CN112473314B - Environment-friendly treatment method for 3-chloropropyl trichlorosilane synthesis tail gas - Google Patents
Environment-friendly treatment method for 3-chloropropyl trichlorosilane synthesis tail gas Download PDFInfo
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Abstract
The invention discloses an environment-friendly treatment method for 3-chloropropyl trichlorosilane synthesis tail gas, which belongs to the technical field of chemical industry, and is characterized in that the synthesis tail gas sequentially passes through a freezing system, an absorption liquid system, a condensing system, a water spraying system, an alkali spraying system and a resin absorption system, finally, the tail gas is discharged after being monitored on line by an incineration system, or a compressed propylene product is obtained by a compression system, all components in the tail gas can be effectively separated or removed from the tail gas, and recycled or subjected to environment-friendly treatment in the next step, so that the environment-friendly problem of the traditional treatment process of the tail gas is solved, the waste is effectively avoided, the environment of a factory is improved, a brand-new thought is provided for the treatment method of the synthesis tail gas, the propylene gas in the tail gas can also be made into products, the added value of byproducts is increased, the production cost of the 3-chloropropyl trichlorosilane is reduced, and the energy conservation and emission reduction are realized.
Description
Technical Field
The invention relates to environmental protection treatment of chemical synthesis tail gas, in particular to an environmental protection treatment method of 3-chloropropyl trichlorosilane synthesis tail gas.
Background
The 3-chloropropyl trichlorosilane is the most basic monomer in the silane coupling agent, is the main production raw material for synthesizing serial products of the silane coupling agent, and is widely applied to synthesizing bis [ propyltriethoxysilane ] polysulfide, aminopropyltriethoxysilane and the like. At present, in large industrial production, the synthesis of 3-chloropropyl trichlorosilane generally adopts addition reaction of trichlorosilane and chloropropene under a platinum catalyst, and silicon tetrachloride, propyl trichlorosilane and propylene which are byproducts are mainly generated in the reaction process, and the principle is as follows:
the main reaction: HSiCl 3 + ClCH 2 CH=CH 2 →ClC 3 H 6 SiCl 3
Trichlorosilane+chloropropene- & gt 3-chloropropyl trichlorosilane
Side reaction: HSiCl 3 + ClCH 2 CH=CH 2 →SiCl 4 +CH 3 CH=CH 2
Trichlorosilane+chloropropene- & gt silicon tetrachloride+propylene
HSiCl 3 +CH 3 CH=CH 2 →CH 3 CH 2 CH 2 SiCl 3
Trichlorosilane + propylene-propyltrichlorosilane
At normal temperature, trichlorosilane has a boiling point of 31.8 ℃, a saturated vapor pressure of 65.8kPa, chloropropene has a boiling point of 44-45 ℃, a saturated vapor pressure of 45.2kPa, silicon tetrachloride has a boiling point of 57.6 ℃, a saturated vapor pressure of 56kPa, propyltrichlorosilane has a boiling point of 123.5 ℃, a saturated vapor pressure of 3.5kPa, and propylene is a gas at normal temperature. The boiling points of the substances are very low at normal temperature and normal pressure, so that the substances such as trichlorosilane, chloropropene, silicon tetrachloride, propyl trichlorosilane, propylene and hydrogen chloride generated by hydrolysis are inevitably contained in the synthesis tail gas of the 3-chloropropyl trichlorosilane, and the principle is that the trichlorosilane and the chloropropene are raw materials which do not react completely, the 3-chloropropyl trichlorosilane is a product, the silicon tetrachloride, the propyl trichlorosilane and the propylene are byproducts, and the propylene is in a gas form; the trichlorosilane and chloropropene are synthesized, the synthesis system is fed with nitrogen or pressurized, and the nitrogen is discharged along with synthesis tail gas, so that the tail gas contains nitrogen; trichlorosilane, 3-chloropropyl trichlorosilane, silicon tetrachloride and propyl trichlorosilane can hydrolyze in water or wet air to release hydrogen chloride gas, and the wet air exists inevitably both from raw material feeding and a synthesis system, so that the tail gas inevitably contains the hydrogen chloride gas. How to treat the synthetic tail gas in an environment-friendly way is always a hot spot of research in the industry.
