CN107042060B - Recycling method of ammonia-containing acidic gas - Google Patents
Recycling method of ammonia-containing acidic gas Download PDFInfo
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- CN107042060B CN107042060B CN201710216412.2A CN201710216412A CN107042060B CN 107042060 B CN107042060 B CN 107042060B CN 201710216412 A CN201710216412 A CN 201710216412A CN 107042060 B CN107042060 B CN 107042060B
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Abstract
A resource method of ammonia-containing acidic gas is to utilize ammonium sulfate solution to absorb ammonia in the ammonia-containing acidic gas, the concentration of the ammonium sulfate solution after ammonia absorption reaches 45% -47%, and then evaporation crystallization is carried out under the vacuum state; controlling the growth of crystals by means of external circulation stirring and vacuum evaporation; the heat that the absorption process produced directly transmits the crystallization process, provides the heat for the evaporation crystallization through direct heat transfer, obtains the ammonium sulfate crystal with the evaporation of water, if the ammonia content among the ammoniacal acid gas is on the low side, when the heat that the absorption process provided is not enough to satisfy heat balance, the heat that another part is not enough provides through outside heat source. The invention has no over high temperature, low requirement on equipment material, long service life, short process flow, less investment, small occupied area and low operating cost; the exothermic reaction and the dilution heat of the sulfuric acid are effectively utilized as the heat for evaporating water, so that the requirements of energy conservation and environmental protection are met; can be suitable for the recovery treatment of gas with 5 to 100 percent of ammonia content.
Description
Technical Field
The invention relates to the technical field of industrial waste gas recycling and treatment, in particular to a recycling method of ammonia-containing acid gas.
Background
In the fields of petrochemical industry and coal chemical industry, acid gas generated by an ammonia desulphurization process contains a large amount of hydrogen sulfide and ammonia. For the treatment of acid gas containing ammonia, the Claus sulfur recovery process is mainly adopted to convert hydrogen sulfide in the acid gas into sulfur. There is also a process for producing sulfuric acid by combusting an acid gas to produce sulfur dioxide from hydrogen sulfide, which is ultimately converted to sulfur trioxide. In both methods, ammonia in the acid gas is combusted at high temperature to produce nitrogen and water, and also contains a small amount of nitrogen oxides. The process for decomposing ammonia through combustion firstly causes waste of ammonia resources and secondly can possibly cause the excessive emission of nitrogen oxides in the final tail gas.
At present, the treatment method of the ammonia-containing gas is mainly by an absorption method. Mainly uses water or dilute acid solution (sulfuric acid, phosphoric acid or hydrochloric acid) to absorb ammonia-containing gas and make it convert into ammonia water and ammonium salt (ammonium sulfate and ammonium chloride). For example, in the coke oven gas purification technology in the coking industry, ammonia is finally generated by absorbing ammonia with water or phosphoric acid solution. Due to the limitation of the application of the ammonia water, most coking enterprises adopt sulfuric acid solution to absorb ammonia to generate ammonium sulfate. Ammonium sulfate is an important agricultural fertilizer. The method for producing ammonium sulfate by adopting ammonia in coke oven gas realizes the resource and comprehensive utilization of ammonia and has better economic benefit.
The above ammonia recovery method generally separates absorption and crystallization into two separate processes. Most of the heat released in the absorption process is taken out by the absorbed gas, the heat required in the crystallization process is provided by an external heat source, and the whole method is only suitable for the gas with low ammonia concentration. If the gas with higher ammonia concentration is treated by the same method, more heat is released in the absorption process, the temperature of an absorption system is higher, and the requirement on equipment materials is correspondingly increased in order to avoid equipment corrosion. Meanwhile, when the gas with higher ammonia concentration is treated, a heat exchanger needs to be added in an absorption system to transfer the heat to a crystallization system indirectly so as to realize the full utilization of the heat, thereby increasing the equipment investment and the operating cost.
Disclosure of Invention
The invention aims to provide a recycling method of ammonia-containing acidic gas, which is a method for treating the acidic gas with higher ammonia content.
In order to achieve the purpose, the invention adopts the following technical scheme:
a resource method of ammonia-containing acidic gas is to utilize sulfuric acid-ammonium sulfate solution to absorb ammonia in the ammonia-containing acidic gas, the concentration of the ammonium sulfate solution after ammonia absorption reaches 45% -47%, and then evaporation crystallization is carried out in a vacuum state; absorption and crystallization process combine together to through the growth of extrinsic cycle stirring with the mode control crystallization of vacuum evaporation, control entire system's temperature not more than 65 ℃ simultaneously, the heat that the absorption process produced directly transmits the crystallization process, provides the heat for the evaporation crystallization through direct heat transfer, obtains the ammonium sulfate crystal with water evaporation, if the ammonia content in the sour gas of containing ammonia is on the low side, when the heat that the absorption process provided is not enough to satisfy heat balance, another part heat that is not enough provides through outside heat source.
