309 is provided to convey the methylene chloride containing water in the methylene chloride caustic wash tank 308 to the methylene chloride azeotropic column 311; the dichloromethane azeotropic tower top condenser 310 is arranged to condense the materials and water from the top of the dichloromethane azeotropic tower 311 and send the materials and water into the dichloromethane alkali washing tank 308; the dichloromethane azeotropic tower 311 is arranged to separate dichloromethane from water, and a product dichloromethane is obtained from the tower kettle; the dichloromethane azeotropic tower reboiler 312 is arranged to heat and gasify the materials in the tower kettle of the dichloromethane azeotropic tower 311; the dichloromethane azeotropic tower bottom cooler 313 is arranged to cool dichloromethane with certain temperature from the tower kettle of the dichloromethane azeotropic tower 311; the methylene dichloride refining tower bottoms delivery pump 314 is configured to deliver the crude trichloromethane from the bottom of the methylene dichloride refining tower 302 to the trichloromethane refining plant 400.

As shown in fig. 5, the chloroform refining apparatus 400 of the present invention comprises a chloroform refining tower feed/discharge heat exchanger 401, a chloroform refining tower 402, a chloroform refining tower reboiler 403, a chloroform refining tower overhead condenser 404, a chloroform refining tower reflux drum 405, a chloroform refining tower reflux pump 406, a chloroform caustic wash pump 407, a chloroform caustic wash tank 408, a chloroform azeotropic tower feed pump 409, a chloroform azeotropic tower overhead condenser 410, a chloroform azeotropic tower 411, a chloroform azeotropic tower reboiler 412, a chloroform azeotropic tower bottom cooler 413, and a chloroform refining tower bottoms delivery pump 414, which are connected in sequence.

The chloroform refining apparatus 400 obtains the chloroform product and provides the raw material for the carbon tetrachloride refining apparatus 500.

The trichloromethane refining tower feeding and discharging heat exchanger 401 is arranged to exchange heat between crude trichloromethane from the dichloromethane refining device 300 and crude carbon tetrachloride mixed liquor from the tower kettle of the trichloromethane refining tower 402; the chloroform refining column 402 is configured to separate chloroform from the chloride mixture; the chloroform refining tower reboiler 403 is configured to heat the material in the tower bottom of the chloroform refining tower 402 by using steam; the condenser 404 at the top of the trichloromethane refining tower is used for condensing the trichloromethane coming out from the top of the trichloromethane refining tower 402; the reflux tank 405 of the chloroform refining tower is arranged to store the condensate liquid sent by the condenser 404 at the top of the chloroform refining tower and feed the condensate liquid to the reflux pump 406 of the chloroform refining tower; the chloroform refining tower reflux pump 406 is configured to pump the condensate into the chloroform refining tower 402 as reflux, and to send a portion of the condensate into the chloroform caustic wash pump 407; the trichloromethane alkali washing pump 407 is arranged to mix the condensate with caustic soda for cyclic deacidification; the trichloromethane alkali washing tank 408 is arranged to mix and separate the materials with caustic soda and simultaneously feed the materials to a trichloromethane azeotropic tower feeding pump 409; a chloroform azeotropic tower feed pump 409 is arranged to convey the chloroform containing water in the chloroform alkaline washing tank 408 to the chloroform azeotropic tower 411; the condenser 410 at the top of the trichloromethane azeotropic tower is used for condensing the materials and water from the top of the trichloromethane azeotropic tower 411 and sending the materials and the water into the trichloromethane alkaline washing tank 408; the chloroform azeotropic tower 411 is arranged to separate chloroform from water, and a product chloroform is obtained from the tower kettle; the chloroform azeotropic tower reboiler 412 is arranged to heat and gasify the materials in the tower kettle of the chloroform azeotropic tower 411; the chloroform azeotropic tower bottom cooler 413 is used for cooling the chloroform with a certain temperature from the tower kettle of the chloroform azeotropic tower 411; the chloroform refining tower bottoms delivery pump 414 is configured to send the crude chloroform in the bottom of the chloroform refining tower 402 to the carbon tetrachloride refining device 500 or the carbon tetrachloride conversion device 600 for producing methane chloride.

As shown in FIG. 6, the carbon tetrachloride refining apparatus 500 of the present invention comprises a carbon tetrachloride refining tower feeding and discharging heat exchanger 501, a carbon tetrachloride refining tower 502, a carbon tetrachloride refining tower reboiler 503, a carbon tetrachloride refining tower overhead condenser 504, a carbon tetrachloride refining tower reflux drum 505, a carbon tetrachloride refining tower reflux pump 506, a carbon tetrachloride alkaline washing pump 507, a carbon tetrachloride alkaline washing tank 508, a carbon tetrachloride azeotropic tower feeding pump 509, a carbon tetrachloride azeotropic tower overhead condenser 510, a carbon tetrachloride azeotropic tower 511, a carbon tetrachloride azeotropic tower reboiler 512, a carbon tetrachloride azeotropic tower bottom cooler 513 and a carbon tetrachloride refining tower bottom liquid delivery pump 514, which are connected in sequence.

