CN217264857U - Concentration and reuse device for chlorine gas drying waste acid - Google Patents
Concentration and reuse device for chlorine gas drying waste acid Download PDFInfo
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- CN217264857U CN217264857U CN202220285745.7U CN202220285745U CN217264857U CN 217264857 U CN217264857 U CN 217264857U CN 202220285745 U CN202220285745 U CN 202220285745U CN 217264857 U CN217264857 U CN 217264857U
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Abstract
The utility model discloses a concentration and reuse device for chlorine gas drying waste acid, which comprises an acid-acid heat exchanger, wherein a cold side inlet of the acid-acid heat exchanger is connected with a raw material acid head tank, a cold side outlet is connected with a feed inlet of a first-level concentration kettle, and a hot side outlet is connected with a hot side inlet of a finished product acid cooler; the primary concentrating kettle liquid phase outlet is connected with a feed inlet of a secondary concentrating kettle, the secondary concentrating kettle liquid phase outlet is connected with a hot side inlet of an acid-acid heat exchanger, the primary concentrating kettle gas phase outlet is directly connected with a defoaming tower, the defoaming tower outlet is connected with a spray condenser, the secondary concentrating kettle gas phase outlet is connected with a washing tower gas phase inlet, and the washing tower gas phase outlet is connected with an inlet of a steam spray pump; a primary heater is arranged in the primary concentration kettle, and a secondary heater is arranged in the secondary concentration kettle. The utility model discloses can effectively solve the dry spent acid cyclic utilization problem of chlorine, have reliable and stable, energy-concerving and environment-protective, advantage that the comprehensive cost is low.
Description
Technical Field
The utility model relates to a concentration and recycling device of waste acid especially relates to a concentration and recycling device of chlorine drying waste acid.
Background
Caustic soda is an important basic chemical raw material, and the production method of the caustic soda in China at present is mainly an ion membrane electrolysis method. In the production process of the caustic soda by the ion membrane electrolysis method, the generated chlorine is generally dried by a sulfuric acid method, and the process consumes about 12kg of 98 percent sulfuric acid per ton of caustic soda. In 2020, the total production of caustic soda in China is 3673.9 ten thousand tons, and the produced waste acid (75%) is about 58.8 ten thousand tons. At present, chlorine gas drying waste acid treatment modes of chlor-alkali enterprises are mainly outsourcing downstream enterprises or adopting a neutralization method for treatment.
In developed economic bodies in Europe and America, almost all waste acid in the chlor-alkali industry is concentrated and recycled. With the continuous improvement of national requirements on energy conservation, environmental protection and resource utilization, the concentration and recycling of waste acid is becoming a consensus of more and more chlor-alkali enterprises, and the recycling is a mainstream development direction.
Prior art 1: sulfuric acid concentration technology (see the application of sulfuric acid concentration technology in the caustic soda production process at the 1 st stage of volume 57 of chlor-alkali industry). In order to realize the recycling of waste acid, the waste acid is preheated and then sent into a primary concentration rectifying tower to be in countercurrent contact with secondary steam, so that the acid content of the secondary steam is reduced, and low-pressure steam is used as a heat source in primary concentration; and (4) overflowing the concentrated acid into a second-stage concentration, wherein the second-stage concentration adopts an immersed electric heating rod, and secondary steam also enters a first-stage rectifying tower. The two-stage concentration is operated under the same vacuum, gas-phase water vapor is condensed and recovered by chilled water, and non-condensable gas enters a vacuum pump and is discharged into an absorption device. The advantage of this technique is that equipment configuration is succinct, make full use of secondary steam heat energy, and the shortcoming is that the second grade concentration adopts multiunit quartz electric heating rod on the one hand, and the quartz rod is easy to split, and fail safe nature reduces, and on the other hand the same vacuum is adopted in the two-stage concentration, and the secondary steam temperature is low, needs to use low temperature refrigerated water condensation recovery in a large number. Therefore, this technique has a drawback of high production cost.
