CN107008107A - The comprehensive processing method and its processing unit of a kind of phenmethylol production waste gas - Google Patents

The comprehensive processing method and its processing unit of a kind of phenmethylol production waste gas Download PDF

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CN107008107A
CN107008107A CN201710233221.7A CN201710233221A CN107008107A CN 107008107 A CN107008107 A CN 107008107A CN 201710233221 A CN201710233221 A CN 201710233221A CN 107008107 A CN107008107 A CN 107008107A
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water
tower
waste gas
absorption
activated carbon
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CN107008107B (en
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危先龙
杨华
肖华青
熊鲲
杜斌
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Hubei Green Home Materials Technology Ltd By Share Ltd
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Hubei Green Home Materials Technology Ltd By Share Ltd
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Abstract

A kind of phenmethylol produces the comprehensive processing method of waste gas, it is characterized in that this method includes following steps:A:The waste gas that benzyl chloride hydrolytic process is produced, enters normal temperature spray-absorption after collection;The waste gas come out from normal temperature spray-absorption enters back into the absorption process of freezing spray micro activated carbon particle;The waste gas come out from freezing spray-absorption enters back into activated carbon tower absorption process;D:The waste gas come out from charcoal absorption is again that 48% sodium hydroxide liquid absorbs by volumetric concentration, and all waste gas are absorbed completely, the hydrolysis of the sodium carbonate reuse of generation to benzyl chloride.

Description

The comprehensive processing method and its processing unit of a kind of phenmethylol production waste gas
Technical field
The present invention relates to the exhaust-gas treatment field in industrial production, the comprehensive processing method that a kind of phenmethylol produces waste gas is referred specifically to And its processing unit.
Background technology
Phenmethylol(Also known as benzylalcohol, hydroxy-methylbenzene), it is highly useful chemical intermediate, is widely used in curing agent, dilution The industries such as agent, spices and essence.Obtained mostly using benzyl chloride with soda ash reaction generation both at home and abroad at present, reaction can produce substantial amounts of The carbon dioxide produced in waste gas, mainly hydrolytic process, and a small amount of benzyl chloride and phenmethylol volatilized, due to benzyl chloride gas The strong and stimulating of body, waste gas directly discharge can not only pollute air, and huge injury can be caused to human body.Many productions at present The treatment facility of producer is all difficult to thoroughly solve the pollution problems such as waste gas, waste water, with the development of the social economy, environmental issue is The problem of through becoming very important, emission reduction even zero-emission turns into society and basic demand of the government to chemical enterprise.
In consideration of it, the present invention proposes comprehensive processing method and its place of a kind of phenmethylol large-scale industrial production waste gas Device is managed, the waste gas in production not only can be thoroughly solved the problems, such as by this method, the standard of zero-emission is reached, and can also be right Waste water is recycled, and advantageously reduces cost.
The content of the invention
It is an object of the present invention to provide a kind of comprehensive processing method of phenmethylol production waste gas and its processing unit, to solve benzene Waste gas problem in methanol production process, realizes the technical problems such as zero-emission truly.
In order to thoroughly solve the problems, such as the waste gas in phenmethylol production process, zero-emission truly, the present invention are realized Propose the comprehensive processing method that a kind of phenmethylol produces waste gas, by this method not only can by whole waste gas absorptions, and The waste water produced in processing procedure all can be with recycling, it is to avoid secondary pollution.
The present invention is adopted the following technical scheme that:A kind of phenmethylol produces the comprehensive processing method of waste gas, it is characterized in that the party Method includes following steps:A:The waste gas that benzyl chloride hydrolytic process is produced, enters normal temperature spray-absorption, normal temperature after collection Add the mixture of triethanolamine and quaternary ammonium base in shower water, mixture account for the mass ratio of normal temperature shower water for 0.001- 0.002, the process can absorb most benzyl chloride in waste gas, the hydrolysis of the waste water recycling of generation to benzyl chloride;
B:The waste gas come out from normal temperature spray-absorption enters back into the absorption process of freezing spray micro activated carbon particle, during being somebody's turn to do, spray The low temperature chilled water gone out has added the black tropine of mass ratio 0.001-0.002, absorbs 90% remaining organic gas in waste gas, produces Waste water recycling to benzyl chloride hydrolysis;
C:The waste gas come out from freezing spray-absorption enters back into activated carbon tower absorption process, and activated carbon utilizes its physical adsorption process It can not will be adsorbed in waste gas by the organic gas of spray-absorption, the waste water recycling that regenerating active carbon process is produced to benzyl chloride Hydrolysis;The a diameter of 2.0-2.8mm of micro activated carbon particle;
D:The waste gas come out from charcoal absorption absorbs by volumetric concentration for 48% sodium hydroxide liquid again, all waste gas quilts Absorb complete, the hydrolysis of the sodium carbonate reuse of generation to benzyl chloride.