In the traditional treatment process in the industry, the tail gas is generally condensed by a condenser, the non-condensable gas enters a water spray washing tower to generate acidic liquid, and the tail gas is directly discharged; the acidic liquid is neutralized by quicklime, caustic soda flakes and the like to generate waste liquid, and the waste liquid is finally formed into dangerous waste which is difficult to treat, and directly discharged into the atmosphere, so that the environment is polluted. With the advent of environmental protection policies, traditional treatment processes have failed to meet the needs of the development of the age.
Disclosure of Invention
1. Technical problem to be solved
Aiming at the problems existing in the prior art, the invention aims to provide an environment-friendly treatment method for the 3-chloropropyl trichlorosilane synthetic tail gas, by the treatment method, each component in the tail gas can be effectively separated or removed from the tail gas, and can be recycled or subjected to the next environmental-friendly treatment, so that the environment-friendly problem of the traditional treatment process of the tail gas is solved, the generation of wastes is avoided, the environment of a factory is improved, a brand-new thought is provided for the environment-friendly treatment method for the 3-chloropropyl trichlorosilane synthetic tail gas, propylene gas in the tail gas can be further made into products, the additional value of byproducts is increased, the production cost of the 3-chloropropyl trichlorosilane is reduced, and the purposes of energy conservation and emission reduction are achieved.
Technical proposal
In order to solve the problems, the invention adopts the following technical scheme.
An environment-friendly treatment method for 3-chloropropyl trichlorosilane synthesis tail gas comprises the following steps:
s1, synthesizing tail gas generated by 3-chloropropyl trichlorosilane by taking trichlorosilane and chloropropene as raw materials;
s2, conveying tail gas flowing out of the synthesis system to a refrigerating system, condensing most of trichlorosilane, chloropropene, 3-chloropropyl trichlorosilane, silicon tetrachloride and propyl trichlorosilane gas carried by the synthesis tail gas into liquid, and collecting the liquid in a storage tank;
s3, continuously conveying the tail gas to an absorption liquid system, and separating liquid drops carried by the gas from the tail gas, namely, removing trichlorosilane, 3-chloropropyl trichlorosilane, silicon tetrachloride and propyl trichlorosilane liquid drops from the tail gas;
s4, continuously conveying the tail gas to a condensing system, removing absorption liquid drops carried by the tail gas, and further removing trichlorosilane, chloropropene, 3-chloropropyl trichlorosilane, silicon tetrachloride and propyl trichlorosilane gases contained in the tail gas;
s5, conveying the tail gas to a water spraying system, further purifying the tail gas, and further removing main hydrogen chloride gas (generated in an absorption liquid system) and trace amounts of trichlorosilane, 3-chloropropyl trichlorosilane, silicon tetrachloride and propyl trichlorosilane in the tail gas;
s6, conveying the tail gas to an alkali spraying system to further purify the tail gas, and further removing hydrogen chloride gas (hydrogen chloride gas which is not absorbed by the water spraying system) and trace amounts of trichlorosilane, 3-chloropropyl trichlorosilane, silicon tetrachloride and propyl trichlorosilane gas in the tail gas;
s7, finally, conveying the tail gas to a resin absorption system, and removing chloropropene gas and other trace chlorine-containing gas by adopting a resin absorption method;
s8, introducing the purified tail gas into an incineration system for incineration, and discharging the VOCs up to standard after the VOCs are qualified through on-line monitoring.
Further, the purified tail gas obtained after the step S7 directly enters a compression system, and propylene gas is compressed and liquefied through a compression technology, so that the tail gas is separated from nitrogen gas, a compressed propylene product with the content of more than 96% is obtained, the effective utilization of byproducts is achieved, and the economic added value is increased.
Further, the freezing medium of the freezing system is a saline solution, the freezing medium is preferably a calcium chloride water solution, and the entering temperature of the freezing medium is controlled to be-35 ℃.
