CN105037075A - Processing technology of hydrogen chloride in propylene preparation process - Google Patents
Processing technology of hydrogen chloride in propylene preparation process Download PDFInfo
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- CN105037075A CN105037075A CN201510261826.8A CN201510261826A CN105037075A CN 105037075 A CN105037075 A CN 105037075A CN 201510261826 A CN201510261826 A CN 201510261826A CN 105037075 A CN105037075 A CN 105037075A
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Abstract
The invention relates to a processing technology of hydrogen chloride in a propylene preparation process. In the invention, chlorides are generated after a chlorination reaction, in which a mixed gas composed of propylene and hydrogen chloride is obtained from the top of a condensation evaporating column. The hydrogen chloride is absorbed through a four-stage absorption technology, comprising a first hydrogen chloride absorption column, a second hydrogen chloride absorption column, an alkaline washing column and a water washing column. Through the processing technology of hydrogen chloride in the invention, the propylene does not completely contain the hydrogen chloride. In addition, the chlorination reaction is stable in temperature and high in yield. The yield of chloropropylene can reach 89.9%.
Description
Technical field
The present invention relates to a kind for the treatment of process preparing hydrogenchloride in propenyl chloride process, belong to Chloropropene production technology field.
Background technology
Propenyl chloride is chloride olefin(e) compound, has the key character of chlorine organic compound and alkene, and chlorine atom and double bond are separated by a saturated carbon atom, are easy to carry out nucleophilic substitution reaction.Utilize its chemical property, can be made into important petrochemical materials.Propenyl chloride is not generally directly made marketing and is sold, but is widely used in synthetic resins, medicine, spices, agricultural chemicals and organic synthesis raw material.Its main application produces epoxy chloropropane; For the synthesis of the raw material of glycerine and synthetic resins, all the other are used for producing vinylcarbinol, allylamine and medicine etc.
The preparation method of propenyl chloride has high-temperature chlorination, propylene oxychlorination method and vinyl carbinol chlorination process etc.Wherein, high-temperature chlorination: obtained by propylene high-temperature instituteization.Reaction equation: CH
3cH=CH
2+ Cl
2→ ClCH
2cH=CH
2+ HCl; Step is: by the propylene of drying through preheating under 350-400 DEG C of condition, liquid chlorine is through heating and gasifying, two kinds of materials mix and react under high-velocity jet state, the proportioning of propylene and chlorine is 4-5: 1 (mol ratio), reactor residence time 1.5-2s, temperature of reaction 470-500 DEG C.Reaction product is chilled to 50-100 DEG C of removing HCl and propylene, more namely obtains product through fractionation.Propylene oxychlorination method: the propylene be mixed in proportion, hydrogenchloride and oxygen react in a fluidized bed reactor, selects catalyzer to be Te, V of being loaded on carrier
2o
5or H
3pO
4, and add nitrogenous thing and do promotor, under 240-260 DEG C of condition, carry out normobaric oxygen chlorination reaction, obtained chlorallylene.Reaction equation is: CH
3cH=CH
2+ HCl+1/2O
2[catalyzer] → CH
2=CHCH
2cl+H
2o.Vinyl carbinol chlorination process: reaction equation is CH
2=CHCH
2oH [Cu
2cl
2, HCl] and → CH
2=CHCH
2cl+H
2o; Preparation process is: instilled in vinyl carbinol, cuprous chloride and hydrochloric acid by sulfuric acid under 10-20 DEG C of condition, dropwises rear insulation reaction 5h, stratification, upper liquid water, 5% sodium carbonate solution, water respectively wash 1 time, after dividing most water, distillation collection more than 40 DEG C cuts, are chlorallylene.