Preferably, the normal temperature spray-absorption process is sprayed using normal temperature soft water, the soft water after absorption is matched somebody with somebody Alkali participates in benzyl chloride hydrolysis.
Preferably, the freezing spray process is sprayed using soft water, the chilled salt solution heat exchange cooling of soft water After use, low temperature soft water after absorption carries out participating in benzyl chloride hydrolysis with alkali.
Preferably, described regenerating active carbon process uses high-temperature steam, the condensed waste water of steam participates in benzyl chloride Hydrolysis.
It is a kind of to realize the processing unit that above-mentioned phenmethylol produces the waste gas comprehensive regulation, including off-gas buffer tank, normal temperature spray Tower, freezing spray column, heat exchanger, refrigerator, brine tank, charcoal trap, absorbing by liquid caustic soda tower, it is characterized in that the waste gas is slow Rush tank to be connected with normal temperature spray tower bottom, normal temperature spray column top exit is connected with freezing spray tower bottom, freezing spray tower top Portion outlet is connected with activated carbon tower bottom, and activated carbon tower top exit is connected with absorbing by liquid caustic soda tower bottom.Preferably, described normal Regular corrugation ceramic filling material is loaded in warm spray column, freezing spray column and absorbing by liquid caustic soda tower.
Preferably, the heat exchanger is provided with cooling water inlet and coolant outlet, the cooling water inlet passes through circulation Pump is connected with brine tank, and brine tank is connected with refrigerator, and the coolant outlet is connected with brine tank.
Preferably, the activated carbon tower is two, an absorption a, parsing is used alternatingly.
Preferably, the activated carbon tower is furnished with a condenser and steam pipe system, for being solved to activated carbon Analysis regeneration.
Preferably, the normal temperature spray column, freezing spray column adsorption system, activated carbon tower, absorbing by liquid caustic soda tower bottom are equal Provided with wastewater discharge pipe, it is connected after each wastewater discharge pipe is in parallel with wastewater collection tank;The wastewater collection tank is also inhaled with a waste water Attached system connection, the waste water adsorption system includes first, second, third adsorbent equipment and two grades, three-level raw water tank, and described the First, it is equipped with temperature sensor in adsorption tower in second, third adsorbent equipment;
The adsorbent equipment includes the first adsorption tower and the second adsorption tower, condenser, parsing water pot, steam pipe, raw water tubes, described Resin is supported in first adsorption tower and the second adsorption tower adsorption tower using multiple water caps, the gap of water cap is handed over less than polystyrene Join the diameter of resin;
First adsorption tower and second absorption tower top provided with processing water outlet pipe, raw water tubes respectively with the first adsorption tower and second Adsorb and be connected at the top of tower bottom connection, Boiler Steam pipe and the first described adsorption tower and the second adsorption tower, the first adsorption tower with It is connected after second adsorption tower bottom steam output pipe is in parallel with condenser;The first adsorbent equipment processing water outlet pipe and two grades of originals Water fills connection, and two grades of raw waters are filled to be connected with the raw water tubes of the second adsorbent equipment;Second adsorbent equipment processing water outlet pipe with Three-level raw water fills connection;Three-level raw water is filled and is connected with the raw water tubes of the 3rd adsorbent equipment;The first, second, third absorption dress The steam output pipe put is connected with three condenser air inlets respectively, is connected after three leaving condenser waters mouthful are in parallel with parsing water pot Connect.