The charging and discharging heat exchanger 501 of the carbon tetrachloride refining tower is used for exchanging heat between crude carbon tetrachloride from the chloroform refining device 400 and heavy component mixed liquid from the tower kettle of the carbon tetrachloride refining tower 502; the carbon tetrachloride refining column 502 is configured to separate carbon tetrachloride from the chloride mixed liquor; the reboiler 503 of the carbon tetrachloride refining tower is arranged to heat the material in the tower kettle of the carbon tetrachloride refining tower 502 by using steam; the condenser 504 at the top of the carbon tetrachloride refining tower is used for condensing carbon tetrachloride coming out from the top of the carbon tetrachloride refining tower 502; the reflux tank 505 of the carbon tetrachloride refining tower is arranged to store the condensate sent by the condenser 504 at the top of the carbon tetrachloride refining tower and supply the condensate to the reflux pump 506 of the carbon tetrachloride refining tower; the carbon tetrachloride refining tower reflux pump 506 is configured to pump the condensate into the carbon tetrachloride refining tower 502 as reflux and to send a portion of the condensate to the carbon tetrachloride caustic wash pump 507; the carbon tetrachloride alkaline washing pump 507 is arranged to mix the condensate with caustic soda for cyclic acid removal; the carbon tetrachloride caustic wash tank 508 is configured to mix and separate the material with caustic soda while supplying the material to the carbon tetrachloride azeotropic tower feed pump 509; a carbon tetrachloride azeotropic column feed pump 509 is provided to convey the carbon tetrachloride containing water in the carbon tetrachloride caustic wash tank 508 to the carbon tetrachloride azeotropic column 511; the condenser 510 at the top of the carbon tetrachloride azeotropic tower is used for condensing the material and water from the top of the trichloromethane azeotropic tower 511 and sending the condensed material and water into the carbon tetrachloride alkaline washing tank 508; the carbon tetrachloride azeotropic tower 511 is arranged to separate carbon tetrachloride from water and obtain a product carbon tetrachloride from the tower kettle; the reboiler 512 of the carbon tetrachloride azeotropic tower is arranged to heat and gasify the material in the tower kettle of the carbon tetrachloride azeotropic tower 511; the tower bottom cooler 513 of the carbon tetrachloride azeotropic tower is arranged to cool carbon tetrachloride with a certain temperature from the tower kettle of the carbon tetrachloride azeotropic tower 511; the carbon tetrachloride refining column bottoms transfer pump 514 is configured to feed heavy components from the column bottoms of the carbon tetrachloride refining column 502 to the post-treatment device.

And a carbon tetrachloride refining device 500 for obtaining a carbon tetrachloride product.

As shown in fig. 7, the apparatus 600 for producing methane chloride by carbon tetrachloride conversion according to the present invention comprises:

the reaction system for producing methane chloride by converting carbon tetrachloride comprises a conversion reactor 608, a quench tower 609, a quench tank 610 and the like, wherein the conversion reactor 608 is mixed with four gas flows to perform gas phase fixed bed catalytic conversion reaction to generate methane chloride, and the four gas flows are respectively:

the first air flow: the methanol is superheated by a second methanol preheater 601, a second methanol vaporizer 602, a second methanol heater 603 and a second methanol superheater 604 which are connected in sequence to obtain superheated methanol;

and (2) airflow II: hydrogen chloride separated by the methane chloride production device (2) by a methane chloride hot chlorination method is superheated by a hydrogen chloride superheater II 605 to obtain superheated hydrogen chloride;

airflow III: the hydrogen chloride separated by the hydrochloric acid deep analysis device is mixed with the hydrogen chloride separated by the methane chloride production device by a methane chloride gas phase thermal chlorination method, and the superheated hydrogen chloride is obtained after the mixture is superheated by a hydrogen chloride superheater II 605;

and (4) airflow: the carbon tetrachloride is superheated through a carbon tetrachloride vaporizer 606 and a carbon tetrachloride superheater 607 which are connected in sequence to obtain superheated carbon tetrachloride;

the second chilling tower 609 is also sequentially connected with a second chilling groove 610, a second acid condenser 611, a second separator 612, a second demister 613, a sulfuric acid drying tower 614, a second sulfuric acid demister 615 and a second methyl chloride compressor 616;

the connection is that the reaction mixed gas from the conversion reactor 608 firstly enters a second quench tower 609 to be quenched, then is condensed by a second acid condenser 611, is separated by a second separator 612 to obtain a hydrochloric acid condensate, and is quenched in the second quench tower 609 by using the hydrochloric acid condensate obtained by separation as a quench liquid;

and the hydrochloric acid from the second quenching tank 610 enters a hydrochloric acid deep analysis device (7), the mixed gas from the second quenching tank 610 is cooled and separated, the condensate liquid is removed from the second cooling tower 609, the uncondensed gas passes through a second demister 613 and then enters a sulfuric acid drying tower 614 for sulfuric acid drying, and then enters a second chloromethane compressor 616.

The crude methane chloride gas formed by compression in the methane chloride compressor II 616 can be sent to the methane chloride production device 200 by methane chloride thermal chlorination method to be used as raw material, and a part of crude methane chloride is condensed and liquefied to obtain liquid crude methane chloride which is stored in the methane chloride primary distillation tower feeding groove 617 and then is conveyed to the methane chloride primary distillation tower by a pump for separation.

