CN103920365A - Method for recycling nitrogen gas and sulfur dioxide from calcining iron pyrite burner gas through variable-voltage variable-frequency adsorption - Google Patents

Method for recycling nitrogen gas and sulfur dioxide from calcining iron pyrite burner gas through variable-voltage variable-frequency adsorption Download PDF

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CN103920365A
CN103920365A CN201410160445.6A CN201410160445A CN103920365A CN 103920365 A CN103920365 A CN 103920365A CN 201410160445 A CN201410160445 A CN 201410160445A CN 103920365 A CN103920365 A CN 103920365A
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sulfur dioxide
gas
furnace gas
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adsorbent
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CN103920365B (en
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卢朝霞
黄福川
司亚楠
毛汉领
曹传东
陈彪
卢誉远
黄伊琳
刘宇恒
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Guangxi University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals

Abstract

The invention discloses a method for recycling nitrogen gas and sulfur dioxide from calcining iron pyrite burner gas through variable-voltage variable-frequency adsorption. The method comprises the following steps: dedusting, purifying, drying and cooling the calcining iron pyrite burner gas, and removing dust particles and rust by a refining sulfuric acid burner gas filter made of a 200-mesh polytetrafluoroethylene material; deeply dehydrating by a refining dehydrating tank in a refining manner, deoxidizing and removing carbon dioxide, separating N2 and SO2 through variable-voltage variable-frequency adsorption, compressing or cooling and performing gas-liquid separation to obtain liquid SO2, bottling the separated nitrogen gas and the liquid SO2 for industrial use, and enabling SO2 which is not liquefied and separated to enter a circulating process of compression or cooling and gas-liquid separation, so as to enable SO2 to be separated continuously. The method realizes comprehensive utilization and zero emission of mixed burner gas containing a great amount of nitrogen gas and sulfur dioxide caused by calcining of iron pyrite, the obtained liquid SO2 has high purity, the process is green, safe and energy-saving, and realizes zero emission and low cost.

Description

Nitrogen in variable-frequency variable-voltage absorption recovery roasting pyrite furnace gas and the method for sulfur dioxide
Technical field
The present invention relates to variable-frequency variable-voltage absorption and reclaim nitrogen in roasting pyrite furnace gas and the method for sulfur dioxide.
Background technology
Liquid sulfur dioxide is the liquid of water white transparency, irritant stink.Its gasification property is strong, and when in air, sulfur dioxide concentration reaches 0.04%～0.05%, sucking human body will be poisoning, and breathing and eyes are had to spread effect.Liquid sulfur dioxide is of many uses, it is a kind of important industrial chemicals, both can be used for producing synthetic fibers (being mainly polyamide fibre), washing agent, rubber chemicals, sodium hydrosulfite (sodium dithionite), plastics, dyestuff, medicine, lubricating oil and asccharin etc., can be used as again cold-producing medium, bleaching powder, extinguishing chemical and disinfectant etc.In recent years, along with the development of China's modern industry, the demand of liquid towards sulfur dioxide is growing, the output increase year after year of sulfur dioxide liquid, and the market demand is increasingly vigorous.
The furnace gas of roasting pyrite or sulfur dioxide in tail gas account for 7%～12% left and right, and sulfur trioxide accounts for 0.05%～0.4%, and sublimed sulfur, oxygen and the acid mist etc. of trace, and all the other are nitrogen.Under sulfur dioxide normal temperature and pressure, be colourless gas, there is intense stimulus smell.Be discharged in atmosphere and can be oxidized to sulfur trioxide, sulfur trioxide is combined with steam and is generated acid mist, thereby corrosion relevant ferrous metal equipment, pipeline and instrument shorten its service life.Therefore, remove or reclaim the furnace gas of roasting pyrite or the sulfur dioxide in tail gas, and being used, changing harmful to treasure, seeming particularly urgent!