The present invention proposes the comprehensive processing method and its processing unit of a kind of phenmethylol large-scale industrial production waste gas, By this method not only can by whole waste gas absorptions, and the waste water produced in processing procedure all can with recycling, Avoid secondary pollution.
Brief description of the drawings
With reference to the accompanying drawings and detailed description, technical scheme is described in further detail.
Fig. 1 is the structural representation of apparatus of the present invention.
Embodiment
Fig. 1 is the structural representation of apparatus of the present invention.As seen from the figure, the device of the phenmethylol production waste gas comprehensive regulation includes Off-gas buffer tank 1, normal temperature spray column 2, freezing spray column 3, heat exchanger, refrigerator, brine tank, charcoal trap 5, liquid caustic soda are inhaled Tower 6 is received, wherein regular corrugation ceramic filling material 7 is loaded in normal temperature spray column 2, freezing spray column 3 and absorbing by liquid caustic soda tower 6.
Off-gas buffer tank 1 is connected with the bottom of normal temperature spray column 2, the top exit of normal temperature spray column 2 and freezing spray column 3 bottom Connection, the freezing top exit of spray column 3 is connected with the bottom of charcoal trap 5, and the top exit of charcoal trap 5 is inhaled with liquid caustic soda Receive the connection of the bottom of tower 6.
Heat exchanger 30 is provided with cooling water inlet 32 and coolant outlet 33, and cooling water inlet 32 passes through circulating pump 31 and salt solution Case is connected, and brine tank is connected with refrigerator, and coolant outlet 33 is connected with brine tank.
Charcoal trap 5 is provided with two, and one is used to adsorb, and one is used to parse, and is used alternatingly;Activated carbon absorbs Tower 5 is furnished with a condenser and steam pipe system 52, for carrying out parsing regeneration to activated carbon.
Its operation principle is:Main component is carbon dioxide, chlorine in the waste gas produced from benzyl chloride hydrolysis, waste gas Change the gases such as benzyl, phenmethylol, benzaldehyde.Waste gas is pooled in off-gas buffer tank 1 first, then from the bottom of normal temperature spray absorber 2 Portion's air inlet enters in tower, and normal temperature spray absorber 2 uses normal temperature soft water, and normal temperature soft water is continuously transported to tower by pump The mixture of triethanolamine and quaternary ammonium base is added in top, normal temperature shower water and the waste gas counter current contact of ejection, normal temperature shower water, is mixed The mass ratio that compound accounts for normal temperature shower water is 0.001-0.002, and the absorption spray phase can absorb most organic in waste gas Gas.Meanwhile, continuously moisturizing and water outlet are carried out to following absorption water tank, it is ensured that the continuity of absorption spraying effect, The waste water that delivery port comes out enters wastewater collection tank.
By normal temperature spray column 2 absorb after waste gas again from freezing spray column 3 bottom inlet enter tower in, by spray inhale The waste gas of receipts enters back into freezing spray process, and normal temperature soft water is continuously transported to the freezing tower top of spray column 3 by pump, in tower Interior and waste gas counter current contact.Unlike, soft water can be down to 0-3 DEG C after refrigerator exchanges heat, and chilled water has added mass ratio 0.001-0.002 black tropine, there is more preferable assimilation effect to organic gas, and the stage can be 90% remaining in basic absorption waste gas Organic gas, meanwhile, continuously moisturizing and water outlet are carried out to following brine tank, it is ensured that absorption spraying effect it is continuous Property, the waste water that delivery port comes out enters wastewater collection tank.
The waste gas come out from freezing spray column 3 enters the bottom of charcoal trap 5 by pipeline fan again, from lower In upper absorption process, it can not will be adsorbed using activated carbon physical adsorption process in waste gas by the organic gas of spray-absorption, it is living The a diameter of 2.0-2.8mm of property carbon particle.Regenerating active carbon process uses high-temperature steam, and the condensed waste water of steam participates in benzyl chloride Hydrolysis.
By the absorption of charcoal trap 5, the organic gas in waste gas is adsorbed completely, and charcoal trap 5 is suction The pattern that attached-parsing is used alternatingly, when a tower absorption, another tower is parsed with high-temperature steam, the height parsed Warm waste gas enters wastewater collection tank after being condensed by condenser 61.