Summary of the invention
In the preparation process of propenyl chloride, according to chlorination reaction, a large amount of hydrogenchloride can be produced, the object of the present invention is to provide a kind for the treatment of process preparing hydrogenchloride in propenyl chloride process.Completely not containing hydrogenchloride in propylene after process of the present invention.Technical scheme of the present invention is as follows:
Prepare a treatment process for hydrogenchloride in propenyl chloride process, concrete steps are as follows:
(1) liquid chlorine of chlorine pot enters Chlorine Buffer Vessel after the gasification of chlorine vaporizer, and the chlorine of gasification enters the mixing section of chlorination reactor after gauger B is quantitative;
(2) when raw material propylene water content is less than 10ppm, propylene directly enters propylene supercooler, when being greater than 10ppm when raw material propylene water content, propylene in propylene tank enters dry propylene tank after water trap dehydration, then propylene supercooler is sent into, propylene is after propylene supercooler heat exchanges, one tunnel is sent to condensation and is steamed the refrigeration of column overhead spray, another road through perchlorhydria water cooler to the cooling entering condensation and steam tower, steamer is entered after propylene self gasification, after being gasified totally in steamer, heat exchanger is entered after gauger A is quantitative, after being preheated to 360-400 DEG C in a heat exchanger, send into the mixing section of chlorination reactor, the mol ratio of propylene and chlorine is 4-6:1, preferably, mol ratio is 5:1, chlorination reaction is completed at chlorination reactor after propylene mixes with chlorine.
The chemical reaction occurred in chlorination process is as follows:
Main reaction:
CH
2＝CH-CH
3+Cl
2→CH
2=CH-CH
2Cl+HCl,ΔH1=-112kJ/mol(1)
Side reaction:
CH
2＝CH-CH
3+Cl
2→CH
2=CCl-CH
3+HCl,ΔH2=-121kJ/mol(2)
CH
2＝CH-CH
3+2Cl
2→CH
2=CCl-CH
2Cl+2HCl,ΔH3=-222kJ/mol(3)
CH
2＝CH-CH
3+3Cl
2→3C+6HCl,ΔH4=-306kJ/mol(4)
(3) steam tower top acquisition propylene and the chlorine hydride mixed gas body of tower in condensation, hydrogenchloride adopts level Four absorption technique, i.e. absorption by Hydrochloric Acid one tower, absorption by Hydrochloric Acid two tower, soda-wash tower and water wash column;
First mixed gas enters absorption by Hydrochloric Acid one tower, absorbs, obtain the hydrochloric acid of mass concentration >=30%, hydrochloric acid is sent into hydrochloric acid basin, after tinning, send battery limit (BL), sell as byproduct through circulating cooling.Propylene containing a small amount of hydrogenchloride after absorption by Hydrochloric Acid one tower absorbs enters absorption by Hydrochloric Acid two tower, water cycle absorbs and obtains dilute hydrochloric acid, hydrochloric acid absorption tower is sent to use, for guaranteeing in propylene not containing hydrogen chloride, this propylene also must enter soda-wash tower, with the NaOH solution circulation cleaning that mass concentration is 3-10%, preferably, the mass concentration of NaOH solution is 7%; Hydrogenchloride is neutralized absorption completely, and the propylene after alkali cleaning again through washing, then enters propylene compressor; Through the HCl gas that hydrochloric acid trough and the dilute acid bath of absorption by Hydrochloric Acid one tower and absorption by Hydrochloric Acid two tower volatilize, enter tail gas absorber water absorption, absorption liquid enters dilute acid bath, and unabsorbed a small amount of HCl gas is emptying through 16m aiutage; The brine waste produced after alkali cleaning, washing is collected.
Be applied to the chloridizing unit of above-mentioned chlorination reaction, constitutive material propylene unit after water trap is in parallel with propylene tank after connecting with dry propylene tank, the outlet of raw material propylene device is connected by pipeline with the import of propylene supercooler, two outlets of propylene supercooler steam tower respectively import with condensation is connected by pipeline with the import of muriate water cooler, another import that outlet and the condensation of muriate water cooler steam tower is connected by pipeline, the outlet that condensation steams tower is connected with the import of steamer by pipeline, the outlet of steamer is connected by pipeline with the import of heat exchanger through gauger A, the outlet of heat exchanger is connected with the import of chlorination reactor by pipeline, another import of chlorination reactor is also connected by pipeline with the outlet of Chlorine Buffer Vessel, the import being provided with gauger B Chlorine Buffer Vessel between chlorination reactor and Chlorine Buffer Vessel is connected by pipeline with the outlet of chlorine vaporizer, the import of chlorine vaporizer is connected by pipeline with chlorine pot.