Further, the condensed liquid in the step S2 is returned to a synthesis system of trichlorosilane and chloropropene to be used as a raw material for the next reaction, so that the purpose of recycling is achieved; the condensed liquid returned to the synthesis system is pressurized by introducing nitrogen gas at a pressure of 100kPa to 1000kPa, preferably 300 kPa to 350kPa, and the refrigeration system employs a graphite heat exchanger, preferably a shell-and-tube graphite heat exchanger.
Further, the absorption liquid of the absorption liquid system is alcohol, the alcohol is one of methanol, ethanol and isopropanol, and is preferably ethanol, the temperature of the absorption liquid is between-15 ℃ and-10 ℃, so that the efficiency of removing liquid drops is facilitated to be improved, the absorption liquid is higher than-10 ℃ and the solution desorption efficiency of the liquid drops is poor, the reaction temperature is lower than-15 ℃ and is low, the liquid drops are not easily removed by the reaction, the energy consumption is high, the concentration of the alcohol in the absorption liquid is not lower than 40%, and the full absorption of the liquid drops is facilitated; the concentration of the absorption liquid can be detected using gas chromatography. Further, the absorption liquid absorption system adopts a standby mode, and two sets of systems are arranged in total; when the operation is started, the A sleeve starts to absorb and the B sleeve is reserved; when the absorption of the sleeve A is saturated, the absorption is cut from the sleeve A to the sleeve B, the sleeve A is replaced by the absorption liquid, and the like; the external part of the absorption liquid absorption system is cooled by adopting a cooling liquid, preferably a calcium chloride aqueous solution at the temperature of minus 15 ℃ is used as the cooling liquid, and the crude alkoxy silane generated by the reaction of the absorption liquid can be prepared into alkoxy (poly) silane through an alkoxy (poly) silane preparation system, so that the purpose of environmental protection treatment is achieved. The absorption liquid system adopts a tower type reaction device, tail gas enters the system from the tower top, and absorption liquid continuously enters the tower top from the tower bottom through pumping circulation to contact with the tail gas for dissolution and reaction.
Further, the freezing medium of the condensing system is a saline solution, preferably a calcium chloride aqueous solution, the entering temperature of the freezing medium is controlled to be-15 ℃ in the step S4, and the cooling liquid obtained through cooling is returned to the absorption liquid absorption system. The condensing system adopts a graphite heat exchanger, preferably a tubular graphite heat exchanger.
Further, the total acidity of the dilute hydrochloric acid generated by the water spraying system under the spraying action is controlled to be not more than 10%, and the total acidity of the dilute hydrochloric acid is too high, so that the thorough hydrolysis of siloxane is not facilitated, and an unstructured waste gas can be generated; the trichlorosilane, 3-chloropropyl trichlorosilane, silicon tetrachloride, propyl trichlorosilane gas and a large amount of water are subjected to complete hydrolysis reaction under the action of hydrogen chloride gas, so that dilute hydrochloric acid is obtained. Along with the reaction, water in the water spraying system is changed into dilute hydrochloric acid, the dilute hydrochloric acid promotes the hydrolysis speed and the hydrolysis degree of trichlorosilane, 3-chloropropyl trichlorosilane, silicon tetrachloride and propyl trichlorosilane gas, the trichlorosilane, 3-chloropropyl trichlorosilane, silicon tetrachloride and propyl trichlorosilane gas are thoroughly hydrolyzed, the complete hydrolysis is carried out to (poly) siloxane residues, and the (poly) siloxane residues are easily removed from the dilute hydrochloric acid through a filtering system, so that the obtained dilute hydrochloric acid is clear and transparent and has no suspended matters. The obtained diluted hydrochloric acid is used as an absorption liquid of hydrogen chloride generated by further alcoholysis reaction of 3-chloropropyl trichlorosilane, and the concentrated hydrochloric acid prepared by further absorbing the hydrogen chloride can be sold as a byproduct hydrochloric acid product.