The waste gas adsorbed from charcoal trap 5 is entered in absorbing by liquid caustic soda tower 6 by its top gas outlet, volumetric concentration Be 48% sodium hydroxide liquid by being pumped at the top of spray column, carry out counter current contact with waste gas, the process will be remaining in waste gas Carbon dioxide all sponge.The soda ash solution that liquid caustic soda is produced with carbon dioxide reaction, waste water tank is entered by delivery port, When the PH of liquid caustic soda water tank is less than setting value, liquid caustic soda is added by mending alkali mouthful.
Normal temperature spray column 2, freezing spray column 3, charcoal trap 5, the bottom of absorbing by liquid caustic soda tower 6 are equipped with discharge of wastewater Pipe, is connected after each parallel connection of wastewater discharge pipe 21,34,51,61 with wastewater collection tank.Waste water in wastewater collection tank can be used for chlorination The hydrolysis of benzyl, can also enter the processing of waste water adsorption system,
The waste water adsorption system includes first, second, third adsorbent equipment and two grades, three-level raw water tank, first, second, third Temperature sensor 42 is equipped with adsorbent equipment in adsorption tower.
Wherein the first adsorbent equipment includes the first adsorption tower A1 and the second adsorption tower A2, condenser, parsing water pot, steam pipe 44th, raw water tubes 46.Resin 4, the seam of water cap 41 are supported using multiple water caps 41 in first adsorption tower A1 and the second adsorption tower A2 Gap is less than the diameter of polystyrene crosslinked resin 4;First adsorption tower A1 and the second adsorption tower A2 tops are provided with processing water outlet pipe 45, Raw water tubes 46 are connected with the first adsorption tower A1 and the second adsorption tower A2 bottoms respectively, the adsorption tower A1 of steam pipe 44 and first and second Connect, be connected after the first adsorption tower A1 and the parallel connection of the second adsorption tower A2 bottoms steam output pipe 47 with condenser at the top of adsorption tower A2. First adsorbent equipment processing water outlet pipe 45 is filled with two grades of raw waters to be connected, and two grades of raw waters fill the raw water tubes 48 with the second adsorbent equipment Connection;Second adsorbent equipment processing water outlet pipe 481 is filled with three-level raw water to be connected;Three-level raw water fills the original with the 3rd adsorbent equipment Water pipe 49 is connected.The steam output pipe 47,481,491 of first, second, third adsorbent equipment respectively with three condenser air inlets Connection, is connected after three leaving condenser waters mouthful are in parallel with parsing water pot.
One-level raw water enters the first adsorption tower A1 bottom by one-level raw water tubes 46 in waste water, then equal by water cap 41 Even by polystyrene crosslinked resin 4, flow is 2-3BV/h, and the water outlet of the first adsorbent equipment processing water outlet pipe 45 is from tower top To two grades of raw water tanks, when water outlet containing alcohol >=0.1%, stop the first adsorption tower A1 absorption, be transferred to resolving, switch simultaneously Continue to adsorb to the second adsorption tower A2.
During the first adsorption tower A1 is adsorbed, the second adsorption tower A2 is in analysis state.High temperature from boiler steams Vapour enters in tower from the second adsorption tower A2 top, and the phenmethylol of resin adsorption is eluted out by high-temperature steam, and desorption temperature is 130 ~ 140 DEG C, high-temperature steam is condensed by bottom steam output pipe 47 from bottom of towe into condenser, finally enters parsing water pot, when From the solution bleed containing alcohol that condenser comes out≤0.001% when, it is believed that parsing is complete, stops steam cooling condensation, and A2 adsorption towers are in State to be adsorbed.First adsorption tower A1 and the second adsorption tower A2 belong to the tower in parallel of primary adsorption, and one adsorbs, a parsing, It is used alternatingly, it is ensured that the continuity of primary adsorption.