In chlorination reaction of the present invention, resultant of reaction material passes through and propylene heat exchange, and reaction propylene is preheated to certain temperature, and reaction mass steams the propylene heat exchange of column overhead again with condensation, arrive muriate water cooler again through the cooling of liquid reactions propylene, be cooled to about-10 DEG C and enter condensation and steam tower.Tower top propylene liquid sprays refrigeration, and control temperature is-44 DEG C, makes the almost all condensations and separating of the chlorinated hydrocarbons in reaction mass.
In chloridizing unit of the present invention, in vaporizer, Heating temperature is 80 DEG C; Pressure in Chlorine Buffer Vessel is 0.4MPa; The temperature of chlorination reaction is 500 DEG C; Condensation steams column overhead control temperature and is-44 DEG C, and tower top pressure is less than or equal to 0.15MPa, and bottom temperature is 70 DEG C, and tower reactor pressure is less than or equal to 0.15MPa.
The present invention compared with prior art has following beneficial effect:
After hydrochlorination art breading of the present invention, completely not containing hydrogenchloride in propylene, and in the present invention, chlorination reaction temperature is stablized, and chlorination reaction yield is high, and the yield of propenyl chloride is up to 89.9%.
Accompanying drawing explanation
Fig. 1 is the chloridizing unit process flow sheet in propenyl chloride production process of the present invention.
Nomenclature:
1. propylene tank, 2. water trap, 3. dry propylene tank, 4. propylene supercooler, 5. condensation steam tower, 6. muriate water cooler, 7. steamer, 8. gauger A, 9. heat exchanger, 10. chlorination reactor, 11. gauger B, 12. Chlorine Buffer Vessel, 13. chlorine vaporizers, 14. chlorine pots.
Embodiment
Further describe the present invention below in conjunction with specific embodiment, advantage and disadvantage of the present invention will be more clear along with description.But embodiment is only exemplary, does not form any restriction to scope of the present invention.It will be understood by those skilled in the art that and can modify to the details of technical solution of the present invention and form or replace down without departing from the spirit and scope of the present invention, but these amendments and replacement all fall within the scope of protection of the present invention.
Embodiment 1 one kinds prepares the treatment process of hydrogenchloride in propenyl chloride process
Step is as follows:
(1) liquid chlorine of chlorine pot enters Chlorine Buffer Vessel after the gasification of chlorine vaporizer, and the chlorine of gasification enters the mixing section of chlorination reactor after gauger B is quantitative;
(2) when raw material propylene water content is less than 10ppm, propylene directly enters propylene supercooler, when being greater than 10ppm when raw material propylene water content, propylene in propylene tank enters dry propylene tank after water trap dehydration, then propylene supercooler is sent into, propylene is after propylene supercooler heat exchanges, one tunnel is sent to condensation and is steamed the refrigeration of column overhead spray, another road through perchlorhydria water cooler to the cooling entering condensation and steam tower, steamer is entered after propylene self gasification, after being gasified totally in steamer, heat exchanger is entered after gauger A is quantitative, after being preheated to 360-400 DEG C in a heat exchanger, send into the mixing section of chlorination reactor, the mol ratio of propylene and chlorine is 5:1, chlorination reaction is completed at chlorination reactor after propylene mixes with chlorine.
The chemical reaction occurred in chlorination process is as follows:
Main reaction:
CH
2＝CH-CH
3+Cl
2→CH
2=CH-CH
2Cl+HCl,ΔH1=-112kJ/mol(1)
Side reaction:
CH
2＝CH-CH
3+Cl
2→CH
2=CCl-CH
3+HCl,ΔH2=-121kJ/mol(2)
CH
2＝CH-CH
3+2Cl
2→CH
2=CCl-CH
2Cl+2HCl,ΔH3=-222kJ/mol(3)
CH
2＝CH-CH
3+3Cl
2→3C+6HCl,ΔH4=-306kJ/mol(4)
(3) steam tower top acquisition propylene and the chlorine hydride mixed gas body of tower in condensation, hydrogenchloride adopts level Four absorption technique, i.e. absorption by Hydrochloric Acid one tower, absorption by Hydrochloric Acid two tower, soda-wash tower and water wash column;
First mixed gas enters absorption by Hydrochloric Acid one tower, absorbs, obtain the hydrochloric acid of mass concentration >=30%, hydrochloric acid is sent into hydrochloric acid basin, after tinning, send battery limit (BL), sell as byproduct through circulating cooling.Propylene containing a small amount of hydrogenchloride after absorption by Hydrochloric Acid one tower absorbs enters absorption by Hydrochloric Acid two tower, water cycle absorbs and obtains dilute hydrochloric acid, hydrochloric acid absorption tower is sent to use, for guaranteeing in propylene not containing hydrogen chloride, this propylene also must enter soda-wash tower, with the NaOH solution circulation cleaning that mass concentration is 7%, preferably, the mass concentration of NaOH solution is 7%; Hydrogenchloride is neutralized absorption completely, and the propylene after alkali cleaning again through washing, then enters propylene compressor; Through the HCl gas that hydrochloric acid trough and the dilute acid bath of absorption by Hydrochloric Acid one tower and absorption by Hydrochloric Acid two tower volatilize, enter tail gas absorber water absorption, absorption liquid enters dilute acid bath, and unabsorbed a small amount of HCl gas is emptying through 16m aiutage; The brine waste produced after alkali cleaning, washing is collected.