Prior art 2: patent document CN108358176A discloses a dilute sulfuric acid vacuum concentration device and method, wherein dilute sulfuric acid is preheated and then concentrated to about 96% by two-stage vacuum concentration, and the generated secondary steam is directly fed into a condenser for condensation and recovery. According to the partial pressure data of sulfuric acid on the sulfuric acid solution, secondary steam generated by secondary concentration in the technology contains more acid, the direct condensation and recovery result in the reduction of the acid recovery rate, the acidity of wastewater is higher, and the difficulty is increased for wastewater treatment.
SUMMERY OF THE UTILITY MODEL
The utility model aims to solve the technical problem that a concentration retrieval and utilization device of dry spent acid of chlorine is provided, can effectively solve the dry spent acid cyclic utilization problem of chlorine, have reliable and stable, energy-concerving and environment-protective, advantage that the comprehensive cost is low.
The utility model provides a concentration and recycling device for chlorine gas drying waste acid, which comprises an acid-acid heat exchanger, wherein, a cold side inlet of the acid-acid heat exchanger is connected with a raw material acid elevated tank, a cold side outlet of the acid-acid heat exchanger is connected with a feed inlet of a first-level concentration kettle, and a hot side outlet of the acid-acid heat exchanger is connected with a hot side inlet of a finished product acid cooler; the primary concentrating kettle liquid phase outlet is connected with a feed inlet of a secondary concentrating kettle, the secondary concentrating kettle liquid phase outlet is connected with a hot side inlet of an acid-acid heat exchanger, the primary concentrating kettle gas phase outlet is directly connected with a defoaming tower, the defoaming tower outlet is connected with a spray condenser, the secondary concentrating kettle gas phase outlet is connected with a washing tower gas phase inlet, and the washing tower gas phase outlet is connected with an inlet of a steam spray pump; a primary heater is arranged in the primary concentration kettle, and a secondary heater is arranged in the secondary concentration kettle.
Furthermore, the primary heater and the secondary heater both adopt tantalum heaters, and a plurality of baffles are arranged in the tantalum heaters.
Furthermore, a concentration condenser is arranged between the gas phase outlet of the gas washing tower and the inlet of the steam jet pump, and the outlet of the concentration condenser is connected with the waste water intermediate tank.
Further, the concentration condenser uses 0 ℃ chilled water as a cooling liquid.
Further, an outlet of the finished product acid cooler is connected with a finished product acid intermediate tank.
Furthermore, the primary heater is filled with low-pressure steam of 0.8MPa to 1.0MPa for heating and concentration, and the secondary heater is filled with steam of 1.6MPa to 2.0MPa for secondary heating and concentration.
Further, the finished acid cooler and the spray condenser adopt circulating water as cooling liquid.
The utility model discloses contrast prior art has following beneficial effect: the utility model provides a concentration retrieval and utilization device of dry spent acid of chlorine adopts the horizontal vacuum evaporation of two-stage, with the evaporation of water in the dilute sulfuric acid under different vacuum, improves liquid phase sulfuric acid concentration. The method has the following specific advantages: firstly, the boiling point of sulfuric acid is greatly reduced by high vacuum, so that the operation temperature of equipment is reduced, and the range of the type selection and material selection of the equipment is wider; the boiling point is reduced, the heat transfer temperature difference is increased under the condition of the same specification of steam, the heat exchange area is further reduced, and the investment is saved; thirdly, a tantalum bayonet tube type heater is adopted, a plurality of baffles are arranged, material backflow is reduced, the material backflow is in countercurrent contact with steam, and the heat transfer driving force is large; fourthly, a foam removing tower is arranged at a gas phase outlet of the primary concentration kettle, so that the foam entrainment of the materials is reduced, and the gas phase of the secondary concentration kettle is washed to remove sulfuric acid, so that the high recovery rate of the sulfuric acid is ensured; a process of condensation and compression is adopted, secondary steam is condensed and then provides high vacuum for the device through a steam jet pump, and steam consumption is saved; sixthly, the primary concentration vacuum degree is lower, the secondary steam can be directly cooled by circulating water, and high-cost chilled water is not needed as a medium.
Drawings
FIG. 1 is a schematic structural view of the concentration and recycling device for the waste acid from chlorine drying.
In the figure:
1-raw acid elevated tank, 2-acid heat exchanger, 3-first level concentration kettle, 4-first level heater, 5-defoaming tower, 6-second level concentration kettle, 7-second level heater, 8-washing tower, 9-washing circulating pump, 10-concentration condenser, 11-steam jet pump, 12-jet condenser, 13-vacuum pump, 14-finished acid cooler, 15-finished acid pump, 16-waste water pump, 17-waste water intermediate tank, 18-finished acid intermediate tank.