Further, the product obtained by the alkali spraying system is sodium chloride aqueous solution, the sodium chloride aqueous solution enters a brine evaporation system to evaporate solid sodium chloride and water, and alkali liquor in the alkali spraying system is sodium hydroxide aqueous solution after being diluted by liquid alkali or being dissolved by adding water into caustic soda flakes.
Furthermore, the product sodium chloride aqueous solution of the alkali spraying system is introduced into a polysulfide silane coupling agent synthesis system to be used as a solvent, and the two treatment modes of the product sodium chloride aqueous solution in the S6 can be subjected to environment-friendly cleaning treatment.
Further, the resin used in the resin absorption system is styrene-divinylbenzene base frame macroporous adsorption resin with high specific area, the resin is integrated after the chloropropene is adsorbed, the chloropropene is recycled in a vacuum, hot air or steam desorption mode, the recycled chloropropene is recycled in a synthesis system of 3-chloropropyl trichlorosilane, and the resin is regenerated and reused; the resin absorption system adopts a mode of one standby, and two sets of absorption columns are arranged in total; when the operation is started, the column I starts to adsorb, and the column II is reserved; when the I column adsorption is saturated, the adsorption is cut from the I column to the II column, the I column is regenerated, and so on. Further, judging whether the discharged gas contains chloropropene gas or not by using the switching standard of the two sets of absorption columns as a standard; further, whether chloropropene is contained in the gas is detected by a gas chromatography-mass spectrometry method.
3. Advantageous effects
Compared with the prior art, the invention has the advantages that:
according to the technical scheme, all components of trichlorosilane, 3-chloropropyl trichlorosilane, silicon tetrachloride, propyl trichlorosilane, chloropropene and propylene in the tail gas generated by synthesizing the 3-chloropropyl trichlorosilane, and possible gases of hydrogen chloride and nitrogen are sequentially removed from the tail gas, and the separated gases are recycled or used for synthesizing other products, so that the purpose of environmental protection treatment is achieved, waste is not generated, the environment is protected, the final tail gas can be discharged up to the standard, and the clean production of the 3-chloropropyl trichlorosilane in large industrial production is ensured.
By adopting the technical scheme of the invention, the gas in the tail gas generated by synthesizing the 3-chloropropyl trichlorosilane can be removed, and the liquid and liquid drops carried by the gas can be removed, so that the removal rate is high, and the environment-friendly cleaning treatment of the subsequent tail gas is effectively ensured.
By adopting the technical scheme of the invention, the chlorine-containing gas in the tail gas is effectively removed, no decomposed chloride is generated after the tail gas is burnt, no acid gas is generated, the corrosion of the chlorine-containing gas to an incineration system is eliminated, the service life and maintenance period of the incineration system, particularly VOCs on-line monitoring equipment, are prolonged, and the equipment cost is reduced.
Compared with the traditional treatment process, the dilute hydrochloric acid obtained by the technical scheme of the invention is clear and transparent, has no suspended matters, and can be further prepared into concentrated hydrochloric acid to be sold as byproduct hydrochloric acid; in addition, the water spraying system has no pipeline blocking phenomenon, ensures the continuity of production, and ensures that 3-chloropropyl trichlorosilane can be continuously produced.
Compared with the prior art, the technical scheme of the invention returns the obtained trichlorosilane and chloropropene condensate to a synthesis system of the trichlorosilane and the chloropropene as the next reaction raw material, and the condensate is recycled under a pressurized state, so that the condensate is maximally and effectively utilized, and the condensate is pressurized by introducing nitrogen, and is matched with the synthesis system by adopting the same pressurizing mode with 3-chloropropyl trichlorosilane synthesis feeding or pressurizing.
Compared with the prior art, the technical scheme of the invention adopts alcohol liquid absorption, particularly ethanol is used as absorption liquid, so that liquid drops in tail gas can be effectively removed, and the ethanol is used as the absorption liquid to obtain an ethoxysilane product, so that the treatment and utilization of subsequent products are further widened.
