CN107008133B - Comprehensive treatment device for waste gas and waste water in benzyl alcohol production - Google Patents
Comprehensive treatment device for waste gas and waste water in benzyl alcohol production Download PDFInfo
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- CN107008133B CN107008133B CN201710232911.0A CN201710232911A CN107008133B CN 107008133 B CN107008133 B CN 107008133B CN 201710232911 A CN201710232911 A CN 201710232911A CN 107008133 B CN107008133 B CN 107008133B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1406—Multiple stage absorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
Abstract
The invention is characterized in that the treatment device comprises a waste gas buffer tank, a normal temperature spray tower, a freezing spray tower, a heat exchanger, a refrigerator, a brine tank, an active carbon absorption tower and a liquid caustic soda absorption tower.
Description
Technical Field
The invention relates to the field of waste gas treatment in industrial production, in particular to a comprehensive treatment device for waste gas and waste water in benzyl alcohol production.
Background
Benzyl alcohol (also known as benzyl alcohol and hydroxy toluene) is a very useful chemical intermediate, and is widely used in industries such as curing agents, diluents, spices and essence. At present, benzyl chloride and sodium carbonate are mostly adopted to react at home and abroad to generate, a large amount of waste gas can be generated through the reaction, mainly carbon dioxide generated in the hydrolysis process, and a small amount of volatilized benzyl chloride and benzyl alcohol. At present, the treatment facilities of a plurality of manufacturers are difficult to thoroughly solve the pollution problem of waste gas, the environmental protection problem becomes a non-negligible problem along with the development of social economy, and emission reduction even zero discharge becomes the basic requirement of society and government on chemical enterprises.
At present, benzyl chloride and soda are mainly used for preparing benzyl alcohol in industry, a large amount of benzyl alcohol is contained in high-salinity wastewater generated by hydrolysis reaction, and if the benzyl alcohol is directly discharged, serious pollution is caused to the environment, and huge economic loss is caused.
Disclosure of Invention
The invention aims to provide a comprehensive treatment device for waste gas and waste water in benzyl alcohol production, which aims to solve the technical problems that the waste gas in the benzyl alcohol production process pollutes the atmosphere, causes harm to human bodies, pollutes the environment by waste water and the like.
In order to thoroughly solve the problem of waste gas in the production process of benzyl alcohol, the invention adopts the following technical scheme: the integrated treatment device for the waste gas and the waste water generated in the benzyl alcohol production is characterized in that the treatment device comprises a waste gas buffer tank, a normal-temperature spray tower, a freezing spray tower, a heat exchanger, a refrigerator, a brine tank, an activated carbon absorption tower and a liquid alkali absorption tower, and is characterized in that the waste gas buffer tank is connected with the bottom of the normal-temperature spray tower, the top outlet of the normal-temperature spray tower is connected with the bottom of the freezing spray tower, the top outlet of the freezing spray tower is connected with the bottom of the activated carbon absorption tower, and the top outlet of the activated carbon absorption tower is connected;
the bottoms of the normal-temperature spray tower, the adsorption system of the freezing spray tower, the activated carbon absorption tower and the liquid caustic soda absorption tower are respectively provided with a wastewater discharge pipe, and the wastewater discharge pipes are connected in parallel and then connected with a wastewater collection tank; the wastewater collection tank is also connected with a wastewater adsorption system, the wastewater adsorption system comprises a first adsorption device, a second adsorption device, a third adsorption device and a second-level raw water tank and a third-level raw water tank, and temperature sensors are arranged in adsorption towers of the first adsorption device, the second adsorption device and the third adsorption device;
the adsorption device comprises a first adsorption tower, a second adsorption tower, a condenser, a desorption water tank, a steam pipe and a raw water pipe, wherein a plurality of water caps are adopted in the first adsorption tower and the second adsorption tower to support resin, and the gap between the water caps is smaller than the diameter of the polystyrene cross-linked resin;
treated water outlet pipes are arranged on the tops of the first adsorption tower and the second adsorption tower, raw water pipes are respectively connected with the bottoms of the first adsorption tower and the second adsorption tower, a boiler steam pipe is connected with the tops of the first adsorption tower and the second adsorption tower, and steam output pipes at the bottoms of the first adsorption tower and the second adsorption tower are connected in parallel and then connected with a condenser; the treated water outlet pipe of the first adsorption device is connected with the secondary raw water tank, and the secondary raw water tank is connected with the raw water pipe of the second adsorption device; the treated water outlet pipe of the second adsorption device is connected with the three-stage raw water tank; the third-stage raw water tank is connected with a raw water pipe of a third adsorption device; and the steam output pipes of the first, second and third adsorption devices are respectively connected with the air inlets of the three condensers, and the water outlets of the three condensers are connected in parallel and then connected with the analysis water tank.