At present, the industrial sulphur dioxide production liquid sulfur dioxide that reclaims from roasting pyrite furnace gas or tail gas mainly contains ammonia-acid system, natrium citricum absorption process, water absorption method, partial condensation method and Wei Sangman---Luo Defa etc. both at home and abroad, first these methods all absorb the sulfur dioxide of flue gas or furnace gas with the absorbents such as organic amine, water or ammonia of easy sulfur dioxide absorption, desorb again, obtains high concentration sulfur dioxide; Then high concentration sulfur dioxide is made to liquid sulfur dioxide with pressurization or freezing.These technology are more or less subject to the restrictions such as requirement of engineering reliability, economic rationality, reagent source regionality, industry production feature and environmental protection.As the ammonia of domestic extensive utilization at present-acid system adopts liquefied ammonia or ammoniacal liquor as absorbent, absorption efficiency is high, desulfurization is thorough, but technological process is complicated, equipment investment is large, operating cost is high, and the source of ammonia is subject to the restriction of region.Calcium method is to adopt limewash or milk of lime washing containing the flue gas of sulfur dioxide, forms calcium sulfite precipitation, generates calcium sulfate.This law technology is ripe, and production cost is low, but absorption rate is slow, absorbability is little, the actual application value of byproduct calcium sulfate little, the output quantity of slag is many, causes equipment Pipe-Line fouling serious.Sodium method is to use the alkaline matters such as natrium citricum, sodium carbonate or NaOH to absorb the flue gas containing sulfur dioxide, generate sodium sulfite or solution of sodium bisulfite, advantage is that absorbability is large, absorption rate is fast, desulfuration efficiency is high, equipment is simple, easy to operate and less scaling, weak point is that raw material soda is more expensive, and production cost is high.The common issue of said method is: 1. desulphurization plant engineering investment cost is large.2. the subsequent treatment of the accessory substance after desulfurization is difficult.Requirement or the environmental protection operating cost that 3. cannot meet environmental protection are high.
Nitrogen is a kind of gas of colorless and odorless odorless; nontoxic; there is good stability and very low boiling point; be widely used in oil exploitation, chemical industry security protection, protection weld metal, filling bulb, breeding, the accumulating of fruit grain, fresh-keeping, fire extinguishing, medical science, pharmacy etc.; it accounts for the 78.12%(volume fraction of atmosphere total amount), be the Main Ingredients and Appearance of air.
At present, both at home and abroad industrial from air the separated main method that reclaims nitrogen have: cryogenic rectification method, pressure swing adsorption method, membrane separation process and chemiadsorption etc., respectively have its pluses and minuses.
Wherein, the mechanism of cryogenic rectification method is by air compressing liquefaction, according to the difference of each component boiling point, separated through rectifying column rectifying, obtains required product.Large-scale industrial production oxygen, nitrogen, take cryogenic rectification method as most economical, occupies firmly dominant position in air separating method; Refrigerating loss simultaneously as far as possible low, institute's calorific requirement is tried one's best few.The double-column process that mainly contains separated oxygen, nitrogen simultaneously of the separated air of low temperature process and simultaneously produce two kinds of the three-column process flows of oxygen, nitrogen and argon.The development trend of low temperature process is: maximize (1), and maximum reaches 220000m 3/ h nitrogen; (2) adopt structured packing, advantage is that flow is large, resistance is little, operating flexibility is large, efficiency is high; (3) combine with other process, reduce energy consumption, improve whole gross efficiency.The equipment operating of cryogenic rectification method is complicated, and investment is large, and energy consumption is large.
Pressure swing adsorption method oxygen be utilize zeolite molecular sieve to the absorption affinity of nitrogen characteristic oxygen separation and the nitrogen higher than the absorption affinity to oxygen, or utilize that the diffusion velocity of oxygen in carbon molecule microcellular system narrow gap is greater than the diffusion velocity of nitrogen, separated oxygen, nitrogen under far from equilibrium condition.Pressure swing adsorption method oxygen, nitrogen carry out at normal temperatures, and technical process has pressurization absorption, normal pressure desorb; Normal pressure absorption, vacuum desorption.Adsorbent increases along with the rising of pressure the adsorbance of gas, along with the reduction of pressure, reduces, and in reducing the process of pressure, emits the gas being adsorbed, and makes adsorbent reactivation.Pressure-variable adsorption is subject to the restriction of two key technologies: the one, and the exploitation of high-efficiency adsorbent; The 2nd, the valve reliability of frequent switch and the raising of flexibility.At present, large-scale PSA device majority is the separated of steel and iron industry hydrogen manufacturing and syngas for synthetic ammonia CO2, and aspect sky divides, at present, separating power majority is 6000m 3device under/h.