The crude methane chloride enters a methane chloride primary distillation tower 618 for separation, the light components from the tower top return to a methane chloride production device 200 by methane chloride thermochlorination, the methane chloride in the tower bottom is pumped into a methane chloride rectifying tower 623 for rectification and separation, and the gas from the tower top is condensed and neutralized to obtain the product methane chloride.

The second methanol preheater 601 is arranged to preheat methanol by using the heat of the steam condensate water collected by the device; the second methanol vaporizer 602 is configured to vaporize methanol using a heating medium of the reforming reactor; the second methanol heater 603 is arranged to further heat the vaporized methanol with steam; the second methanol superheater 604 is configured to utilize the heating medium of the reforming reactor to heat the methanol gas to the feed temperature required by the reforming reactor. The second hydrogen chloride superheater 605 is configured to heat the hydrogen chloride gas to a feed temperature required by the shift reactor using a heating medium of the shift reactor. The carbon tetrachloride vaporizer 606 is configured to vaporize carbon tetrachloride with steam; carbon tetrachloride superheater 607 is configured to heat the carbon tetrachloride gas to the feed temperature required by the conversion reactor using the heat medium of the conversion reactor. The reforming reactor 608 is configured to perform a gas phase fixed bed catalytic reforming reaction of superheated hydrogen chloride, methanol, and carbon tetrachloride at a temperature and a pressure to produce methyl chloride. The second quench tower 609 is configured to rapidly cool the reaction mixture with liquid acid. The second quench tank 610 is configured to separate acid from the gas. And the second acid condenser 611 is used for performing fractional condensation on the gas discharged from the chilling tank. The second separator 612 is configured to separate the gas and the liquid of the material sent by the second acid condenser 611. The second demister 613 is configured to intercept mist in the gas sent from the second separator 612. The sulfuric acid drying tower 614 is configured to dry the reaction gas. The second sulfuric acid demister 615 is arranged to intercept mist in the gas. The methyl chloride compressor two 616 is configured to boost the pressure of the crude methyl chloride gas. The crude methane chloride storage tank 617 is configured to store qualified methane chloride liquid. The methane chloride primary distillation tower 618 is arranged to separate light components in the crude methane chloride and condense the light components from the top of the tower, and the methane chloride from the bottom of the tower is pumped into a methane chloride rectifying tower 623; the methane chloride primary distillation tower reboiler 619 is set to heat and gasify the liquid in the tower bottom of the methane chloride primary distillation tower 618 by using steam; the top condenser 620 of the methane chloride primary distillation tower is used for condensing light components from the top of the methane chloride primary distillation tower and sending condensate into a reflux tank 621 of the methane chloride primary distillation tower; a methane chloride primary distillation tower reflux tank 621 is arranged to store liquid light components and feed the liquid light components to a methane chloride primary distillation tower reflux pump 622; the methane chloride primary tower reflux pump 622 is set to pump a part of the liquid light components into the methane chloride primary tower 618 as reflux liquid, and a part of the liquid light components are sent to the methane chloride device 200 for producing methane chloride by a methane chloride thermal chlorination method; the methane chloride rectifying tower reboiler 624 is set to heat and gasify the liquid in the tower bottom of the methane chloride rectifying tower 623 by using steam; a methane chloride rectifying tower bottom liquid conveying pump 625 is arranged to convey heavy components in the tower bottom of the methane chloride rectifying tower 623 to a methane chloride production device (2) by a methane chloride thermal chlorination method; the top condenser 626 of the methane chloride rectifying tower is arranged to condense methane chloride gas from the top of the methane chloride rectifying tower by using cooling water and send the condensed gas to a reflux tank 627 of the methane chloride rectifying tower; the methane chloride rectification tower reflux tank 627 is configured to store condensate and feed the condensate to a methane chloride rectification tower reflux pump 628; the methane chloride rectifying tower reflux pump 628 is configured to pump a portion of the liquid methane chloride into the methane chloride rectifying tower 623 as reflux, and a portion is sent to a methane chloride cooler 629; the methane chloride cooler 629 is configured to cool methane chloride with cooling water and send the cooled methane chloride to the methane chloride neutralizer 630; the methane chloride neutralizer 630 is configured to remove acidity in methane chloride using solid caustic soda and feed to the methane chloride cryocooler 631; the monochloromethane cryocooler 631 is arranged to cool the monochloromethane using low temperature dichloromethane; the cooled methane chloride is sent into a methane chloride finished product tank 632; a methyl chloride finished product tank 632 is configured to store methyl chloride and feed the methyl chloride finished product to a methyl chloride finished product conveying pump 633; the methane chloride finished product delivery pump 633 is arranged to deliver the product methane chloride to the package.

As shown in fig. 8, the hydrochloric acid deep analysis device 700 of the present invention includes a mixer 701, a hydrochloric acid deep analysis tower 702, a first-stage condenser 703, a first-stage separator 704, a second-stage condenser 705, a second-stage separator 706, a hydrochloric acid demister 707, a hydrochloric acid analysis tower heater 708, a vacuum concentration tower feed pump 709, a vacuum concentration tower 710, a vacuum concentration tower heater 711, a mixer feed pump 712, a vacuum concentration tower top condenser 713, a separator 714, a vacuum ejector pump 715, a wastewater storage tank 716, and a wastewater transfer pump 717, which are connected in this order.