Preferably, the heat exchanger is provided with a cooling water inlet and a cooling water outlet, the cooling water inlet is connected with the brine tank through a circulating pump, the brine tank is connected with the refrigerator, and the cooling water outlet is connected with the brine tank.
Preferably, the number of the activated carbon absorption towers is two, one adsorption tower and one desorption tower are alternately used.
Preferably, the activated carbon absorption tower is provided with a condenser and a vapor piping system.
Preferably, regular corrugated ceramic packing is filled in the normal temperature spray tower, the freezing spray tower and the liquid caustic soda absorption tower.
The invention provides a comprehensive treatment device for waste gas and waste water in benzyl alcohol production, which can absorb all waste gas, ensure that COD (chemical oxygen demand) of the waste water generated in the treatment process can reach the national discharge standard, ensure that equipment can be recycled, and is beneficial to enterprises to save production cost. The recovery process of the benzyl alcohol adopts the physical adsorption capacity of the resin, and other chemical reagents are not added; the elution process of the resin adopts high-temperature steam, and other chemical impurities are not introduced into the system; all the processes adopt an adsorption-desorption alternative use mode, so that the continuity of the adsorption process is ensured, and the operation is stable; the analysis water generated in the analysis process can be used for participating in alkali preparation, no redundant waste water is generated, the recovered benzyl alcohol enters the system again, and the secondary pollution is avoided by rectification and recovery. Realizing zero emission in the real sense.
Drawings
The technical solution of the present invention is further described in detail with reference to the accompanying drawings and the detailed description.
FIG. 1 is a schematic view of the structure of the apparatus of the present invention.
Detailed Description
FIG. 1 is a schematic diagram of the structure of the apparatus of the present invention. As can be seen from figure 1, the comprehensive treatment device for the waste gas and the waste water in the benzyl alcohol production comprises a waste gas buffer tank 1, a normal temperature spray tower 2, a freezing spray tower 3, a heat exchanger, a refrigerator, a brine tank, an activated carbon absorption tower 6 and a liquid caustic soda absorption tower 7, wherein regular corrugated ceramic packing 8 is filled in the normal temperature spray tower 2, the freezing spray tower 3 and the liquid caustic soda absorption tower 7.
The waste gas buffer tank 1 is connected with the bottom of the normal temperature spray tower 2, the top outlet of the normal temperature spray tower 2 is connected with the bottom of the freezing spray tower 3, the top outlet of the freezing spray tower 3 is connected with the bottom of the active carbon absorption tower 6, and the top outlet of the active carbon absorption tower 6 is connected with the bottom of the liquid caustic soda absorption tower 7.
The bottoms of the normal temperature spray tower 2, the freezing spray tower 3, the activated carbon absorption tower 6 and the liquid caustic soda absorption tower 7 are respectively provided with a waste water discharge pipe, and the waste water discharge pipes 21, 31, 61 and 71 are connected in parallel and then connected with a waste water collecting tank; the waste water collecting tank is also connected with a waste water adsorption system, the waste water adsorption system comprises a first adsorption device, a second adsorption device, a third adsorption device, a second-level raw water tank and a third-level raw water tank, and temperature sensors 92 are arranged in the adsorption towers of the first adsorption device, the second adsorption device and the third adsorption device.