For the chloridizing unit of chlorination reaction in embodiment 2 one kinds of propenyl chloride production processes
As shown in Figure 1, in described chloridizing unit water trap 2 after connecting with dry propylene tank 3 in parallel with propylene tank 1 after constitutive material propylene unit, the outlet of raw material propylene device is connected by pipeline with propylene supercooler 4 import, two outlets of propylene supercooler 4 steam tower 5 respectively import with condensation is connected by pipeline with the import of muriate water cooler 6, another import that outlet and the condensation of muriate water cooler 6 steam tower 5 is connected by pipeline, the outlet that condensation steams tower 5 is connected by the import of pipeline with steamer 7, the outlet of steamer 7 is connected by pipeline with the import of heat exchanger 9 through gauger A8, the outlet of heat exchanger 9 is connected by the import of pipeline with chlorination reactor 10, another import of chlorination reactor 10 is also connected by pipeline with the outlet of Chlorine Buffer Vessel 12, gauger B11 is provided with between chlorination reactor 10 and Chlorine Buffer Vessel 12, the import of Chlorine Buffer Vessel 12 is connected by pipeline with the outlet of chlorine vaporizer 13, the import of chlorine vaporizer 13 is connected by pipeline with chlorine pot 14.
Resultant of reaction material through and propylene heat exchange, reaction propylene is preheated to certain temperature, and reaction mass steams the propylene heat exchange of column overhead again with condensation, then cools to muriate water cooler through liquid reactions propylene, is cooled to about-10 DEG C and enters condensation and steam tower.In vaporizer, Heating temperature is 80 DEG C; Pressure in Chlorine Buffer Vessel is 0.4MPa; The temperature of chlorination reaction is 500 DEG C; Condensation steams column overhead control temperature and is-44 DEG C, and tower top pressure is less than or equal to 0.15MPa, and bottom temperature is 70 DEG C, and tower reactor pressure is less than or equal to 0.15MPa.
Claims (8)
1. prepare a treatment process for hydrogenchloride in propenyl chloride process, it is characterized in that, concrete steps are as follows:
(1) liquid chlorine of chlorine pot enters Chlorine Buffer Vessel after the gasification of chlorine vaporizer, and the chlorine of gasification enters the mixing section of chlorination reactor after gauger B is quantitative;
(2) when raw material propylene water content is less than 10ppm, propylene directly enters propylene supercooler, when being greater than 10ppm when raw material propylene water content, propylene in propylene tank enters dry propylene tank after water trap dehydration, then propylene supercooler is sent into, propylene is after propylene supercooler heat exchanges, one tunnel is sent to condensation and is steamed the refrigeration of column overhead spray, another road through perchlorhydria water cooler to the cooling entering condensation and steam tower, steamer is entered after propylene self gasification, after being gasified totally in steamer, heat exchanger is entered after gauger A is quantitative, after being preheated to 360-400 DEG C in a heat exchanger, send into the mixing section of chlorination reactor, the mol ratio of propylene and chlorine is 4-6:1, chlorination reaction is completed at chlorination reactor after propylene mixes with chlorine,
(3) steam tower top acquisition propylene and the chlorine hydride mixed gas body of tower in condensation, hydrogenchloride adopts level Four absorption technique, i.e. absorption by Hydrochloric Acid one tower, absorption by Hydrochloric Acid two tower, soda-wash tower and water wash column;
First mixed gas enters absorption by Hydrochloric Acid one tower, absorb through circulating cooling, obtain the hydrochloric acid of mass concentration >=30%, hydrochloric acid is sent into hydrochloric acid basin, the propylene containing a small amount of hydrogenchloride after absorption by Hydrochloric Acid one tower absorbs enters absorption by Hydrochloric Acid two tower, water cycle absorbs and obtains dilute hydrochloric acid, sending hydrochloric acid absorption tower to use, then propylene is entered soda-wash tower, is the NaOH solution circulation cleaning of 3-10% by mass concentration, propylene after alkali cleaning again through washing, then enters propylene compressor; Through the HCl gas that hydrochloric acid trough and the dilute acid bath of absorption by Hydrochloric Acid one tower and absorption by Hydrochloric Acid two tower volatilize, enter tail gas absorber water absorption, absorption liquid enters dilute acid bath, and unabsorbed a small amount of HCl gas is emptying through 16m aiutage; The brine waste produced after alkali cleaning, washing is collected.