The mixer 701 is arranged to spray calcium water sent by a mixer feeding pump 712, and fully mix the calcium water with hydrochloric acid sent by a methanol gas phase hydrochlorination methane production device 100 and a carbon tetrachloride conversion methane production device 600 to enter a hydrochloric acid deep resolution tower 702; the hydrochloric acid deep analysis tower 702 is used for carrying out deep analysis on hydrochloric acid to obtain hydrogen chloride gas from the tower top; the primary condenser 703 is arranged to cool the hydrogen chloride coming out of the top of the hydrochloric acid deep resolution tower 702 by using cooling water and condense the entrained water; the primary separator 704 is configured to perform gas-liquid separation on the material sent by the primary condenser 703, and the separated liquid returns to the hydrochloric acid deep resolution tower 702; the secondary condenser 705 is arranged to cryogenically cool the gas sent from the primary separator 704 by using a refrigerant to further condense the moisture in the material; the secondary separator 706 is configured to perform gas-liquid separation on the material sent by the secondary condenser 705, and the separated liquid returns to the hydrochloric acid deep desorption tower 702; the hydrochloric acid demister 707 is arranged to carry out defoaming on the hydrogen chloride gas sent by the secondary separator 706, and the hydrogen chloride gas after defoaming is sent to the methane chloride gas phase hydrochlorination method production methane chloride device 100 and the methane chloride device 600 by carbon tetrachloride conversion; the hydrochloric acid desorption tower reboiler 708 is arranged for heating and gasifying the liquid at the lower part of the hydrochloric acid deep desorption tower by using steam; the vacuum concentration tower feeding pump 709 is arranged for pumping the tower bottom materials of the hydrochloric acid deep analysis tower 702 into the vacuum concentration tower 710; the vacuum concentration column 710 is configured to concentrate the calcium water at a certain vacuum level; the vacuum concentration tower heater 711 is arranged to heat the liquid at the bottom of the vacuum concentration tower 710 by using steam, and part of the water is evaporated and sucked out from the top of the tower; a mixer feed pump 712 is configured to pump the vacuum concentrator column 710 bottoms liquid into the mixer 701; the vacuum concentration tower overhead condenser 713 is configured to condense water coming out of the top of the vacuum concentration tower 710 with cooling water and then send the water to the separator 714; separator 714 is configured to separate the condensate from vacuum concentrator overhead condenser 713 and water is fed to waste water storage tank 716; the vacuum jet pump 715 is configured to jet using the water pumped by the wastewater delivery pump as a power source to draw out the gas in the separator 714; a waste water storage tank 716 is provided for waste water from the storage tank separator 714 and also serves as a spray water circulation tank; the wastewater transfer pump 717 is configured to transfer a portion of the wastewater to the vacuum jet pump 715, and a portion of the wastewater as wastewater to a wastewater treatment center for treatment. The dilute hydrochloric acid generated by the system is completely deeply resolved, and the resolved hydrogen chloride is completely used for producing methane chloride, so that the chlorine is utilized for three times, and the utilization rate of the chlorine is improved to more than 99%. As the chlorine is a high-energy-consumption product, the utilization rate of the chlorine is improved, the effects of energy conservation and emission reduction can be achieved, and the carbon emission is reduced.

The process for producing methane chloride by a methanol gas phase hydrochlorination dry method comprises the following steps: the method comprises the steps of preheating methanol by a methanol preheater, feeding the preheated methanol into a methanol vaporizer for vaporization, heating by a methanol heater, feeding the preheated methanol into a methanol superheater for superheating, then superheating by a hydrogen chloride superheater together with hydrogen chloride separated from methane chloride produced by methane chloride gas-phase thermal chlorination, mixing three materials obtained by vaporizing recovered methanol by a recovered methanol vaporizer, feeding the mixture into a hydrochlorination reactor for gas-phase fixed-bed catalytic hydrochlorination to generate methane chloride, wherein all reaction heat is used for heating raw materials, the reaction mixed gas is firstly fed into a quench tower for quenching, a hydrochloric acid condensate obtained by acid condenser condensation and acid separator separation is used as a quench liquid for quenching the reaction mixed gas, and hydrochloric acid discharged from a quench tank enters a methanol recovery system. And (3) cooling and separating the mixed gas from the first chilling tank, enabling the condensate to remove the chilling tower, enabling the uncondensed gas to sequentially enter a sulfuric acid drying tower I, a sulfuric acid drying tower II and a sulfuric acid drying tower III after passing through a demister, then entering a sulfuric acid demister I to obtain dry methane chloride, pressurizing by using a compressor, enabling a part of the gas to enter a methane chloride rectification system for separation to obtain a product methane chloride, and enabling a part of the product methane chloride to enter a methane chloride storage tank, and enabling a part of the crude methane chloride and the light component coming out of the top of the tower to enter the next process together to serve as raw materials. And (4) allowing hydrochloric acid discharged from the quenching tank I to enter a hydrochloric acid deep analysis device 7 for analysis, and returning hydrogen chloride to be recycled as a raw material.