The method for absorbing ammonia in ammonia-containing acid gas by using the ammonium sulfate solution comprises the following specific steps:
1) The ammonia-containing acid gas firstly enters an upper absorption section of the absorption crystallizer and contacts with a circulating ammonium sulfate solution of the upper absorption section, ammonia in the ammonia-containing acid gas is absorbed by sulfuric acid in the ammonium sulfate solution to generate ammonium sulfate, the deaminated acid gas is combined into one strand along the rear side of an annular absorption chamber, and after being continuously sprayed and washed by the ammonium sulfate solution, the deaminated acid gas enters a cyclone demister in the annular absorption chamber along the tangential direction, and after mist drops carried by the acid gas are separated, the acid gas is discharged to a downstream user from the top of the absorption crystallizer;
2) The ammonium sulfate solution for absorbing ammonia overflows from the upper absorption section of the absorption crystallizer, flows into a guide cylinder of the lower crystallization section of the absorption crystallizer after passing through the liquid seal of an external upper section liquid seal tank, and the reaction heat and the sulfuric acid dilution heat in the absorption process are also brought into the lower crystallization section of the absorption crystallizer along with the ammonium sulfate solution for absorbing ammonia;
3) In a lower crystallization section of the absorption crystallizer, ammonium sulfate solution is pumped out from the upper liquid level through a stirring pump and is conveyed to the upper part of a guide cylinder through a heater, and the ammonium sulfate solution flows to the bottom of the absorption crystallizer from top to bottom in the guide cylinder and then flows upwards to the upper part of the liquid level, so that a flow field for growth of ammonium sulfate crystals is formed, and flow field distribution is controlled through the flow of the stirring pump;
4) After the ammonium sulfate solution in the lower crystallization section of the absorption crystallizer overflows into a lower liquid seal tank for liquid seal, pumping the ammonium sulfate solution by using a small circulating pump and then sending the ammonium sulfate solution to the upper absorption section of the absorption crystallizer for spraying and washing;
5) Pumping ammonium sulfate solution from the upper part of the lower crystallization section of the absorption crystallizer by a large circulating pump, and conveying the ammonium sulfate solution to the upper absorption section of the absorption crystallizer for spraying and washing;
6) Adding sulfuric acid to maintain the acid balance of the whole system at the liquid seal tank 3;
7) Vacuum evaporation is carried out in the lower crystallization section of the absorption crystallizer, the vacuum evaporation process is carried out by using a vacuum pump for vacuum pumping, the liquid level temperature in the vacuum evaporation process is controlled to be 40-65 ℃, and the pressure is maintained to be 7.4-25kPa; the water vapor at the top of the liquid surface of the crystallization section at the lower part of the absorption crystallizer is firstly removed with entrained fog drops through a mist catcher, then enters a condenser to condense the water vapor into condensed water and returns to a system or is partially discharged, and finally the non-condensable gas from the condenser is pumped to an ammonia-containing acid gas inlet pipeline through a vacuum pump;
8) The ammonium sulfate solution is circularly concentrated in the above process, so that ammonium sulfate crystal particles continuously grow up to finally obtain ammonium sulfate particles with the particle size of about 500-1500 mu m, the grown ammonium sulfate crystals are deposited at the bottom of the absorption crystallizer and pumped to an ammonium sulfate crystallization separation drying system by a crystallization pump, and finally an ammonium sulfate product is obtained.
The absorption crystallizer comprises an upper absorption section and a lower crystallization section, the upper absorption section and the lower crystallization section are mutually sealed and isolated, an annular absorption chamber is arranged at the top of the upper absorption section, a cyclone demister is arranged in the annular absorption chamber, and a spraying device is arranged and is respectively connected with a small circulating pump and a large circulating pump; the small circulating pump is connected with a lower section liquid seal tank which is communicated with an ammonium sulfate solution overflow port of the lower crystallization section; the large circulation pump is directly connected with the lower crystallization section, and the connection position of the large circulation pump is arranged below the overflow port of the ammonium sulfate solution; an ammonium sulfate solution overflow port of the upper absorption section is communicated with an upper section liquid seal groove, and the upper section liquid seal groove is communicated with a guide cylinder of the lower crystallization section; the lower section liquid seal tank is also provided with a sulfuric acid replenishing pipeline;
the guide cylinder is arranged in the lower end crystallization section and is directly communicated with the bottom of the lower end crystallization section, a communicating port connected with a stirring pump is further arranged below an ammonium sulfate solution overflow port of the lower end crystallization section, the stirring pump is connected with a heater, and the heater is connected with the guide cylinder;
the lower end of the lower end crystallization section is provided with a communication port connected with a crystallization pump;
a communicating port connected with a mist catcher is arranged above the overflow port of the ammonium sulfate solution at the lower end crystallization section, the mist catcher is connected with a condenser, and the condenser is connected with a vacuum pump.