2. process for refining according to claim 1, is characterized in that, in described step (2), the mol ratio of propylene and chlorine is 5:1.
3. for the chloridizing unit of the chlorination reaction in process for refining as claimed in claim 1, it is characterized in that, in described chloridizing unit water trap connect with dry propylene tank after in parallel with propylene tank after constitutive material propylene unit, the outlet of raw material propylene device is connected by pipeline with the import of propylene supercooler, two outlets of propylene supercooler steam tower respectively import with condensation is connected by pipeline with the import of muriate water cooler, another import that outlet and the condensation of muriate water cooler steam tower is connected by pipeline, the outlet that condensation steams tower is connected with the import of steamer by pipeline, the outlet of steamer is connected by pipeline with the import of heat exchanger through gauger A, the outlet of heat exchanger is connected with the import of chlorination reactor by pipeline, another import of chlorination reactor is also connected by pipeline with the outlet of Chlorine Buffer Vessel, the import being provided with gauger B Chlorine Buffer Vessel between chlorination reactor and Chlorine Buffer Vessel is connected by pipeline with the outlet of chlorine vaporizer, the import of chlorine vaporizer is connected by pipeline with chlorine pot.
4. chloridizing unit according to claim 3, is characterized in that, in described vaporizer, Heating temperature is 80 DEG C.
5. chloridizing unit according to claim 3, is characterized in that, the pressure in described Chlorine Buffer Vessel is 0.4MPa.
6. chloridizing unit according to claim 3, is characterized in that, the temperature of described chlorination reaction is 500 DEG C.
7. chloridizing unit according to claim 3, is characterized in that, described condensation steams column overhead control temperature and is-44 DEG C, and tower top pressure is less than or equal to 0.15MPa, and bottom temperature is 70 DEG C, and tower reactor pressure is less than or equal to 0.15MPa.
8. process for refining according to claim 1, is characterized in that, propylene is entered soda-wash tower in (3) by described step, and the mass concentration of NaOH solution is 7%.
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|---|---|---|---|
| CN201510261826.8A CN105037075A (en) | 2015-05-21 | 2015-05-21 | Processing technology of hydrogen chloride in propylene preparation process |
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|---|---|---|---|
| CN201510261826.8A CN105037075A (en) | 2015-05-21 | 2015-05-21 | Processing technology of hydrogen chloride in propylene preparation process |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724155A (en) * | 2013-12-19 | 2014-04-16 | 山东海益化工科技有限公司 | Chloropropene production process |
| CN103724158A (en) * | 2013-12-19 | 2014-04-16 | 山东海益化工科技有限公司 | Device for producing chloropropene |
| CN103724157A (en) * | 2013-12-19 | 2014-04-16 | 山东海益化工科技有限公司 | Chlorination process in chloropropene production |
-
2015
- 2015-05-21 CN CN201510261826.8A patent/CN105037075A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724155A (en) * | 2013-12-19 | 2014-04-16 | 山东海益化工科技有限公司 | Chloropropene production process |
| CN103724158A (en) * | 2013-12-19 | 2014-04-16 | 山东海益化工科技有限公司 | Device for producing chloropropene |
| CN103724157A (en) * | 2013-12-19 | 2014-04-16 | 山东海益化工科技有限公司 | Chlorination process in chloropropene production |
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