Membrane separation process has strong adaptability, efficiency is high, flow process is short, equipment is simple, without running gear, easy to operate, floor space is little, small investment, energy-conservation, advanced technology, low power consumption and other advantages, development prospect and application are wide.But the cost of film is very high, and reliability is low!
Chemical absorption method refers to that high-temperature alkaline fused salt mixt can absorb airborne oxygen under catalyst action, then emits oxygen through step-down or intensification desorb.The oxygen of deviating from from fused salt, purity is 98%～99.5%.This method has very large future for Large Air Separation Devices oxygen, and oxygen output is more than 500t/d, and with traditional low temperature process oxygen comparison, efficiency can improve approximately 50%, also can produce a large amount of high-temperature water vapors simultaneously.
In sum, utilize at present pressure swing adsorption from the mixing furnace gas of roasting pyrite, to improve the sulfur dioxide of furnace gas and the concentration of nitrogen, obtain liquid sulfur dioxide and nitrogen-rich gas rarely has report simultaneously both at home and abroad.Therefore, be necessary to propose a kind of transformation absorption technology of utilizing and reclaim nitrogen in roasting pyrite furnace gas and the method for sulfur dioxide, overcome tradition and reclaim the problem that valuable gases exists equipment investment large, follow-up accessory substance processing difficulty and cannot meet environmental requirement, realize the comprehensive utilization of roasting pyrite flue gas and zero-emission.
Summary of the invention
The technical problem to be solved in the present invention is to provide the absorption of a kind of variable-frequency variable-voltage and reclaims nitrogen in roasting pyrite furnace gas and the method for sulfur dioxide, by the method, obtain liquid sulfur dioxide and nitrogen-rich gas simultaneously, realize the comprehensive utilization of roasting pyrite flue gas, product diversification, its process is green, safety, zero-emission, and without separately purchasing raw material, cost is low.
The present invention solves the problems of the technologies described above with following technical scheme:
Nitrogen in variable-frequency variable-voltage absorption recovery roasting pyrite furnace gas and the method for sulfur dioxide, processing step is as follows:
(1) by the fluidized bed furnace of the roasting pyrite furnace gas containing sulfur dioxide out after waste heat recovery cooling, cyclone dust removal and the electric precipitation of high-temperature residual heat boiler in temperature purify and low temperature purification, dedusting, except sulfur trioxide, dry and cooling, now, furnace gas temperature is 35 ℃～40 ℃, containing sulfur dioxide, be 7%～12%, CO 2and O 2content lower than 1%, N 2be 87%～92%;
(2) furnace gas after step (1) purge drying removes through the filter for refined sulfuric acid furnace gas of polytetrafluoroethylene (PTFE) material grit and the iron rust of carrying secretly in furnace gas again;
(3) adsorbent that step (2) gained furnace gas combines the de-tank of essence of carbon molecular sieve by loading is removed micro-water, the O in furnace gas 2and CO 2, now, the reduced water content in furnace gas is to 2.1mg/kg～3.2mg/kg, and the content of sulfur dioxide is 7.5%～12.5%, N 2content be 87.5%～92.5%;
(4) step (3) gained furnace gas enters surge tank, and the compression through with frequency converter compressor enters adsorption tower at the bottom of adsorption tower, and the sulfur dioxide in furnace gas is adsorbed the adsorbent absorption on agent bed, realizes nitrogen separated with sulfur dioxide; The sulfur dioxide being adsorbed, after depressurization desorption, by the vavuum pump suction surge tank of frequency converter, obtains liquid sulfur dioxide with pressurization or freezing; Containing the gas-liquid mixture of liquid sulfur dioxide and gaseous sulfur dioxide, enter gas-liquid separator and carry out gas-liquid separation, gained liquid sulfur dioxide is drained into be collected stand-byly in steel cylinder, and its purity is 98.6%～99.5%; Adsorbent obtains holomorphosis simultaneously; After adsorbent bed being evacuated, using and ejecting from adsorption tower the nitrogen that purity is 98.5%～99.8%, pressure is 0.11MPa～0.53MPa is 0.10MPa～0.50MPa to the adsorbent bed reverse adsorptive pressure that boosts to, and adsorbent bedly just starts to enter next sorption cycle process;
(5) the separated a small amount of SO that is not liquefied 2loop that step (4) is compressed or cooling, gas-liquid separation, sulfur dioxide wherein is constantly separated;
(6) by adsorption tower tower top nitrogen gas purity out, be 98.5%～99.8%, enter surge tank, then it be stand-by to bottle.