The method comprises the steps of enabling methane chloride, chlorine and light methane chloride mixed gas to enter a thermal chlorination reactor with an electric heating function after being highly mixed through double injection to carry out gas-phase high-temperature thermal chlorination reaction to produce crude methane chloride mixed gas, enabling the crude methane chloride mixed gas to enter a thermal chlorination reaction thermal byproduct steam system for rapid cooling and byproduct steam, enabling the crude methane chloride mixed gas to enter a chilling tower for rapid cooling, enabling the crude methane chloride mixed gas to enter a primary condenser for cooling with cooling water, enabling part of condensate to return to the chilling tower for recycling as chilling liquid, enabling part of condensate to enter a light component separation system for separation to obtain crude methane chloride mixed liquid, and enabling the mixed liquid to enter a dichloromethane refining device for separation. And returning the light components from the top of the light component separation tower to the thermal chlorination reactor. The non-condensable gas from the first-stage condenser enters a heat exchanger and exchanges heat with low-temperature condensate obtained by low-temperature cooling of a deep condenser, the non-condensable gas from the tube pass of the heat exchanger enters the deep condenser and is subjected to deep cooling separation by using R22 as a refrigerant, the non-condensable gas mainly comprises hydrogen chloride, the hydrogen chloride enters a methanol dry-process hydrochlorination system to produce methane chloride, chlorine elements are recycled, and the condensate from the tube pass of the heat exchanger is collected as crude methane chloride. The low-temperature gas coming out of the heat exchanger returns to the thermal chlorination reactor. And the hydrogen chloride from the deep condenser completely enters a methane chloride production device by a methanol hydrochlorination method and a methane chloride production device by carbon tetrachloride conversion to be used as raw materials for producing methane chloride.

And (3) feeding the crude methane chloride mixed solution into a dichloromethane refining system for high-precision separation, obtaining dichloromethane from the top of the tower, feeding the dichloromethane into an alkali washing azeotropic system for neutralization to remove acidity, simultaneously removing moisture in the dichloromethane, and obtaining a high-quality dichloromethane product from a dichloromethane azeotropic tower kettle.

And (3) feeding the tower bottom liquid of the dichloromethane refining tower into a trichloromethane refining system for high-precision separation, obtaining trichloromethane from the tower top, feeding the trichloromethane into an alkaline washing azeotropic system for neutralization to remove acidity, and simultaneously removing moisture in the trichloromethane to obtain a high-quality trichloromethane product from the tower bottom of the trichloromethane azeotropic tower.

The liquid in the tower bottom of the trichloromethane refining tower is sent into a carbon tetrachloride refining system for high-precision separation, carbon tetrachloride is obtained from the tower top, then the obtained liquid is sent into an alkaline washing azeotropic system for neutralization and acidity removal, and simultaneously moisture in the carbon tetrachloride is removed, so that a high-quality carbon tetrachloride product is obtained from the tower bottom of the carbon tetrachloride azeotropic tower.

The carbon tetrachloride enters a system for producing methane chloride through carbon tetrachloride conversion, the vaporized carbon tetrachloride, the vaporized methanol, the recovered methanol and the hydrogen chloride obtained by the previous separation are preheated, heated and mixed and then enter a gas-solid phase carbon tetrachloride conversion reactor for gas-solid phase hydrochlorination, all reaction heat is used for heating raw materials, the reaction mixed gas firstly enters a second chilling tower and a second chilling groove for chilling, acid condensate obtained by a rear system is used as chilling liquid for chilling the reaction mixed gas, and hydrochloric acid discharged from the second chilling groove enters a methanol recovery system. And cooling and separating the mixed gas from the second quenching tank, de-exciting the second cooling tower by using the condensate, drying the non-condensed gas by using sulfuric acid, pressurizing by using a compressor, and then sending the non-condensed gas to a chloromethane thermal chlorination reaction system to serve as a raw material. The liquid crude methane chloride is sent into a methane chloride refining system for refining and separation, a methane chloride primary distillation tower is utilized to separate light components in the crude methane chloride and return the light components to a methane chloride production device by a methane chloride thermal chlorination method to be used as raw materials, the crude methane chloride after light removal is separated again by the methane chloride refining tower to remove heavy components, and the methane chloride from the top of the methane chloride refining tower is subjected to condensation, condensate separation, condensate cooling, condensate neutralization and other steps to obtain a high-quality methane chloride product.

The hydrochloric acid deep analysis device is used for analyzing hydrochloric acid generated by a methane chloride production device by a methanol gas phase hydrochlorination method and a methane chloride production device by carbon tetrachloride conversion to obtain hydrogen chloride and organic matters which are returned to the two systems for recycling. The hydrochloric acid and calcium water are fully mixed and enter a hydrochloric acid deep analysis tower, a tower kettle heater is used for heating, analyzed hydrogen chloride comes out from the top of the tower, water cooling and separation are carried out, deep cooling and separation are carried out, and the hydrogen chloride after defoaming treatment is returned to a system for secondary utilization. And (3) extracting water from the top of the vacuum concentration tower by using a vacuum concentration system at a certain temperature and a certain vacuum degree, so that the concentration of the calcium water reaches the specified requirement. And delivering the water obtained by vacuum concentration as wastewater to a sewage treatment system for treatment.

In general, the full process of the multifunctional methane chloride production system adopts the most advanced production concept and the most advanced process technology, so that the ratio of products can be infinitely adjusted, meanwhile, the purity grade of the products can meet various downstream production requirements, the multifunctional production system is realized, the adjustment is carried out according to the market condition, and the economic benefit is maximized.