Second level adsorbent equipment and third level adsorbent equipment are similar with primary adsorption.Two grades from first order adsorbent equipment Raw water enters two grade of first adsorption tower B1, when water outlet containing alcohol >=0.05%, stops absorption.When two grade of first adsorption tower B1 inhales When attached, two grade of second adsorption tower B2 is in analysis state, and two grade of first adsorption tower B1 and the second adsorption tower B2 adsorption towers alternately make With, it is ensured that the continuity of secondary absorption, secondary absorption water outlet COD is 300 ~ 500mg/l.Three-level from second level adsorbent equipment Raw water enters three-level the first adsorption tower C1, when water outlet containing alcohol >=0.01%, stops absorption.When the first adsorption tower of three-level C1 inhales During attached tower absorption, the second adsorption tower of three-level C2 is in analysis state, and three-level the first adsorption tower C1 and the second adsorption tower C2 alternately make With, it is ensured that the continuity of three-level absorption, the mg/l of three-level absorption water outlet COD < 100.
Phenmethylol waste water containing alcohol < 0.01% by three-level resin adsorption, the rate of recovery reaches 99%;Parse simultaneously Bleed is solved after sedimentation layering, lower floor's oil phase obtains phenmethylol by rectifying, upper strata solution bleed can be used for participating in chlorine with alkali Change the hydrolytic process of benzyl;The waste water COD < 100mg/l adsorbed by three-level, reach discharging standards.
Normal temperature more than absorbs, freezing absorbs, activated carbon absorbs and absorbing by liquid caustic soda process.Benzyl chloride hydrolytic process is produced Raw waste gas is all absorbed complete, reaches the standard of zero-emission, meanwhile, the various waste water that the process is produced are adsorbed by three-level Waste water COD < 100mg/l, reach discharging standards, it is to avoid secondary pollution.
Waste water COD of the present invention can be recycled up to discharging standards, and equipment, be conducive to enterprise to save production Cost.The removal process of phenmethylol uses the physical absorption ability of resin, does not add other chemical reagent;Resin is stripped Cheng Caiyong high-temperature steams, other chemical impurities are not introduced in system;All processes use the side that absorption-parsing is used alternatingly Formula, it is ensured that the continuity of adsorption process, operates steadily;The solution bleed that resolving is produced can be used for participating in matching somebody with somebody alkali, not have Unnecessary waste water is produced, the phenmethylol of recovery is reentered into system, reclaimed by rectifying.
Finally it is pointed out that above embodiment is only the more representational example of invention.Obviously, the present invention not It is limited to above-mentioned embodiment, there can also be many deformations.Every technical spirit according to the present invention is embodied to more than Any simple modification, equivalent variations and modification that mode is made, are considered as belonging to protection scope of the present invention.

Claims (9)

1. a kind of phenmethylol produces the comprehensive processing method of waste gas, it is characterized in that this method includes following steps:A:By chlorine Change the waste gas that benzyl hydrolytic process is produced, enter after collection and triethanolamine and season are added in normal temperature spray-absorption, normal temperature shower water The mixture of ammonium alkali, the mass ratio that mixture accounts for normal temperature shower water is 0.001-0.002, and the process can absorb big in waste gas Partial benzyl chloride, the hydrolysis of the waste water recycling of generation to benzyl chloride;
B:The waste gas come out from normal temperature spray-absorption enters back into the absorption process of freezing spray micro activated carbon particle, during being somebody's turn to do, spray The low temperature chilled water gone out has added the black tropine of mass ratio 0.001-0.002, absorbs 90% remaining organic gas in waste gas, produces Waste water recycling to benzyl chloride hydrolysis;
C:The waste gas come out from freezing spray-absorption enters back into activated carbon tower absorption process, and activated carbon utilizes its physical adsorption process It can not will be adsorbed in waste gas by the organic gas of spray-absorption, the waste water recycling that regenerating active carbon process is produced to benzyl chloride Hydrolysis;The a diameter of 2.0-2.8mm of micro activated carbon particle;
D:The waste gas come out from charcoal absorption absorbs by volumetric concentration for 48% sodium hydroxide liquid again, all waste gas quilts Absorb complete, the hydrolysis of the sodium carbonate reuse of generation to benzyl chloride.