The method for absorbing ammonia in ammonia-containing acid gas by using the ammonium sulfate solution comprises the following specific steps:
1) The ammonia-containing acidic gas firstly enters an upper absorption section of the absorption crystallizer 1 and is in countercurrent contact with a spraying liquid of a circulating ammonium sulfate solution, ammonia in the ammonia-containing acidic gas is absorbed by sulfuric acid in the ammonium sulfate solution to generate ammonium sulfate, and the deaminated acidic gas passes through a cyclone separator or a mist catching device at the upper part, separates out mist drops carried by the acidic gas and then is discharged to downstream users from the top of the absorption crystallizer 1;
2) The upper absorption section of the absorption crystallizer 1 is communicated with the guide shell of the lower crystallization section, the ammonium sulfate solution for absorbing ammonia automatically flows into the guide shell of the lower crystallization section from the upper absorption section of the absorption crystallizer 1, and the reaction heat and the sulfuric acid dilution heat in the absorption process are carried into the lower crystallization section of the absorption crystallizer 1 along with the ammonium sulfate solution for absorbing ammonia;
3) In a lower crystallization section of the absorption crystallizer, ammonium sulfate solution is pumped out from the upper liquid level through a stirring pump and is conveyed to the upper part of a guide cylinder through a heater, and the ammonium sulfate solution flows to the bottom of the absorption crystallizer from top to bottom in the guide cylinder and then flows upwards to the upper part of the liquid level, so that a flow field for growth of ammonium sulfate crystals is formed, and flow field distribution is controlled through the flow of the stirring pump;
4) After overflowing the ammonium sulfate solution in the lower crystallization section of the absorption crystallizer, entering a lower section liquid seal tank for liquid seal, pumping the solution by a small circulating pump, and then conveying the solution to the upper absorption section of the absorption crystallizer for spraying and washing;
5) The large circulating pump pumps out ammonium sulfate solution from the upper part of the lower crystallization section of the absorption crystallizer and sends the ammonium sulfate solution to the upper absorption section of the absorption crystallizer for spraying and washing;
6) Adding sulfuric acid to maintain the acid balance of the whole system at the liquid seal tank 3;
7) Vacuum evaporation is carried out in the lower crystallization section of the absorption crystallizer, the vacuum evaporation process is carried out by using a vacuum pump for vacuum pumping, the liquid level temperature in the vacuum evaporation process is controlled to be 40-65 ℃, and the pressure is maintained to be 7.4-25kPa; the method comprises the following steps that firstly, vapor at the top of the liquid surface of a crystallization section at the lower part of an absorption crystallizer is subjected to mist drop removal through a mist catcher, then the vapor enters a condenser to be condensed into condensed water to be returned to a system or partially discharged, and finally non-condensable gas discharged from the condenser is conveyed to an ammonia-containing acid gas inlet pipeline through a vacuum pump;
8) The ammonium sulfate solution is circularly concentrated in the above process to continuously grow ammonium sulfate crystal particles to finally obtain ammonium sulfate particles with the particle size of about 500-1500 mu m, the grown ammonium sulfate crystals are deposited at the bottom of the absorption crystallizer and pumped to an ammonium sulfate crystal separation drying system by a crystallization pump to finally obtain an ammonium sulfate product.
The absorption crystallizer comprises an upper absorption section and a lower crystallization section, the upper absorption section is communicated with a guide cylinder in the lower crystallization section, a cyclone separator or a mist catching device is arranged at the top of the upper absorption section, and a spraying device is arranged and is respectively connected with a small circulating pump and a large circulating pump; the small circulating pump is connected with a lower section liquid seal tank which is communicated with an ammonium sulfate solution overflow port of the lower crystallization section; the large circulation pump is directly connected with the lower crystallization section, and the connection position of the large circulation pump is arranged below the overflow port of the ammonium sulfate solution; the lower section liquid seal tank is also provided with a sulfuric acid replenishing pipeline;
the guide flow cylinder is arranged in the lower end crystallization section and is directly communicated with the bottom of the lower end crystallization section, a communication port connected with a stirring pump is also arranged below an ammonium sulfate solution overflow port of the lower end crystallization section, the stirring pump is connected with a heater, and the heater is connected with the guide flow cylinder;
the lower end of the lower end crystallization section is provided with a communication port connected with a crystallization pump;
a communicating port connected with a mist catcher is arranged above the overflow port of the ammonium sulfate solution at the lower end crystallization section, the mist catcher is connected with a condenser, and the condenser is connected with a vacuum pump.
Compared with the prior art, the invention has the beneficial effects that:
1) The recycling method of ammonia-containing acid gas has the advantages of no overhigh temperature, low requirement on equipment materials, difficult damage in the using process, long service life, short process flow, less investment, small occupied area, low operating cost and safe and reliable operation, and the temperature of the whole system is controlled below 65 ℃.
2) The invention effectively utilizes the exothermic reaction and the dilution heat of the sulfuric acid as the heat for evaporating water, does not need excessive supplementary heat, and better meets the requirements of energy conservation and environmental protection.
3) The device for recycling the ammonia-containing acidic gas has the advantages that the absorption and crystallization processes are completed in one device, and the integration is high.
4) The invention can effectively utilize ammonia in the ammonia-containing acidic gas, and finally generate an ammonium sulfate crystallization product so as to achieve the recycling of ammonia resources, and can be suitable for the recycling treatment of gas with 5-100% of ammonia content.
Drawings
FIG. 1 is a process flow diagram of example 1 of the present invention.
FIG. 2 is a flow diagram of the ammonia-containing acidic gas in the annular absorption chamber in example 1.