The first adsorption device comprises a first adsorption tower A1, a second adsorption tower A2, a condenser, a desorption water tank, a steam pipe 94 and a raw water pipe 96, wherein a plurality of water caps 91 are adopted in the first adsorption tower A1 and the second adsorption tower A2 to support the resin 9, and the gap of each water cap 91 is smaller than the diameter of the polystyrene cross-linked resin 9; treated water outlet pipes 95 are arranged at the tops of the first adsorption tower A1 and the second adsorption tower A2, a raw water pipe 96 is respectively connected with the bottoms of the first adsorption tower A1 and the second adsorption tower A2, a steam pipe 94 is connected with the tops of the first adsorption tower A1 and the second adsorption tower A2, and a steam outlet pipe 97 at the bottom of the first adsorption tower A1 and the second adsorption tower A2 are connected in parallel and then connected with a condenser. The treated water outlet pipe 95 of the first adsorption device is connected with a secondary raw water tank, and the secondary raw water tank is connected with a raw water pipe 101 of a second adsorption device; the second adsorption device treated water outlet pipe 104 is connected with the third-stage raw water tank; the third-level raw water tank is connected with a raw water pipe 103 of the third adsorption device. The steam output pipes 97, 102 and 105 of the first, second and third adsorption devices are respectively connected with the air inlets of the three condensers, and the water outlets of the three condensers are connected in parallel and then connected with the analysis water tank.
The heat exchanger is provided with a cooling water inlet 41 and a cooling water outlet 42, the cooling water inlet 41 is connected with a brine tank through a circulating pump 51, the brine tank is connected with the refrigerator, and the cooling water outlet 42 is connected with the brine tank.
The two activated carbon absorption towers 6 are arranged, one is used for adsorption, and the other is used for desorption and is used alternately; the activated carbon absorption tower 6 is provided with a condenser 61 and a steam piping system 62 for desorption regeneration of the activated carbon.
The working principle is as follows: the waste gas is generated from benzyl chloride hydrolysis reaction, and the main components in the waste gas are carbon dioxide, benzyl chloride, benzyl alcohol, benzaldehyde and other gases. Waste gas firstly collects in the waste gas buffer tank 1, and then enters the normal temperature spray absorption tower 2 from the bottom air inlet of the tower, the normal temperature spray absorption tower 2 adopts normal temperature soft water, the normal temperature soft water is continuously conveyed to the top of the tower through a pump, the sprayed normal temperature spray water is in convection contact with the waste gas, a mixture of triethanolamine and quaternary ammonium base is added into the normal temperature spray water, the mass ratio of the mixture to the normal temperature spray water is 0.001-0.002, and most organic gases in the waste gas can be absorbed in the adsorption spray stage. Meanwhile, the lower adsorption water tank is continuously replenished with water and discharged with water, the continuity of the adsorption spraying effect is ensured, and the wastewater discharged from the water outlet enters the wastewater collecting tank.
The waste gas absorbed by the normal temperature spray tower 2 enters the tower from the inlet at the bottom of the freezing spray tower 3, the waste gas absorbed by spraying enters the freezing spray process, and normal temperature soft water is continuously conveyed to the top of the freezing spray tower 3 through a pump and is in convection contact with the waste gas in the tower. The difference is that soft water can be reduced to 0-3 ℃ after heat exchange of a refrigerator, the frozen water is added with the urotropine with the mass ratio of 0.001-0.002, the soft water has a better absorption effect on organic gas, 90% of residual organic gas in waste gas can be basically absorbed in the stage, meanwhile, continuous water replenishing and water discharging are carried out on a brine tank below, the continuity of the absorption spraying effect is ensured, and waste water discharged from a water outlet enters a waste water collecting tank.
The waste gas from the freezing spray tower 3 enters the bottom of the active carbon absorption tower 6 through a pipeline fan, organic gas which cannot be absorbed through spraying in the waste gas is absorbed by utilizing the active carbon physical absorption process in the absorption process from bottom to top, and the diameter of active carbon particles is 2.0-2.8 mm. High-temperature steam is adopted in the regeneration process of the activated carbon, and the waste water after steam condensation participates in the hydrolysis reaction of benzyl chloride.
Through the absorption of active carbon absorption tower 6, the organic gas in the waste gas is adsorbed completely, and active carbon absorption tower 6 is the absorption-desorption mode of alternative use, and when a tower adsorbs, another tower is carried out the analysis with high temperature steam, and the high temperature waste gas of analyzing out enters into waste water collection tank after passing through condenser 61 condensation.