Compared with the prior art, the method adopts the resin adsorption system to mainly remove chloropropene and trace chlorine-containing gas, is beneficial to the next environmental protection treatment of tail gas, completely removes the chloropropene from the tail gas, solves the problem that the chloropropene in the tail gas is difficult to remove, and can enrich and recycle the chloropropene in the synthesis system of 3-chloropropyl trichlorosilane, thereby increasing the added value.
Compared with the prior art, the invention mainly uses propylene as clean tail gas to be made into products by compression technology, thereby achieving effective utilization of byproducts and increasing economic added value.
Drawings
Fig. 1 is a main flow chart of the present invention.
Detailed Description
The drawings in the embodiments of the present invention will be combined; the technical scheme in the embodiment of the invention is clearly and completely described; obviously; the described embodiments are only a few embodiments of the present invention; but not all embodiments, are based on embodiments in the present invention; all other embodiments obtained by those skilled in the art without undue burden; all falling within the scope of the present invention.
In the description of the present invention, it should be noted that the positional or positional relationship indicated by the terms such as "upper", "lower", "inner", "outer", "top/bottom", etc. are based on the positional or positional relationship shown in the drawings, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the apparatus or elements referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "configured to," "engaged with," "connected to," and the like are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
Example 1
Referring to fig. 1, an environmental protection treatment method for synthesis tail gas of 3-chloropropyl trichlorosilane is disclosed, wherein tail gas generated by synthesizing 3-chloropropyl trichlorosilane by using trichlorosilane and chloropropene as raw materials flows out of a synthesis system, sequentially passes through a freezing system, an absorption liquid system, a condensing system, a water spraying system, an alkali spraying system and a resin absorption system, finally passes through an incineration system to be monitored on line, discharges the tail gas, or finally passes through a compression system to obtain a compressed propylene product.
Refrigeration system: firstly, the initial tail gas passes through a refrigeration system at the temperature of minus 35 ℃ to obtain condensate, and when the next batch of 3-chloropropyl trichlorosilane is synthesized, the condensate is pressurized to 320kPa through nitrogen and is recycled to the 3-chloropropyl trichlorosilane synthesis system;
absorption liquid system: the tail gas discharged by the refrigerating system enters an ethanol absorption liquid system A, the absorption liquid system is kept warm by adopting chilled water at the temperature of minus 15 ℃, after the continuous operation is carried out for 48 hours, the ethanol absorption liquid is detected by adopting a gas chromatography, the concentration of ethanol in the absorption liquid reaches 42%, the tail gas discharge is switched to an ethanol absorption liquid system B, and the ethanol absorption liquid in the group A is transferred into an alkoxy (poly) silane preparation system for preparing alkoxy (poly) silane;
condensing system: tail gas discharged from the absorption liquid system enters a condensation system at the temperature of minus 15 ℃, and cooling liquid of the condensation system is continuously transferred into a standby absorption liquid system;
water spray system: the tail gas discharged by the condensing system enters a water spraying system, water is filled in the water spraying system, after the water spraying system continuously runs for 48 hours, the HCl concentration of dilute hydrochloric acid in the water spraying system is tested to be 4%, the appearance is clear and transparent, no suspended matters exist, the dilute hydrochloric acid in the water spraying system is diverted away, and the dilute hydrochloric acid is used as an absorption liquid of hydrogen chloride generated by further alcoholysis reaction of 3-chloropropyl trichlorosilane. The water spraying system runs continuously for 2 months without pipeline blockage and the like;
alkali spraying system: the tail gas discharged by the water spraying system enters the alkali spraying system, the concentration of sodium hydroxide is 15%, after one month of operation, the pH value of the alkali spraying absorption liquid is tested to be 8, the absorption liquid in the alkali spraying is transferred away, and the absorption liquid enters the sodium chloride aqueous solution treatment system; the sodium chloride aqueous solution is clear and transparent in appearance;
resin absorption system: the resin absorption system is provided with two sets of absorption columns I and II, the tail gas discharged by the alkali spraying system firstly enters the I column, after the continuous operation is carried out for 30 days, a gas mass spectrometry method is adopted to detect whether the tail gas discharged by the resin absorption system contains chloropropene, a gas phase peak of the chloropropene appears in a 45 th weather phase chromatogram, a tail gas inlet is timely switched to the II column, and the I column is regenerated. The regeneration of the I column adopts a hot air blowing mode, and the blown chloropropene is reused in a 3-chloropropyl trichlorosilane synthesis system after being subjected to molecular sieve water removal treatment.