FIG. 3 is a process flow diagram of example 2 of the present invention.
In the figure: 1. an absorption crystallizer; 2. an upper section liquid seal groove; 3. a lower section liquid seal tank; 4. a small circulation pump; 5. a stirring pump; 6. a vacuum pump; 7. a large circulation pump; 8. a crystallization pump; 9. a heater; 10. a condenser; 11. a mist catcher; 12. an upper absorption section; 13. a draft tube; 14. a lower crystallization section; 15-a cyclone demister; 16-annular absorption chamber.
Detailed Description
The following further describes embodiments of the present invention in conjunction with the attached figures:
the invention relates to a resource method of ammonia-containing acidic gas, which is characterized in that a sulfuric acid-ammonium sulfate solution is used for absorbing ammonia in the ammonia-containing acidic gas, the concentration of the ammonium sulfate solution after ammonia absorption reaches 45-47%, and then evaporation crystallization is carried out in a vacuum state; absorption and crystallization process combine together to through the growth of extrinsic cycle stirring and vacuum evaporation's mode control crystallization, control entire system's temperature not more than 65 ℃ simultaneously, the heat that the absorption process produced directly transmits to the crystallization process, provides the heat for evaporation crystallization through direct heat transfer, obtains the ammonium sulfate crystal with moisture evaporation, if the ammonia content in the ammoniacal acid gas is on the low side, when the heat that the absorption process provided is not enough to satisfy heat balance, another part insufficient heat was provided through outside heat source.
Example 1:
referring to fig. 1, the method for absorbing ammonia in ammonia-containing acid gas by using ammonium sulfate solution comprises the following specific steps:
1) The ammonia-containing acid gas firstly enters an upper absorption section 12 of the absorption crystallizer 1 and contacts with a circulating ammonium sulfate solution of the upper absorption section 12, ammonia in the ammonia-containing acid gas is absorbed by sulfuric acid in the ammonium sulfate solution to generate ammonium sulfate, the deaminated acid gas is combined into a strand along the rear side of an annular absorption chamber 16, the ammonia-containing acid gas continuously sprays and washes the ammonium sulfate solution and then enters a cyclone demister 15 (shown in figure 2) in the absorption annular absorption chamber 16 along the tangential direction, and mist droplets carried by the acid gas are separated and then discharged to downstream users from the top of the absorption crystallizer 1;
2) The ammonium sulfate solution for absorbing ammonia overflows from the upper absorption section 12 of the absorption crystallizer 1, flows into a guide shell 13 of a lower crystallization section 14 of the absorption crystallizer 1 after being subjected to liquid seal by an external upper-section liquid seal tank 2, and the reaction heat and the sulfuric acid dilution heat in the absorption process are also brought into the lower crystallization section 14 of the absorption crystallizer 1 along with the ammonium sulfate solution for absorbing ammonia;
3) In a lower crystallization section 14 of the absorption crystallizer 1, ammonium sulfate solution is pumped out from the upper liquid level through a stirring pump 5 and is sent to the upper part of a guide cylinder 13 through a heater 9, the ammonium sulfate solution flows to the bottom of the absorption crystallizer 1 from top to bottom in the guide cylinder 13 and then flows upwards to the upper part of the liquid level, so that a flow field for growth of ammonium sulfate crystals is formed, and the flow field distribution is controlled through the flow of the stirring pump 5;
4) After the ammonium sulfate solution in the lower crystallization section 14 of the absorption crystallizer 1 overflows into the lower liquid seal tank 3 for liquid seal, pumping the ammonium sulfate solution by using a small circulating pump 4 and then sending the ammonium sulfate solution to the upper absorption section 12 of the absorption crystallizer 1 for spraying and washing;
5) The large circulating pump 7 draws the ammonium sulfate solution from the upper part of the lower crystallization section 14 of the absorption crystallizer 1 and sends the ammonium sulfate solution to the upper absorption section 12 of the absorption crystallizer 1 for spraying and washing;
6) Adding sulfuric acid to maintain the acid balance of the whole system at the liquid seal tank 3;
7) Vacuum evaporation is carried out in a lower crystallization section 14 of the absorption crystallizer 1, the vacuum evaporation process is vacuum-pumped by a vacuum pump 6, the liquid level temperature in the vacuum evaporation process is controlled to be 40-65 ℃, and the pressure is maintained to be 7.4-25kPa (a); the method comprises the following steps that water vapor at the top of the liquid surface of a crystallization section 14 at the lower part of an absorption crystallizer 1 is subjected to entrained fog drop removal through a mist catcher 11, then enters a condenser 10 to be condensed into condensed water to be returned to a system or partially discharged, and finally non-condensable gas discharged from the condenser 10 is sent to an ammonia-containing acid gas inlet pipeline through a vacuum pump 6;
8) The ammonium sulfate solution is circularly concentrated in the process, so that ammonium sulfate crystal particles continuously grow up to finally obtain ammonium sulfate particles with the particle size of about 500-1500 mu m, the grown ammonium sulfate crystals are deposited at the bottom of the absorption crystallizer 1 and pumped to an ammonium sulfate crystallization separation drying system by a crystallization pump 8, and finally an ammonium sulfate product is obtained.