The waste gas absorbed from the active carbon absorption tower 6 enters the liquid alkali absorption tower 7 from a gas outlet at the top of the tower, the sodium hydroxide liquid with the volume concentration of 48% is conveyed to the top of the spray tower through a pump and is in convection contact with the waste gas, and the residual carbon dioxide in the waste gas is completely absorbed in the process. And (3) allowing a soda ash solution generated by the reaction of the liquid caustic soda and the carbon dioxide to enter the wastewater tank through the water outlet, and replenishing the liquid caustic soda through the soda replenishing port when the PH of the liquid caustic soda water tank is less than a set value. The wastewater in the wastewater collection tank enters a wastewater adsorption system for treatment, enters the bottom of a first adsorption tower A1 through a raw water pipe 96, uniformly passes through a polystyrene cross-linked resin 9 through a water cap 91 at a flow rate of 2-3BV/h, passes through a treated water outlet pipe 95 from the top of the tower to a secondary raw water tank, stops the adsorption of the first adsorption tower A1 when the alcohol content in the outlet water is more than or equal to 0.1%, switches to an analytic process, and switches to a second adsorption tower A2 to continue adsorption.
The second adsorption column a2 was in a desorption state during the adsorption by the first adsorption column a 1. High-temperature steam from a boiler enters the second adsorption tower A2 from the top of the tower, the high-temperature steam elutes benzyl alcohol adsorbed by the polystyrene cross-linked resin 9, the desorption temperature is 130-140 ℃, the high-temperature steam enters a condenser from a steam output pipe 97 at the bottom of the tower for condensation, and finally enters a desorption water tank. When the alcohol content of the desorption water from the condenser is less than or equal to 0.001 percent, the desorption is considered to be complete, the temperature reduction and condensation of the steam are stopped, and the A2 adsorption tower is in a state of waiting for adsorption. The first adsorption tower A1 and the second adsorption tower A2 belong to parallel towers of first-stage adsorption, one adsorption tower and one desorption tower are alternately used, and the continuity of the first-stage adsorption is ensured.
The second stage adsorption device and the third stage adsorption device are similar to the first stage adsorption. And (3) the secondary raw water from the primary adsorption device enters a secondary first adsorption tower B1, and the adsorption is stopped when the alcohol content of the effluent is more than or equal to 0.05 percent. When the second-stage first adsorption tower B1 adsorbs, the second-stage second adsorption tower B2 is in an analytic state, the second-stage first adsorption tower B1 and the second adsorption tower B2 are alternately used, the continuity of the second-stage adsorption is ensured, and the COD of the second-stage adsorbed effluent is 300-500 mg/l. And the tertiary raw water from the second-stage adsorption device enters a tertiary first adsorption tower C1, and the adsorption is stopped when the alcohol content of the effluent is more than or equal to 0.01 percent. When the three-stage first adsorption tower C1 is used for adsorption, the three-stage second adsorption tower C2 is in an analytic state, the three-stage first adsorption tower C1 and the third adsorption tower C2 are alternately used, the continuity of three-stage adsorption is ensured, and COD (chemical oxygen demand) of three-stage adsorption effluent is less than 100 mg/l.
The benzyl alcohol wastewater adsorbed by the three-stage resin contains less than 0.01 percent of alcohol, and the recovery rate reaches 99 percent; meanwhile, after the resolved water is settled and layered, the lower oil phase is rectified to obtain benzyl alcohol, and the upper resolved water can be used for being matched with alkali to participate in the hydrolysis process of benzyl chloride; the COD of the wastewater after the three-stage adsorption is less than 100mg/l, which reaches the national discharge standard.
Through the processes of normal temperature absorption, freezing absorption, activated carbon absorption and liquid caustic soda absorption. The waste gas generated in the benzyl chloride hydrolysis process is completely absorbed to reach the zero discharge standard, and simultaneously, COD (chemical oxygen demand) of various waste water generated in the process after three-stage adsorption is less than 100mg/l, so that the waste water reaches the national discharge standard, and secondary pollution is avoided.
Finally, it should be noted that the above embodiments are merely representative examples of the invention. It will be clear that the invention is not limited to the specific embodiments described above, but that many variations are possible. Any simple modification, equivalent change and modification made to the above embodiments in accordance with the technical spirit of the present invention should be considered to be within the scope of the present invention.