The embodiments of the present invention are disclosed as the preferred embodiments, but not limited thereto, and those skilled in the art can easily understand the spirit of the present invention and make various extensions and changes without departing from the spirit of the present invention.

Claims

1. Multifunctional methane chloride production system, including methyl alcohol gaseous phase hydrochlorination method production methane chloride device (100), its characterized in that:

the device (100) for producing methane chloride by the methanol gas phase hydrochlorination method is sequentially connected with a device (200) for producing methane chloride by the methane chloride thermochlorination method, a dichloromethane refining device (300), a trichloromethane refining device (400), a carbon tetrachloride refining device (500), a device (600) for producing methane chloride by converting carbon tetrachloride and a device (700) for deeply resolving hydrochloric acid, and methanol reacts with hydrogen chloride from the device (200) for producing methane chloride by the methane chloride thermochlorination method and the device (700) for deeply resolving hydrochloric acid to generate methane chloride;

the device (200) for producing methane chloride by the methane chloride hot chlorination method comprises the steps of reacting methane chloride with chlorine to obtain a methane chloride mixed solution, feeding the methane chloride mixed solution serving as a raw material to a dichloromethane refining device (300) to prepare dichloromethane, and simultaneously using heat energy of a high-temperature reaction mixed gas for byproduct steam;

the dichloromethane refining device (300), the trichloromethane refining device (400), the carbon tetrachloride refining device (500) and the carbon tetrachloride conversion methane production device (600) sequentially separate and refine the obtained methane chloride mixed solution, dichloromethane mixed solution, trichloromethane mixed solution and carbon tetrachloride mixed solution one by one so as to simultaneously, sectionally or intermittently obtain dichloromethane products, trichloromethane products and carbon tetrachloride products in required production proportions;

the hydrochloric acid deep analysis device (700) carries out deep analysis on dilute hydrochloric acid generated by a methane chloride production device (100) by a methanol gas-phase hydrochlorination method and a methane chloride production device (600) by a carbon tetrachloride conversion method to obtain hydrogen chloride, and returns the hydrogen chloride obtained by analysis to the methane chloride production device (100) by the methanol gas-phase hydrochlorination method and the methane chloride production device (600) by the carbon tetrachloride conversion method to be used as raw materials.

2. The multi-functional methane chloride production system of claim 1, wherein:

the hydrochloric acid deep analysis device (700) comprises a mixer (701), a hydrochloric acid deep analysis tower (702) and a vacuum concentration tower (710) which are connected in sequence;

the mixer (701) is used for obtaining calcium water from a mixer feed pump (712) to spray so as to fully mix hydrochloric acid sent by a device (100) for producing methane chloride by a methanol gas phase hydrochlorination method and a device (600) for producing methane chloride by carbon tetrachloride conversion;

the hydrochloric acid deep desorption tower (702) is used for desorbing hydrogen chloride, and the obtained hydrogen chloride is defoamed by a primary condenser (703), a primary separator (704), a secondary condenser (705), a secondary separator (706) and a hydrochloric acid demister (707) in sequence and then supplied to a methane chloride production device (100) by a methanol gas phase hydrochlorination method and/or a methane chloride production device (600) by carbon tetrachloride conversion for reaction; feeding the concentrated feed to the vacuum concentration column (710) at the bottom via a vacuum concentration column feed pump (709);

the vacuum concentration tower (710) concentrates the calcium chloride aqueous solution under a vacuum environment.

3. The multi-functional methane chloride production system of claim 2, wherein:

the bottom of the vacuum concentration tower (710) is connected with a vacuum concentration tower heater (711) for steam heating, and the heated calcium chloride solution is supplied to the mixer (702) through a mixer feeding pump (712).

4. A multi-functional methane chloride production system according to claim 3, characterized in that:

the bottom of the hydrochloric acid deep resolution tower (702) is also connected with a hydrochloric acid resolution tower reboiler (708).

5. The multi-functional methane chloride production system of claim 4, wherein:

the top of the vacuum concentration tower (710) is sequentially connected with a condenser (713) at the top of the vacuum concentration tower, a separator (714) at the top of the vacuum concentration tower, a vacuum jet pump (715), a waste water storage tank (716) and a waste water delivery pump (717).

6. The multifunctional methane chloride production system according to any one of claims 1-5, wherein:

the device (100) for producing the methane chloride by the methanol gas phase hydrochlorination method comprises a hydrochlorination reactor (106), a quenching tower I (107) and a quenching tank I (108);

the hydrochlorination reactor (106) is mixed with three gas flows to carry out gas-phase fixed bed catalytic hydrochlorination to generate methane chloride, wherein the three gas flows are respectively as follows:

the first air flow: the methanol is superheated through a methanol preheater I (101), a methanol vaporizer I (102), a methanol heater I (103) and a methanol superheater I (104) which are connected in sequence to obtain superheated methanol;

and (2) airflow II: hydrogen chloride separated by a methane chloride production device (200) by a methane chloride hot chlorination method is superheated by a hydrogen chloride superheater I (105) to obtain superheated hydrogen chloride;

airflow III: the hydrogen chloride separated by the hydrochloric acid deep analysis device (700) is mixed with the hydrogen chloride separated by a methane chloride gas phase thermal chlorination method methane chloride production device, and then the mixture is superheated by a hydrogen chloride superheater I (105) to obtain superheated hydrogen chloride.