The absorption crystallizer 1 comprises an upper absorption section 12 and a lower crystallization section 14, the upper absorption section 12 and the lower crystallization section 14 are mutually sealed and isolated, an annular absorption chamber 16 is arranged at the top of the upper absorption section 12, a cyclone demister 15 is arranged in the annular absorption chamber 16, and a spraying device is arranged and is respectively connected with a small circulating pump 4 and a large circulating pump 7; the small circulating pump 4 is connected with the lower section liquid seal tank 3, and the lower section liquid seal tank 3 is communicated with an ammonium sulfate solution overflow port of the lower crystallization section 14; the large circulating pump 7 is directly connected with the lower crystallization section 14, and the connection position of the large circulating pump is arranged below the overflow port of the ammonium sulfate solution; an overflow port of the ammonium sulfate solution of the upper absorption section 14 is communicated with the upper section liquid seal groove 2, and the upper section liquid seal groove 2 is communicated with a guide cylinder 13 of the lower crystallization section 14; the lower section liquid seal tank 3 is also provided with a sulfuric acid supplementing pipeline;
the guide flow cylinder 13 is arranged in the lower end crystallization section 14 and is directly communicated with the bottom of the lower end crystallization section 14, a communication port connected with the stirring pump 5 is also arranged below an ammonium sulfate solution overflow port of the lower end crystallization section 14, the stirring pump 5 is connected with the heater 9, and the heater 9 is connected with the guide flow cylinder 13;
the lower end of the lower end crystallization section 14 is provided with a communication port connected with the crystallization pump 8;
a communicating port connected with a mist catcher 11 is arranged above an overflow port of the ammonium sulfate solution in the lower end crystallization section 14, the mist catcher 11 is connected with a condenser 10, and the condenser 10 is connected with a vacuum pump 6.
The device adopts vacuum evaporation, and in order to prevent acid gas from entering the lower crystallization section 14 of the absorption crystallizer 1, the liquid level of the lower crystallization section of the absorption crystallizer 1 needs to be about 15m higher than the ground, and the lower liquid seal tank 3 can be placed in a pit when the equipment is arranged.
Example 2:
referring to fig. 3, the method for absorbing ammonia in ammonia-containing acidic gas by using ammonium sulfate solution includes the following specific steps:
1) The ammonia-containing acid gas firstly enters an upper absorption section 12 of the absorption crystallizer 1 and is in countercurrent contact with a spraying liquid of a circulating ammonium sulfate solution, ammonia in the ammonia-containing acid gas is absorbed by sulfuric acid in the ammonium sulfate solution to generate ammonium sulfate, the deaminated acid gas passes through a cyclone separator or a mist catching device (a cyclone mist eliminator 15 is adopted in the embodiment) at the upper part, and mist drops carried by the acid gas are separated out and then discharged to a downstream user from the top of the absorption crystallizer 1;
2) The upper absorption section 12 of the absorption crystallizer 1 is communicated with the guide shell 13 of the lower crystallization section 14, the ammonium sulfate solution for absorbing ammonia flows into the guide shell 13 of the lower crystallization section 14 from the upper absorption section 12 of the absorption crystallizer 1, and the reaction heat and the sulfuric acid dilution heat in the absorption process are carried into the lower crystallization section 14 of the absorption crystallizer 1 along with the ammonium sulfate solution for absorbing ammonia;
3) In a lower crystallization section 14 of the absorption crystallizer 1, ammonium sulfate solution is pumped out from the upper liquid level through a stirring pump 5 and is sent to the upper part of a guide cylinder 13 through a heater 9, and the ammonium sulfate solution flows to the bottom of the absorption crystallizer 1 from top to bottom in the guide cylinder 13 and then flows upwards to the upper part of the liquid level, so that a flow field for growth of ammonium sulfate crystals is formed;
4) The ammonium sulfate solution in the lower crystallization section 14 of the absorption crystallizer 1 overflows into a lower liquid seal tank 3 for liquid seal, and is pumped out by a small circulating pump 4 and then is sent to the upper absorption section 12 of the absorption crystallizer 1 for spraying and washing;
5) The large circulating pump 7 draws ammonium sulfate solution from the upper part of the lower crystallization section 14 of the absorption crystallizer 1 and sends the ammonium sulfate solution to the upper absorption section 12 of the absorption crystallizer 1 for spraying and washing;
6) Adding sulfuric acid to maintain the acid balance of the whole system at the liquid seal tank 3;
7) Vacuum evaporation is carried out in a lower crystallization section 14 of the absorption crystallizer 1, the vacuum evaporation process is vacuum-pumped by a vacuum pump 6, the liquid level temperature in the vacuum evaporation process is controlled to be 40-65 ℃, and the pressure is maintained to be 7.4-25kPa (a); the method comprises the following steps that water vapor at the top of the liquid surface of a crystallization section 14 at the lower part of an absorption crystallizer 1 is subjected to entrained fog drop removal through a mist catcher 11, then enters a condenser 10 to be condensed into condensed water to be returned to a system or partially discharged, and finally non-condensable gas discharged from the condenser 10 is sent to an ammonia-containing acid gas inlet pipeline through a vacuum pump 6;
8) The ammonium sulfate solution is circularly concentrated in the process, so that ammonium sulfate crystal particles continuously grow up to finally obtain ammonium sulfate particles with the particle size of about 500-1500 mu m, the grown ammonium sulfate crystals are deposited at the bottom of the absorption crystallizer 1 and pumped to an ammonium sulfate crystallization separation drying system by a crystallization pump 8, and finally an ammonium sulfate product is obtained.