Incineration system: the device of the incineration system sequentially comprises a liquid separating tank, a liquid sealing tank, a torch and VOCs on-line monitoring, tail gas exhausted by the resin absorption system enters the incineration system to be incinerated, the incinerated gas is discharged after passing through the VOCs on-line monitoring and detecting, the exhaust gas from the incineration system is tested by wet pH test paper, and the pH value is shown as 6.5.
Comparative example 1:
the other systems were the same as in example 1, except that the tail gas of this comparative example did not pass through the absorption liquid system, the condensation system, and the resin absorption system.
The results of the tail gas treatment show that: the appearance of the dilute hydrochloric acid in the water spraying system is turbid and suspended matters, and the appearance of the dilute hydrochloric acid does not accord with the standard of industrial byproduct hydrochloric acid; the water spray system is operated continuously for 15 days, and the blocking condition of the water spray pipeline occurs. The alkali spraying system was operated for 20 days, and the alkali sprayed absorption liquid was found to float with a trace of silane hydrolyzed white suspended matter. The gas exiting the incineration system was tested using a wet pH paper, and the pH was shown to be 3.0.
Comparative example 2:
the other systems were the same as in example 1, except that the off-gas of this comparative example did not pass through the resin absorption system.
The results of the treatment showed that the gas exiting the incineration system was tested using a wet pH paper, and the pH was shown to be 3.5. After a period of continuous operation, the devices of the incineration system comprise VOCs on-line monitoring equipment which are all corroded.
Example 2
Refrigeration system: firstly, the initial tail gas passes through a refrigeration system at the temperature of minus 35 ℃ to obtain condensate, and when the next batch of 3-chloropropyl trichlorosilane is synthesized, the condensate is pressurized to 320kPa through nitrogen and is recycled to the 3-chloropropyl trichlorosilane synthesis system;
absorption liquid system: the tail gas discharged by the refrigerating system enters an ethanol absorption liquid system A, the absorption liquid system is kept warm by adopting chilled water at the temperature of minus 15 ℃, after the continuous operation is carried out for 48 hours, the ethanol absorption liquid is detected by adopting a gas chromatography, the concentration of ethanol in the absorption liquid reaches 42%, the tail gas discharge is switched to an ethanol absorption liquid system B, and the ethanol absorption liquid in the group A is transferred into an alkoxy (poly) silane preparation system for preparing alkoxy (poly) silane;
condensing system: tail gas discharged from the absorption liquid system enters a condensation system at the temperature of minus 15 ℃, and cooling liquid of the condensation system is continuously transferred into a standby absorption liquid system;
water spray system: the tail gas discharged by the condensing system enters a water spraying system, water is filled in the water spraying system, after the water spraying system continuously runs for 48 hours, the HCl concentration of dilute hydrochloric acid in the water spraying system is tested to be 4%, the appearance is clear and transparent, no suspended matters exist, the dilute hydrochloric acid in the water spraying system is diverted away, and the dilute hydrochloric acid is used as an absorption liquid of hydrogen chloride generated by further alcoholysis reaction of 3-chloropropyl trichlorosilane;
alkali spraying system: the tail gas discharged by the water spray system enters an alkali spray system, the concentration of sodium hydroxide is 15%, after one month of operation, the pH value of the alkali spray absorption liquid is tested to be 8, the absorption liquid in the alkali spray is diverted away, and the alkali spray absorption liquid enters a sodium chloride water solution treatment system;
resin absorption system: the resin absorption system is provided with two sets of absorption columns I and II, the tail gas discharged by the alkali spraying system firstly enters the I column, after the continuous operation is carried out for 30 days, a gas mass spectrometry method is adopted to detect whether the tail gas discharged by the resin absorption system contains chloropropene, a gas phase peak of the chloropropene appears in a 45 th weather phase chromatogram, a tail gas inlet is timely switched to the II column, and the I column is regenerated. The regeneration of the I column adopts a hot air blowing mode, and the blown chloropropene is reused in a 3-chloropropyl trichlorosilane synthesis system after being dehydrated;
compression system: and (3) introducing tail gas discharged by the resin absorption system into a compression system to obtain a compressed and liquefied propylene product, wherein the content of propylene is 97.2% through detection.