7. The multi-functional methane chloride production system of claim 6, wherein:

the first chilling tower (107) is also sequentially connected with a first acid condenser (109), a first separator (110), a first chilling tank (108), a first demister (111), a sulfuric acid drying tower I (112), a sulfuric acid drying tower II (113), a sulfuric acid drying tower III (114), a sulfuric acid demister (115) and a first compressor (116);

the hydrochloric acid discharged from the quenching tank I (108) enters a hydrochloric acid deep analysis device (700), the discharged mixed gas is cooled and separated to obtain condensate, the condensate is discharged from a cooling tower I (107), the obtained uncondensed gas passes through a demister (111) and then sequentially enters a sulfuric acid drying tower I (112), a sulfuric acid drying tower II (113) and a sulfuric acid drying tower III (114) to be subjected to deep condensation sulfuric acid drying, and then enters a compressor I (116);

the first compressor (116) compresses crude methane chloride gas, and liquid crude methane chloride obtained directly or through liquefaction of condensate is stored in a crude methane chloride storage tank (117) and then is used as a raw material to be supplied to a methane chloride production device (200) by a methane chloride thermal chlorination method.

8. The multi-functional methane chloride production system of claim 6, wherein:

the methane chloride production device (200) by the methane chloride gas phase thermal chlorination method is provided with a methane chloride chlorination reactor (206), a quenching tower (209) and a primary separation tower (218);

the input end of the methane chloride chlorination reactor (206) inputs mixed vaporized gas into the mixed gas heater (204) through a methane chloride vaporizer (201), a dichloromethane vaporizer (202) and a chloroform vaporizer (203) which are connected in parallel, and the reaction mixed gas at the output end sequentially enters a waste heat boiler (207), a chilling tower II (209), a primary condenser (210), a primary separator (211), a heat exchanger (213), a secondary separator (214), a deep condenser (215) and a deep condensation separator (216);

the first-stage separator (211) is connected with the coarse material storage tank (212), the primary separation tower bottom heat exchanger (219) and the primary separation tower bottom cooler (220) in sequence so as to provide a methane chloride mixed solution for the dichloromethane refining device (300).

9. The multi-functional methane chloride production system of claim 8, wherein:

the top of the primary tower (218) is sequentially connected with a primary tower top condenser (221), a light component storage tank (222) and a mixed gas heater (204).

10. The multi-functional methane chloride production system of claim 8, wherein:

the dichloromethane refining device (300) comprises a dichloromethane refining tower (302) and a dichloromethane azeotropic tower (311), wherein:

the dichloromethane refining tower (302) is characterized in that sufficient trichloromethane mixed liquid is provided for a trichloromethane refining device (400) at the bottom of the tower through a dichloromethane refining tower feeding and discharging heat exchanger (301), a dichloromethane refining tower reboiler (303) and a dichloromethane refining tower bottom liquid conveying pump (314), and a dichloromethane refining tower top condenser (304), a dichloromethane refining tower reflux tank (305), a dichloromethane refining tower reflux pump (306), a dichloromethane alkali washing pump (307), a dichloromethane alkali washing tank (308) and a dichloromethane azeotropic tower feeding pump (309) are sequentially connected at the top of the dichloromethane refining tower so as to provide a dichloromethane raw material for a dichloromethane azeotropic tower (311);

meanwhile, the top of the dichloromethane azeotropic tower (311) is connected with a dichloromethane alkali washing tank (308) through a dichloromethane azeotropic tower top condenser (310) for circulating cooling, and the bottom of the dichloromethane azeotropic tower (311) is connected with a dichloromethane azeotropic tower reboiler (312) and a dichloromethane azeotropic tower bottom cooler (313) for directly obtaining a dichloromethane product;

the dichloromethane refining tower reflux pump (306) supplies crude dichloromethane to the methane chloride production device (200) by the methane chloride thermal chlorination method.

11. The multi-functional methane chloride production system of claim 10, wherein:

the chloroform refining device (400) comprises a chloroform refining tower (402) and a chloroform azeotropic tower (411), wherein:

the chloroform refining tower (402) obtains chloroform mixed liquor prepared by a dichloromethane refining device (300) at the bottom through a chloromethane refining tower feeding and discharging heat exchanger (401), obtains crude carbon tetrachloride through a chloroform refining tower reboiler (403), the chloromethane refining tower feeding and discharging heat exchanger (401) and a chloroform refining tower residue conveying pump (414) and supplies the crude carbon tetrachloride to a carbon tetrachloride refining device (500) and/or a chloromethane device (600) produced through carbon tetrachloride conversion, and provides raw materials for a chloroform azeotropic tower (411) through a chloroform refining tower top condenser (404), a chloroform refining tower reflux tank (405), a chloroform refining tower reflux pump (406), a chloroform alkaline washing pump (407), a chloroform alkaline washing tank (408) and a chloroform azeotropic tower feeding pump (409) which are sequentially connected at the top;

the chloroform azeotropic tower (411) separates chloroform from water, and a tower kettle is connected with a chloroform azeotropic tower reboiler (412) and a chloroform azeotropic tower bottom cooler (413) to obtain a chloroform product;

the reflux pump (406) of the trichloromethane refining tower is connected with a methane chloride production device (200) by a methane chloride thermal chlorination method to supply trichloromethane.