2. phenmethylol according to claim 1 produces the comprehensive processing method of waste gas, it is characterized in that normal temperature spray is inhaled Receipts process is sprayed using normal temperature soft water, and the soft water after absorption carries out participating in benzyl chloride hydrolysis with alkali.
3. phenmethylol according to claim 1 produces the comprehensive processing method of waste gas, it is characterized in that the freezing was sprayed Cheng Caiyong soft water is sprayed, and is used after the chilled salt solution heat exchange cooling of soft water, the low temperature soft water after absorption carries out matching somebody with somebody alkali Participate in benzyl chloride hydrolysis.
4. phenmethylol according to claim 1 produces the comprehensive processing method of waste gas, it is characterized in that described activated carbon is again Raw process uses high-temperature steam, and the condensed waste water of steam participates in benzyl chloride hydrolysis.
5. the processing unit that phenmethylol described in claim 1 produces the waste gas comprehensive regulation is realized a kind of, including off-gas buffer tank, often Warm spray column, freezing spray column, heat exchanger, refrigerator, brine tank, charcoal trap, absorbing by liquid caustic soda tower, it is characterized in that described Off-gas buffer tank is connected with normal temperature spray tower bottom, and normal temperature spray column top exit is connected with freezing spray tower bottom, freezing spray Drench top of tower outlet to be connected with activated carbon tower bottom, activated carbon tower top exit is connected with absorbing by liquid caustic soda tower bottom;Preferably, Regular corrugation ceramic filling material is loaded in the normal temperature spray column, freezing spray column and absorbing by liquid caustic soda tower.
6. phenmethylol according to claim 5 produces the comprehensive processing method of waste gas, it is characterized in that the heat exchanger is provided with Cooling water inlet and coolant outlet, the cooling water inlet are connected by circulating pump with brine tank, and brine tank connects with refrigerator Connect, the coolant outlet is connected with brine tank.
7. phenmethylol according to claim 5 produces the comprehensive processing method of waste gas, it is characterized in that the activated carbon tower is Two, an absorption a, parsing is used alternatingly.
8. phenmethylol according to claim 5 produces the comprehensive processing method of waste gas, it is characterized in that the activated carbon tower is matched somebody with somebody There are a condenser and steam pipe system, for carrying out parsing regeneration to activated carbon.
9. phenmethylol according to claim 7 produces the comprehensive processing method of waste gas, it is characterized in that the normal temperature spray column, Freezing spray column adsorption system, activated carbon tower, absorbing by liquid caustic soda tower bottom are equipped with wastewater discharge pipe, after each wastewater discharge pipe is in parallel It is connected with wastewater collection tank;The wastewater collection tank is also connected with a waste water adsorption system, the waste water adsorption system include first, It is equipped with second, third adsorbent equipment and two grades, three-level raw water tank, first, second, third adsorbent equipment in adsorption tower Temperature sensor;
The adsorbent equipment includes the first adsorption tower and the second adsorption tower, condenser, parsing water pot, steam pipe, raw water tubes, described Resin is supported in first adsorption tower and the second adsorption tower adsorption tower using multiple water caps, the gap of water cap is handed over less than polystyrene Join the diameter of resin;
First adsorption tower and second absorption tower top provided with processing water outlet pipe, raw water tubes respectively with the first adsorption tower and second Adsorb and be connected at the top of tower bottom connection, Boiler Steam pipe and the first described adsorption tower and the second adsorption tower, the first adsorption tower with It is connected after second adsorption tower bottom steam output pipe is in parallel with condenser;The first adsorbent equipment processing water outlet pipe and two grades of originals Water fills connection, and two grades of raw waters are filled to be connected with the raw water tubes of the second adsorbent equipment;Second adsorbent equipment processing water outlet pipe with Three-level raw water fills connection;Three-level raw water is filled and is connected with the raw water tubes of the 3rd adsorbent equipment;The first, second, third absorption dress The steam output pipe put is connected with three condenser air inlets respectively, is connected after three leaving condenser waters mouthful are in parallel with parsing water pot Connect.
CN201710233221.7A 2017-04-11 2017-04-11 Comprehensive treatment method and treatment device for waste gas in benzyl alcohol production Active CN107008107B (en)

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