According to the embodiment and the comparative example, the appearance of the obtained dilute hydrochloric acid is clear and transparent, no suspension exists, the appearance standard of industrial byproduct hydrochloric acid is met, white suspended matters caused by silane hydrolysis do not exist in alkali spraying absorption liquid, in addition, chlorine-containing gas, especially chloropropene gas in tail gas is completely removed through a resin absorption system, chlorine-containing gas does not exist in tail gas entering an incineration system, chlorine-containing substances are not generated by decomposition, the discharged gas does not contain acid gas, the pH value is not less than 6.0, standard emission can be achieved, corrosion of the acid gas to the incineration system is eliminated, maintenance cost of the incineration system is reduced, and the service life of VOCs on-line monitoring equipment is prolonged.
The synthetic tail gas sequentially passes through a refrigerating system, an absorption liquid system, a condensing system, a water spraying system, an alkali spraying system and a resin absorbing system, finally, the tail gas is discharged after being subjected to online monitoring through an incineration system, or a compressed propylene product is obtained through a compression system, all components in the tail gas can be effectively separated or removed from the tail gas, and are recycled or subjected to environmental protection treatment in the next step, so that the environmental protection problem of the traditional tail gas treatment process is solved, the generation of wastes is effectively avoided, the environment of a factory is improved, a brand new thought is provided for the treatment method of the synthetic tail gas, propylene gas in the tail gas can be made into products, the added value of byproducts is increased, the production cost of 3-chloropropyl trichlorosilane is reduced, and the energy conservation and emission reduction are realized.
The above; is only a preferred embodiment of the present invention; the scope of the invention is not limited in this respect; any person skilled in the art is within the technical scope of the present disclosure; equivalent substitutions or changes are made according to the technical proposal of the invention and the improved conception thereof; are intended to be encompassed within the scope of the present invention.
Claims (9)
1. An environment-friendly treatment method for 3-chloropropyl trichlorosilane synthesis tail gas is characterized by comprising the following steps of: the method comprises the following steps:
s1, synthesizing tail gas generated by 3-chloropropyl trichlorosilane by taking trichlorosilane and chloropropene as raw materials;
s2, conveying tail gas flowing out of the synthesis system to a refrigerating system, condensing and converting trichlorosilane, chloropropene, 3-chloropropyl trichlorosilane, silicon tetrachloride and propyl trichlorosilane gas which are carried by the synthesis tail gas and can be refrigerated by the refrigerating system into liquid, and collecting the liquid in a storage tank;
s3, continuously conveying the tail gas to an absorption liquid system, and removing trichlorosilane, 3-chloropropyl trichlorosilane, silicon tetrachloride and propyl trichlorosilane liquid drops carried by the gas from the tail gas;
s4, continuously conveying the tail gas to a condensing system, removing absorption liquid drops carried by the tail gas, and removing trichlorosilane, chloropropene, 3-chloropropyl trichlorosilane, silicon tetrachloride and propyl trichlorosilane gases which are contained in the tail gas and can be cooled down by the condensing system;
s5, conveying the tail gas to a water spray system, further purifying the tail gas, and removing hydrogen chloride gas generated by the tail gas in an absorption liquid system and trichlorosilane, 3-chloropropyl trichlorosilane, silicon tetrachloride and propyl trichlorosilane which can be absorbed by the water spray system;
s6, conveying the tail gas to an alkali spraying system to further purify the tail gas, and removing hydrogen chloride gas which is not absorbed by the water spraying system and trichlorosilane, 3-chloropropyl trichlorosilane, silicon tetrachloride and propyl trichlorosilane gas which can be absorbed by the alkali spraying system;
s7, finally, conveying the tail gas to a resin absorption system, and removing chloropropene gas which cannot be completely removed in the steps S2-S6 and other trace chlorine-containing gas by adopting a resin absorption method;
s8, introducing the purified tail gas into an incineration system for incineration, and discharging the VOCs up to standard after the VOCs are qualified through on-line monitoring;
the absorption liquid of the absorption liquid system is alcohol.