Claims (5)
1. The integrated treatment device for the waste gas and the waste water generated in the benzyl alcohol production is characterized in that the treatment device comprises a waste gas buffer tank, a normal-temperature spray tower, a freezing spray tower, a heat exchanger, a refrigerator, a brine tank, an activated carbon absorption tower and a liquid alkali absorption tower, and is characterized in that the waste gas buffer tank is connected with the bottom of the normal-temperature spray tower, the top outlet of the normal-temperature spray tower is connected with the bottom of the freezing spray tower, the top outlet of the freezing spray tower is connected with the bottom of the activated carbon absorption tower, and the top outlet of the activated carbon absorption tower is connected;
the bottoms of the normal-temperature spray tower, the adsorption system of the freezing spray tower, the activated carbon absorption tower and the liquid caustic soda absorption tower are respectively provided with a wastewater discharge pipe, and the wastewater discharge pipes are connected in parallel and then connected with a wastewater collection tank; the wastewater collection tank is also connected with a wastewater adsorption system, the wastewater adsorption system comprises a first adsorption device, a second adsorption device, a third adsorption device and a second-level raw water tank and a third-level raw water tank, and temperature sensors are arranged in adsorption towers of the first adsorption device, the second adsorption device and the third adsorption device;
the adsorption device comprises a first adsorption tower, a second adsorption tower, a condenser, a desorption water tank, a steam pipe and a raw water pipe, wherein a plurality of water caps are adopted in the first adsorption tower and the second adsorption tower to support resin, and the gap between the water caps is smaller than the diameter of the polystyrene cross-linked resin;
treated water outlet pipes are arranged on the tops of the first adsorption tower and the second adsorption tower, raw water pipes are respectively connected with the bottoms of the first adsorption tower and the second adsorption tower, a boiler steam pipe is connected with the tops of the first adsorption tower and the second adsorption tower, and steam output pipes at the bottoms of the first adsorption tower and the second adsorption tower are connected in parallel and then connected with a condenser; the treated water outlet pipe of the first adsorption device is connected with the secondary raw water tank, and the secondary raw water tank is connected with the raw water pipe of the second adsorption device; the treated water outlet pipe of the second adsorption device is connected with the three-stage raw water tank; the third-stage raw water tank is connected with a raw water pipe of a third adsorption device; and the steam output pipes of the first, second and third adsorption devices are respectively connected with the air inlets of the three condensers, and the water outlets of the three condensers are connected in parallel and then connected with the analysis water tank.
2. The integrated treatment device for the waste gas and wastewater from benzyl alcohol production according to claim 1, which is characterized in that: the heat exchanger is equipped with cooling water inlet and cooling water outlet, the cooling water inlet passes through the circulating pump and is connected with the brine tank, and the brine tank is connected with the refrigerator, the cooling water outlet is connected with the brine tank.
3. The integrated treatment device for the waste gas and wastewater from benzyl alcohol production according to claim 1, which is characterized in that: the active carbon absorption towers are two, one is used for adsorption and the other is used for desorption, and the active carbon absorption towers are used alternately.
4. The integrated treatment device for the waste gas and wastewater from benzyl alcohol production according to claim 1, which is characterized in that: the activated carbon absorption tower is provided with a condenser and a steam pipeline system.
5. The integrated treatment device for the waste gas and wastewater from benzyl alcohol production according to claim 1, which is characterized in that: regular corrugated ceramic packing is filled in the normal-temperature spray tower, the freezing spray tower and the liquid caustic soda absorption tower.
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| CN112275089A (en) * | 2020-10-15 | 2021-01-29 | 河南中烟工业有限责任公司 | Effluent disposal polluted gas purification system |
| CN112774396A (en) * | 2020-12-23 | 2021-05-11 | 产学研(广州)环境服务有限公司 | VOCs device is retrieved in high-efficient absorption |
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| CN101050165A (en) * | 2007-05-21 | 2007-10-10 | 鄂州海丰化工实业有限公司 | Wastewater treatment for benzoic alcohol, and technique for recovering benzoic alcohol |
| CN101721832B (en) * | 2008-10-28 | 2012-02-29 | 中国石油化工股份有限公司 | Method for treating discharged waste gas of acid water tank area |
| US8840706B1 (en) * | 2011-05-24 | 2014-09-23 | Srivats Srinivasachar | Capture of carbon dioxide by hybrid sorption |
| CN105498446A (en) * | 2016-01-08 | 2016-04-20 | 浙江大学 | Method for recycling organic matter through organic waste gas adsorption, steam desorption and fractional condensation |
| CN205760480U (en) * | 2016-07-16 | 2016-12-07 | 湖北绿色家园精细化工股份有限公司 | The device for absorbing tail gas that a kind of benzyl alcohol produces |
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