The absorption crystallizer 1 comprises an upper absorption section 12 and a lower crystallization section 14, wherein the upper absorption section 12 is communicated with a guide cylinder 13 in the lower crystallization section 14, the top of the upper absorption section 14 is provided with a cyclone demister 15 (cyclone separator or mist catching device), and a spraying device is simultaneously connected with a small circulating pump 4 and a large circulating pump 7 respectively; the small circulating pump 4 is connected with the lower section liquid seal tank 3, and the lower section liquid seal tank 3 is communicated with an ammonium sulfate solution overflow port of the lower crystallization section 14; the large circulating pump 7 is directly connected with the lower crystallization section 14, and the connection position of the large circulating pump is arranged below the overflow port of the ammonium sulfate solution; the lower section liquid seal tank 3 is also provided with a sulfuric acid supplementing pipeline;
the guide flow cylinder 13 is arranged in the lower end crystallization section 14 and is directly communicated with the bottom of the lower end crystallization section 14, a communication port connected with the stirring pump 5 is also arranged below an ammonium sulfate solution overflow port of the lower end crystallization section 14, the stirring pump 5 is connected with the heater 9, and the heater 9 is connected with the guide flow cylinder 13;
the lower end of the lower end crystallization section 14 is provided with a communication port connected with the crystallization pump 8;
a communicating port connected with a mist catcher 11 is arranged above an overflow port of the ammonium sulfate solution in the lower end crystallization section 14, the mist catcher 11 is connected with a condenser 10, and the condenser 10 is connected with a vacuum pump 6.
The device adopts vacuum evaporation, and in order to prevent acid gas from entering the lower crystallization section of the absorption crystallizer 1, the liquid level of the lower crystallization section of the absorption crystallizer 1 needs to be about 15m higher than the ground.
The operating temperature of vacuum crystallization is 40-65 ℃, in step 3 of the embodiment of the invention, if the ammonia content in the ammonia-containing acid gas is high and the heat provided in the absorption process can meet the requirement of evaporative crystallization, the heater 9 does not heat. When the heat provided by the absorption process can not meet the requirement of evaporative crystallization, the heater 9 provides heat to heat the ammonium sulfate solution, so that the superfine crystal particles are eliminated, and meanwhile, heat is provided for the evaporative crystallization process.
The crystallization system of the invention achieves the stirring effect through external circulation, the circulating ammonium sulfate solution is pumped out from the upper part of the liquid level of the crystallization system by using the stirring pump 5 and is sent into the upper part of the guide cylinder 13 in the crystallization system, and the guide cylinder 13 extends into the bottom of the crystallization system from top to bottom, so that the ammonium sulfate solution in the crystallization system is fully disturbed and mixed. The possibility of system leakage due to the use of the stirrer is reduced.
Meanwhile, the invention arranges an ammonium sulfate solution washing (spraying device) at the inlet of the whole system to achieve the functions of pre-washing and cooling. The acid gas is provided with a cyclone separator or a mist catching device at the outlet of the whole system to catch the mist drops carried by the acid gas in the absorption process.
In the evaporative crystallization process, vacuum is pumped by a vacuum pump 6 in a crystallization system, and evaporated water vapor in the crystallization system is condensed into water to be discharged outside or used as system water supplement to maintain the water balance of the system before the vacuum pump 6. The non-condensable gas of the system at the outlet of the vacuum pump 6 returns to the acid gas inlet and is discharged out of the whole system along with the absorption process.