2. The method for environmental protection treatment of 3-chloropropyl trichlorosilane synthesis tail gas according to claim 1, which is characterized in that: the freezing medium of the freezing system is saline solution, and the entering temperature of the freezing medium is controlled to be minus 35 ℃.
3. The method for environmental protection treatment of 3-chloropropyl trichlorosilane synthesis tail gas according to claim 1, which is characterized in that: returning the condensed liquid in the step S2 to a synthesis system of trichlorosilane and chloropropene to be used as a raw material for the next reaction; the condensed liquid returned to the synthesis system is pressurized by introducing nitrogen gas at a pressure of 100kPa to 1000kPa.
4. The method for environmental protection treatment of 3-chloropropyl trichlorosilane synthesis tail gas according to claim 1, which is characterized in that: the alcohol is one of methanol, ethanol and isopropanol, the temperature of the absorption liquid is between-15 ℃ and-10 ℃, and the concentration of the alcohol in the absorption liquid is not lower than 40%.
5. The method for environmental protection treatment of 3-chloropropyl trichlorosilane synthesis tail gas according to claim 1, which is characterized in that: the freezing medium of the condensing system is saline solution, and the entering temperature of the freezing medium is controlled to be-15 ℃ in the step S4.
6. The method for environmental protection treatment of 3-chloropropyl trichlorosilane synthesis tail gas according to claim 1, which is characterized in that: the total acidity of the dilute hydrochloric acid generated by the water spraying system under the spraying action is controlled to be not more than 10 percent in terms of HCl component fraction.
7. The method for environmental protection treatment of 3-chloropropyl trichlorosilane synthesis tail gas according to claim 1, which is characterized in that: and the product obtained by the alkali spraying system is sodium chloride aqueous solution, and the sodium chloride aqueous solution enters a brine evaporation system to evaporate solid sodium chloride and water.
8. The method for environmental protection treatment of 3-chloropropyl trichlorosilane synthesis tail gas according to claim 1, which is characterized in that: and (3) introducing the sodium chloride aqueous solution of the alkali spraying system into a polysulfide silane coupling agent synthesis system to be used as a solvent.
9. The method for environmental protection treatment of 3-chloropropyl trichlorosilane synthesis tail gas according to claim 1, which is characterized in that: the resin used in the resin absorption system is styrene-divinylbenzene base frame macroporous adsorption resin with high specific area, the resin is integrated after the chloropropene is adsorbed, the chloropropene is recycled in a vacuum, hot air or steam desorption mode, the recycled chloropropene is recycled in a synthesis system of 3-chloropropyl trichlorosilane, and the resin is regenerated and reused.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN202968434U (en) * | 2012-11-20 | 2013-06-05 | 江西晨光新材料有限公司 | Separation and recovery device for chloropropthyl trichlorosilane tail gas |
| CN109553635A (en) * | 2018-12-06 | 2019-04-02 | 黄山利臻新材料科技有限公司 | A kind of γ-chloropropyl trichloro-silane production solvent recovery technology from vent gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN202968434U (en) * | 2012-11-20 | 2013-06-05 | 江西晨光新材料有限公司 | Separation and recovery device for chloropropthyl trichlorosilane tail gas |
| CN109553635A (en) * | 2018-12-06 | 2019-04-02 | 黄山利臻新材料科技有限公司 | A kind of γ-chloropropyl trichloro-silane production solvent recovery technology from vent gas |
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