Detailed Description
The invention is further described with reference to the following figures and examples.
FIG. 1 is a schematic structural view of the concentration and recycling device for the waste acid from chlorine drying.
Referring to fig. 1, the concentration and recycling device for chlorine drying waste acid provided by the present invention comprises an acid-acid heat exchanger 2, wherein a cold side inlet of the acid-acid heat exchanger 2 is connected to a raw material acid head tank 1, a cold side outlet of the acid-acid heat exchanger 2 is connected to a feed inlet of a first-stage concentration kettle 3, and a hot side outlet of the acid-acid heat exchanger 2 is connected to a hot side inlet of a finished product acid cooler 14; the liquid phase outlet of the first-stage concentration kettle 3 is connected with the feed inlet of the second-stage concentration kettle 6, the liquid phase outlet of the second-stage concentration kettle 6 is connected with the hot side inlet of the acid-acid heat exchanger 2, the gas phase outlet of the first-stage concentration kettle 3 is directly connected with the defoaming tower 5, the outlet of the defoaming tower 5 is connected with the injection condenser 12, the gas phase outlet of the second-stage concentration kettle 6 is connected with the gas phase inlet of the washing tower 8, and the gas phase outlet of the gas washing tower 8 is connected with the inlet of the steam injection pump 11;
a primary heater 4 is arranged in the primary concentration kettle 3, and a secondary heater 7 is arranged in the secondary concentration kettle 6; the spray condenser 12 is used as a first-stage condenser, the concentration condenser 10 is used as a second-stage condenser and is positioned between the gas phase outlet of the scrubber tower 8 and the inlet of the steam spray pump 11, and the outlet of the concentration condenser 10 is connected with the waste water intermediate tank 17.
The process treatment flow of the utility model is as follows:
raw material waste acid outside the boundary area enters a raw material acid elevated tank 1, part of the waste acid overflows out of the boundary area, and the rest waste acid enters a primary concentration kettle 3 after exchanging heat with hot finished product sulfuric acid through an acid-acid heat exchanger 2 through flow control.
The dilute sulfuric acid entering the primary concentration kettle 3 is heated and concentrated to a process concentration, such as 83-88%, by a primary heater 4 under a vacuum condition; the concentrated sulfuric acid automatically flows into a second-stage concentration kettle 6, and is heated and concentrated to the sulfuric acid concentration of more than 96% by a second-stage heater 7 under the vacuum condition. The 96% hot acid exchanges heat with the raw waste acid, then is mixed with the cooled high-concentration sulfuric acid (more than 96%), enters a finished product acid cooler 14, is cooled to below 45 ℃, and enters a finished product acid intermediate tank. Part of the cooled high-concentration sulfuric acid is mixed with 96% hot acid after heat exchange by controlling the inlet temperature of a finished product acid cooler 14, and the rest is sent out of a battery limit by controlling the liquid level of a finished product acid intermediate tank 18 by a finished product acid pump 15.
The water vapor evaporated by the first-stage concentration is defoamed by a defoaming tower 5 and then is directly sent to a jet condenser 12 for condensation and cooling; the water vapor evaporated from the second-stage concentration is sprayed and washed by circulating washing liquid provided by a washing circulating pump 9 through a washing tower 8, and acid mist carried in the vapor is collected and returned to the first-stage concentration kettle 3. The acidic water vapor after being deacidified and cooled by the washing tower 8 is condensed by a concentration condenser 10, and then is condensed by a vapor injection pump 11 after being compressed by vapor and then is sent to an injection condenser 12. The condensed water enters a waste water intermediate tank 17; the non-condensable gas enters the working solution buffer tank in a gas-liquid mixture form for gas-liquid separation under the action of a vacuum pump 13, and the gas is sent to the outside of the battery compartment for treatment; the working fluid is cooled and recycled by a working fluid cooler (not shown). The vacuum of the primary concentration process is generated by a vacuum pump 13, and the vacuum of the secondary concentration process is generated by the steam jet pump 11 and the vacuum pump 13 together. The acid wastewater part is used as make-up water for the vacuum pump 13, and the rest is sent out of the battery limits by the wastewater pump 16 through controlling the liquid level of the wastewater intermediate tank 17 for treatment.