12. The multi-functional methane chloride production system of claim 11, wherein:

the carbon tetrachloride refining device (500) comprises a carbon tetrachloride refining tower (502) and a carbon tetrachloride azeotropic tower (511), wherein:

the bottom of the carbon tetrachloride refining tower (502) is used for obtaining crude carbon tetrachloride prepared by a trichloromethane refining device (400) through a carbon tetrachloride refining tower feeding and discharging heat exchanger (501), heavy component waste liquid treatment equipment is obtained through a carbon tetrachloride refining tower reboiler (503), the carbon tetrachloride refining tower feeding and discharging heat exchanger (501) and a trichloromethane refining tower bottom liquid conveying pump (514), and the top of the carbon tetrachloride refining tower (502) is used for providing raw materials for a carbon tetrachloride azeotropic tower (511) through a carbon tetrachloride refining tower top condenser (504), a carbon tetrachloride refining tower reflux tank (505), a carbon tetrachloride refining tower reflux pump (506), an alkali washing pump (507), a carbon tetrachloride alkali washing tank (508) and a carbon tetrachloride azeotropic tower feeding pump (509) which are sequentially connected;

the carbon tetrachloride azeotropic tower (511) separates carbon tetrachloride from water, and a tower kettle is sequentially connected with a carbon tetrachloride azeotropic tower reboiler (512) and a chloroform azeotropic tower bottom cooler (513) to prepare products of carbon tetrachloride and crude carbon tetrachloride;

and the carbon tetrachloride refining tower reflux pump (506) is connected with the carbon tetrachloride refining tower (502) to circularly prepare the carbon tetrachloride.

13. The multi-functional methane chloride production system of claim 12, wherein:

the device (600) for producing methane chloride through carbon tetrachloride conversion comprises a carbon tetrachloride conversion reactor (608), a second chilling tower (609), a second chilling tank (610), a sulfuric acid drying tower (614), a methane chloride primary distillation tower (618), a methane chloride primary distillation tower reboiler (619), a methane chloride rectifying tower (623), a methane chloride cooler (629), a methane chloride neutralizer (630) and a methane chloride finished product tank (632), wherein:

the carbon tetrachloride conversion reactor (608) carries out gas phase fixed bed catalytic conversion reaction on overheated hydrogen chloride, methanol and carbon tetrachloride to generate methane chloride, and the tower kettle is sequentially connected with a second chilling tower (609), a second acid condenser (611), a second separator (612), a second chilling tank (610), a second sulfuric acid demister (613), a sulfuric acid drying tower (614), a second sulfuric acid demister (615), a second methyl chloride compressor (616), a first methyl chloride primary distillation tower feeding tank (617), a first methyl chloride primary distillation tower (618) and a first methyl chloride rectifying tower (623).

14. The multi-functional methane chloride production system of claim 13, wherein:

the bottom of the second quenching tank (610) conveys the dilute hydrochloric acid separated from the second quenching tank (610) to a hydrochloric acid deep analysis device (700) for analysis, the separated mixed gas at the top is sequentially introduced into an acid condenser II (611) and a separator II (612) for condensation and separation, and the obtained condensate is input into a second quenching tower (609); after being separated from the second separator (612), the condensed gas passes through a second sulfuric acid demister (613), a second sulfuric acid drying tower (614), a second sulfuric acid demister (615), a second chloromethane compressor (616), a chloromethane primary distillation tower feeding tank (617), a chloromethane primary distillation tower (618), a chloromethane primary distillation tower reboiler (619) and a chloromethane rectification tower (623) in sequence;

the top of the methane chloride primary distillation tower (618) is sequentially connected with a methane chloride primary distillation tower top condenser (620), a methane chloride primary distillation tower reflux tank (621), a methane chloride primary distillation tower reflux pump (622) and the top of the tower to form a closed loop, and the bottom of the tower is sequentially connected with a methane chloride primary distillation tower reboiler (619) and a methane chloride rectification tower (623);

the methane chloride primary distillation tower reflux pump (622) is used for refluxing a part of the obtained methane chloride into the tower, and a part of the obtained methane chloride is sent to a methane chloride device (200) for producing methane chloride by a methane chloride thermal chlorination method;

the top of the methane chloride rectifying tower (623) is sequentially connected with a methane chloride rectifying tower top condenser (626), a methane chloride rectifying tower reflux tank (627), a methane chloride rectifying tower reflux pump (628), a methane chloride cooler (629), a methane chloride neutralizer (630), a methane chloride cryocooler (631), a methane chloride finished product tank (632) and a methane chloride finished product conveying pump (633) to prepare a product methane chloride, and the bottom of the methane chloride rectifying tower is sequentially connected with a methane chloride rectifying tower reboiler (624) and a methane chloride rectifying tower kettle liquid conveying pump (625) to obtain crude methane chloride, and the crude methane chloride is sent to a methane chloride thermal chlorination device (200).

15. The multi-functional methane chloride production system of claim 14, wherein: and the methane chloride from the compressor II (616) and the methane chloride primary distillation tower reflux pump (622) is directly sent to a methane chloride device (200) for producing methane chloride by a methane chloride thermal chlorination method for cyclic reaction.