In the two embodiments of the invention, both absorption and crystallization integrated equipment are adopted, the absorption section and the crystallization section can be separated into two independent equipment according to actual requirements, and the recycling method of the ammonia-containing acid gas can also be realized.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (4)
1. A resource method of ammonia-containing acidic gas is characterized in that ammonia in the ammonia-containing acidic gas is absorbed by using sulfuric acid-ammonium sulfate solution, the concentration of the ammonium sulfate solution after ammonia absorption reaches 45% -47%, and then evaporation crystallization is carried out under a vacuum state; the absorption and crystallization processes are integrated, the growth of crystals is controlled in a mode of external circulation stirring and vacuum evaporation, the temperature of the whole system is controlled to be not higher than 65 ℃, heat generated in the absorption process is directly transferred to the crystallization process, heat is provided for evaporation crystallization through direct heat exchange, water is evaporated to obtain ammonium sulfate crystals, and if the content of ammonia in ammonia-containing acid gas is low, the heat provided in the absorption process is not enough to meet heat balance, the other part of insufficient heat is provided through an external heat source;
the method comprises the following specific steps:
1) The ammonia-containing acidic gas firstly enters an upper absorption section of the absorption crystallizer and contacts with a circulating ammonium sulfate solution of the upper absorption section, ammonia in the ammonia is absorbed by sulfuric acid in the ammonium sulfate solution to generate ammonium sulfate, the deaminated acidic gas is combined into one strand along the rear side of an annular absorption chamber, and after being continuously sprayed and washed by the ammonium sulfate solution, the deaminated acidic gas enters a cyclone demister in the annular absorption chamber along the tangential direction, and is discharged to downstream users from the top of the absorption crystallizer after fog drops carried by the acidic gas are separated;
2) The ammonium sulfate solution for absorbing ammonia overflows from the upper absorption section of the absorption crystallizer, flows into a guide cylinder of the lower crystallization section of the absorption crystallizer after passing through the liquid seal of an external upper section liquid seal tank, and the reaction heat and the sulfuric acid dilution heat in the absorption process are also brought into the lower crystallization section of the absorption crystallizer along with the ammonium sulfate solution for absorbing ammonia;
3) In a lower crystallization section of the absorption crystallizer, ammonium sulfate solution is pumped out from the upper liquid level through a stirring pump and is conveyed to the upper part of a guide cylinder through a heater, and the ammonium sulfate solution flows to the bottom of the absorption crystallizer from top to bottom in the guide cylinder and then flows upwards to the upper part of the liquid level, so that a flow field for growth of ammonium sulfate crystals is formed, and flow field distribution is controlled through the flow of the stirring pump;
4) After the ammonium sulfate solution in the lower crystallization section of the absorption crystallizer overflows into a lower liquid seal tank for liquid seal, pumping the ammonium sulfate solution by using a small circulating pump and then conveying the ammonium sulfate solution to the upper absorption section of the absorption crystallizer for spraying and washing;
5) The large circulating pump pumps out ammonium sulfate solution from the upper part of the lower crystallization section of the absorption crystallizer and sends the ammonium sulfate solution to the upper absorption section of the absorption crystallizer for spraying and washing;
6) Adding sulfuric acid to maintain the acid balance of the whole system at the liquid seal tank 3;
7) Vacuum evaporation is carried out in the lower crystallization section of the absorption crystallizer, the vacuum evaporation process is carried out by using a vacuum pump for vacuum pumping, the liquid level temperature in the vacuum evaporation process is controlled to be 40-65 ℃, and the pressure is maintained to be 7.4-25kPa; the method comprises the following steps that firstly, vapor at the top of the liquid surface of a crystallization section at the lower part of an absorption crystallizer is subjected to mist drop removal through a mist catcher, then the vapor enters a condenser to be condensed into condensed water to be returned to a system or partially discharged, and finally non-condensable gas discharged from the condenser is conveyed to an ammonia-containing acid gas inlet pipeline through a vacuum pump;
8) The ammonium sulfate solution is circularly concentrated in the process, so that ammonium sulfate crystal particles grow continuously to finally obtain ammonium sulfate particles of 500-1500 mu m, the grown ammonium sulfate crystals are deposited at the bottom of the absorption crystallizer, and pumped to an ammonium sulfate crystal separation drying system by a crystallizing pump to finally obtain an ammonium sulfate product.
2. A resource method of ammonia-containing acid gas according to claim 1, characterized in that the absorption crystallizer comprises an upper absorption section and a lower crystallization section, the upper absorption section and the lower crystallization section are mutually sealed and isolated, an annular absorption chamber is arranged at the top of the upper absorption section, a cyclone demister is arranged in the annular absorption chamber, and a spraying device is arranged to be respectively connected with a small circulation pump and a large circulation pump; the small circulating pump is connected with a lower section liquid seal tank which is communicated with an ammonium sulfate solution overflow port of the lower crystallization section; the large circulation pump is directly connected with the lower crystallization section, and the connection position of the large circulation pump is arranged below the overflow port of the ammonium sulfate solution; an ammonium sulfate solution overflow port of the upper absorption section is communicated with an upper section liquid seal groove, and the upper section liquid seal groove is communicated with a guide cylinder of the lower crystallization section; the lower section liquid seal tank is also provided with a sulfuric acid replenishing pipeline;
the guide cylinder is arranged in the lower end crystallization section and is directly communicated with the bottom of the lower end crystallization section, a communicating port connected with a stirring pump is further arranged below an ammonium sulfate solution overflow port of the lower end crystallization section, the stirring pump is connected with a heater, and the heater is connected with the guide cylinder;
the lower end of the lower end crystallization section is provided with a communication port connected with a crystallization pump;
a communicating port connected with a mist catcher is arranged above the overflow port of the ammonium sulfate solution at the lower end crystallization section, the mist catcher is connected with a condenser, and the condenser is connected with a vacuum pump.