The finished product acid cooler 14, the spray condenser 12 and the working fluid cooler adopt circulating water as cooling fluid, and the concentration condenser 10 adopts 0 ℃ chilled water as cooling fluid.
The primary heater 4 and the secondary heater 7 both adopt tantalum heaters, wherein the primary heater 4 is heated by 0.8-1.0 MPa steam; the secondary heater 7 is heated by 1.6-2.0 MPa steam, preferably 1.6-1.8 MPa steam, and condensed water is sent out of a boundary area for comprehensive utilization.
(5) Example of the implementation
Pumping 70-80% dilute sulfuric acid into a raw acid elevated tank 1 by a raw acid pump outside a battery compartment, exchanging heat with high-temperature finished acid discharged from a secondary concentration kettle 6 by utilizing potential difference to automatically flow into an acid heat exchanger 2, and automatically flowing the preheated raw acid into a primary concentration kettle 3; under the absolute pressure of 65-75 mmHg, raw material acid sequentially flows through a plurality of concentrating chambers in a concentrating kettle, the acid liquor backflow is prevented by the concentrating chambers due to the existence of partition plates, the acid concentration in the concentrating chambers is sequentially improved, and the raw material acid is concentrated to 83-88% under the heating of low-pressure steam of 0.8-1.0 MPa (G);
acid from the first-stage concentration kettle 3 automatically flows into a second-stage concentration kettle 6, the structure of the second-stage concentration kettle 6 is similar to that of the first-stage concentration kettle 3, the concentration kettle is divided into a plurality of concentration chambers, the acid concentration is sequentially improved, finally, the sulfuric acid reaches more than 96% under the condition of absolute pressure of 12-20 mmHg, and the sulfuric acid is discharged out of the second-stage concentration kettle 6;
removing mist from the secondary steam generated by the primary concentration kettle 3 through a mist removing tower 5, mixing the secondary steam with the gas from a steam jet pump 11, feeding the mixture into a jet condenser 12, condensing the steam, feeding the condensed steam into a waste water intermediate tank 17, pumping out non-condensable gas, a small amount of steam and the like through a vacuum pump 13, and finally discharging the condensed steam to a tail gas purification tower (not shown in the figure) for treatment; acid-containing water vapor generated by the second-stage concentration kettle 6 is sprayed and washed through the washing tower 8 to remove sulfuric acid in the water vapor, a part of spray liquid and raw material acid are mixed and enter the first-stage concentration kettle 3, acid waste water is used as spray circulation liquid for supplementing water, the water vapor coming out of the washing tower 8 enters the concentration condenser 10, freezing water is used for condensation and cooling, non-condensable gas, a small amount of water vapor and the like are pumped out by the steam jet pump 11, and the water vapor discharged by the steam jet pump 11 and secondary steam discharged by the first-stage concentration kettle 3 are mixed and enter the jet condenser 12.
The waste acid is required to be concentrated to more than 93% for recycling when being dried by the chlorine, and according to the data of the water feeding and the sulfuric acid partial pressure of the sulfuric acid solution, the secondary steam contains more sulfuric acid, and if the secondary steam enters a condenser, the secondary steam has stronger corrosivity, the waste water has high acid content, and the waste of the sulfuric acid is caused. Therefore, the utility model adopts the spray washing mode to remove the sulfuric acid, reduces the acid content of the waste water, and improves the recovery rate of the sulfuric acid. The two-stage concentration has different vacuum degrees, proper operation pressure is selected according to the relation between the boiling point of the material and the pressure, and the primary concentrated secondary steam can be condensed by circulating water, so that the defect that high-cost chilled water must be adopted under high vacuum is overcome. The utility model discloses can effectively solve the dry spent acid cyclic utilization problem of chlorine to a stable and reliable, energy-concerving and environment-protective, the solution that comprehensive cost is low is provided. The method has the following specific advantages:
(1) the entrainment phenomenon of secondary steam is reduced by arranging the defoaming tower 5, the secondary steam contains higher sulfuric acid steam due to high acid concentration in the secondary concentration, the washing tower 8 for spraying can effectively wash away the sulfuric acid in the secondary steam, the acid content of the wastewater is reduced, the use safety of subsequent equipment is protected, the sulfuric acid recovery rate of the device is further ensured, and the device is more environment-friendly;
(2) the device adopts middle and low pressure steam as a heat source, and the heater adopts a tantalum bayonet tube type with high reliability, so that compared with a quartz electric heating tube which is easy to crack, the device has stable operation and high reliability.
(3) The process device only consumes steam and electricity, and is provided with the high-temperature acid-acid heat exchanger, thereby fully utilizing the heat energy of high-quality products; the circulating water replenishing of the vacuum system adopts process condensate water, so that the wastewater discharge is reduced; the vacuum system adopts a standard device, namely a water ring vacuum pump, so that the vacuum degree is stable, and the maintenance and the replacement are convenient.
(4) The concentration of sulfuric acid in the product acid is more than or equal to 96 percent, and the content of chloride ions is less than or equal to 10ppm, so that the recycling requirement of a chlorine drying procedure is completely met; the recovery rate of waste acid is high, only a small amount of fresh 98 percent sulfuric acid needs to be supplemented every year to meet the requirement of recycling, and a large amount of purchasing cost of sulfuric acid is saved.
(5) The utility model discloses technology has obvious advantage in energy saving and consumption reduction aspect, according to public data, several kinds of technology public works consume to such as following the table. Process 1 is prior art 1 of the background section and process 2 is prior art 2 of the background section.
Although the present invention has been described with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (6)
1. A concentration and recycling device for chlorine drying waste acid comprises an acid-acid heat exchanger (2), and is characterized in that a cold side inlet of the acid-acid heat exchanger (2) is connected with a raw material acid elevated tank (1), a cold side outlet of the acid-acid heat exchanger (2) is connected with a feed inlet of a first-stage concentration kettle (3), and a hot side outlet of the acid-acid heat exchanger (2) is connected with a hot side inlet of a finished product acid cooler (14); the liquid phase outlet of the first-stage concentration kettle (3) is connected with the feed inlet of the second-stage concentration kettle (6), the liquid phase outlet of the second-stage concentration kettle (6) is connected with the hot side inlet of the acid-acid heat exchanger (2), the gas phase outlet of the first-stage concentration kettle (3) is directly connected with the defoaming tower (5), the outlet of the defoaming tower (5) is connected with the jet condenser (12), the gas phase outlet of the second-stage concentration kettle (6) is connected with the gas phase inlet of the washing tower (8), and the gas phase outlet of the washing tower (8) is connected with the inlet of the steam jet pump (11);
a primary heater (4) is arranged in the primary concentration kettle (3), and a secondary heater (7) is arranged in the secondary concentration kettle (6).
2. The concentration and recycling device of chlorine gas drying waste acid as claimed in claim 1, wherein the primary heater (4) and the secondary heater (7) both adopt tantalum heaters, and a plurality of baffles are arranged in the tantalum heaters.
3. The apparatus for concentrating and recycling chlorine gas dried waste acid as claimed in claim 1, wherein a concentration condenser (10) is arranged between the gas phase outlet of the washing tower (8) and the inlet of the steam jet pump (11), and the outlet of the concentration condenser (10) is connected with the waste water intermediate tank (17).
4. The concentration and recycling device of chlorine gas drying waste acid as claimed in claim 3, wherein the concentration condenser (10) uses 0 ℃ chilled water as cooling liquid.
5. The apparatus for concentrating and recycling chlorine gas dried waste acid as claimed in claim 1, wherein the outlet of the finished acid cooler (14) is connected to the finished acid intermediate tank (18).
6. The concentration and recycling device for chlorine drying waste acid as claimed in claim 1, wherein the finished product acid cooler (14) and the injection condenser (12) use circulating water as cooling liquid.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114455551A (en) * | 2022-02-11 | 2022-05-10 | 宣达实业集团有限公司 | Concentration and reuse device for chlorine gas drying waste acid and control method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114455551A (en) * | 2022-02-11 | 2022-05-10 | 宣达实业集团有限公司 | Concentration and reuse device for chlorine gas drying waste acid and control method thereof |
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