3. A resource method of ammonia-containing acidic gas is characterized in that ammonia in the ammonia-containing acidic gas is absorbed by using sulfuric acid-ammonium sulfate solution, the concentration of the ammonium sulfate solution after ammonia absorption reaches 45% -47%, and then evaporation crystallization is carried out under a vacuum state; the absorption and crystallization processes are integrated, the growth of crystals is controlled by means of external circulation stirring and vacuum evaporation, the temperature of the whole system is controlled to be not higher than 65 ℃, heat generated in the absorption process is directly transferred to the crystallization process, heat is provided for evaporation crystallization through direct heat exchange, water is evaporated to obtain ammonium sulfate crystals, and if the content of ammonia in ammonia-containing acid gas is low and the heat provided in the absorption process is insufficient to meet heat balance, the other part of insufficient heat is provided through an external heat source;
the method comprises the following specific steps:
1) The ammonia-containing acid gas firstly enters an upper absorption section of the absorption crystallizer 1 and is in countercurrent contact with a spraying liquid of a circulating ammonium sulfate solution, ammonia in the ammonia-containing acid gas is absorbed by sulfuric acid in the ammonium sulfate solution to generate ammonium sulfate, and the deaminated acid gas passes through a cyclone separator or a mist catching device at the upper part, separates out mist drops carried by the acid gas and then is discharged to a downstream user from the top of the absorption crystallizer 1;
2) The upper absorption section of the absorption crystallizer 1 is communicated with the guide cylinder of the lower crystallization section, the ammonium sulfate solution for absorbing ammonia automatically flows into the guide cylinder of the lower crystallization section from the upper absorption section of the absorption crystallizer 1, and the reaction heat and the sulfuric acid dilution heat in the absorption process are also brought into the lower crystallization section of the absorption crystallizer 1 along with the ammonium sulfate solution for absorbing ammonia;
3) In a lower crystallization section of the absorption crystallizer, ammonium sulfate solution is pumped out from the upper liquid level through a stirring pump and is conveyed to the upper part of a guide cylinder through a heater, and the ammonium sulfate solution flows to the bottom of the absorption crystallizer from top to bottom in the guide cylinder and then flows upwards to the upper part of the liquid level, so that a flow field for growth of ammonium sulfate crystals is formed, and flow field distribution is controlled through the flow of the stirring pump;
4) After overflowing the ammonium sulfate solution in the lower crystallization section of the absorption crystallizer, entering a lower section liquid seal tank for liquid seal, pumping the solution by a small circulating pump, and then conveying the solution to the upper absorption section of the absorption crystallizer for spraying and washing;
5) The large circulating pump pumps out ammonium sulfate solution from the upper part of the lower crystallization section of the absorption crystallizer and sends the ammonium sulfate solution to the upper absorption section of the absorption crystallizer for spraying and washing;
6) Adding sulfuric acid to maintain the acid balance of the whole system at the liquid seal tank 3;
7) Vacuum evaporation is carried out in the lower crystallization section of the absorption crystallizer, the vacuum evaporation process is carried out by using a vacuum pump for vacuum pumping, the liquid level temperature in the vacuum evaporation process is controlled to be 40-65 ℃, and the pressure is maintained to be 7.4-25kPa; the method comprises the following steps that firstly, vapor at the top of the liquid surface of a crystallization section at the lower part of an absorption crystallizer is subjected to mist drop removal through a mist catcher, then the vapor enters a condenser to be condensed into condensed water to be returned to a system or partially discharged, and finally non-condensable gas discharged from the condenser is conveyed to an ammonia-containing acid gas inlet pipeline through a vacuum pump;
8) The ammonium sulfate solution is circularly concentrated in the above process, so that ammonium sulfate crystal particles continuously grow up to finally obtain ammonium sulfate particles of 500-1500 mu m, the grown ammonium sulfate crystals are deposited at the bottom of the absorption crystallizer and pumped to an ammonium sulfate crystal separation drying system by a crystallization pump, and finally an ammonium sulfate product is obtained.
4. A resource method of ammonia-containing acid gas as claimed in claim 3, wherein the absorption crystallizer comprises an upper absorption section and a lower crystallization section, the upper absorption section is communicated with a guide shell in the lower crystallization section, a cyclone separator or a mist catching device is arranged at the top of the upper absorption section, and a spraying device is arranged and connected with a small circulating pump and a large circulating pump respectively; the small circulating pump is connected with a lower section liquid seal tank which is communicated with an ammonium sulfate solution overflow port of the lower crystallization section; the large circulation pump is directly connected with the lower crystallization section, and the connection position of the large circulation pump is arranged below the overflow port of the ammonium sulfate solution; the lower section liquid seal tank is also provided with a sulfuric acid supplementing pipeline;
the guide flow cylinder is arranged in the lower end crystallization section and is directly communicated with the bottom of the lower end crystallization section, a communication port connected with a stirring pump is also arranged below an ammonium sulfate solution overflow port of the lower end crystallization section, the stirring pump is connected with a heater, and the heater is connected with the guide flow cylinder;
the lower end of the lower end crystallization section is provided with a communication port connected with a crystallization pump;
a communicating port connected with a mist catcher is arranged above the overflow port of the ammonium sulfate solution at the lower end crystallization section, the mist catcher is connected with a condenser, and the condenser is connected with a vacuum pump.
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| CN1143535A (en) * | 1995-08-22 | 1997-02-26 | 东洋工程株式会社 | Exhaust gas desulfurization process |
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