In described step (2), filter for refined sulfuric acid furnace gas is 200 orders.
The composition that loads the adsorbent of the de-tank of essence that combines carbon molecular sieve in described step (3) is: from the bottom up, the bottom is that quality is the silochrom of adsorbent mass 30%～40%, the second layer is that quality is the Kiselgel A of adsorbent mass 20%～30%, the 3rd layer is that quality is the sodium bentonite of adsorbent mass 10%～20%, the 4th layer is that quality is adsorbent mass 5%～10%13X molecular sieve, the superiors are that quality is the carbon molecular sieve of adsorbent mass 15%～20%, and the mass percent summation of above-mentioned each component is 100%.
Pressure at expulsion with frequency converter compressor in described step (4) is 0.13MPa～0.55MPa, and delivery temperature is 35 ℃～41 ℃.
Adsorbent described in described step (4) is to take active carbon that natural pond slag makes as basis, adds multiple Compound Supplement, and its each component and mass percent thereof are as follows:
The mass percent summation of each component is 100% above.
Described natural pond slag active carbon be take natural pond slag as raw material, and its preparation method is: with the natural pond slag after methane-generating pit fermentation, through cleaning, filtration, removal of impurities and screw extruder or three roller extruders, carry out extrusion dehydration, making its moisture content is 8%～10%; Through mass ratio, be that 10%-20%, temperature are that the liquor zinci chloridi of 30 ℃～40 ℃ soaks 35～40 hours again; Through screw extruder or three roller extruder extrusion dehydrations, dry or dry, making its moisture content is 5%～10%; The microwave irradiation charing that it is 2000W～3000W through irradiation power that gained natural pond slag is placed in the crucible of porcelain or carborundum, exposure time is 20 minutes～30 minutes, naturally after cooling, with after 30 ℃～40 ℃ rinsed with deionized water, dry 25 hours again, efflorescence is 200～400 order attritive powders again, obtains described natural pond slag active carbon.
Described methane tank sludge carbonized material be take marsh gas fermentation pool mud as raw material, its preparation method is: marsh gas fermentation pool mud is after screening precipitation drains, adding mass concentration is that 10%-20%, temperature are that the liquor zinci chloridi of 30 ℃～40 ℃ soaks 20 hours, drain rear baking 24h, the microwave irradiation charing that to be placed in the crucible of porcelain or carborundum be 2000W～3000W through irradiation power, exposure time is 10 minutes～20 minutes, with after 30 ℃～40 ℃ rinsed with deionized water, dry 25 hours again, efflorescence becomes 200～400 order attritive powders, obtains described methane tank sludge carbonized material.
Method of the present invention has the following advantages:
1, can from roasting pyrite furnace gas, obtain nitrogen and liquid sulfur dioxide simultaneously, realized the comprehensive utilization of roasting pyrite furnace gas, and cost be low, process is green, safety, zero-emission.
2, avoid the huge construction investment of enterprise's desulphurization plant and the environmental protection operating cost of great number, also avoided the difficult disposal of sweetening process accessory substance simultaneously.
Accompanying drawing explanation
Fig. 1 is the process chart that the method for nitrogen in roasting pyrite furnace gas and sulfur dioxide is reclaimed in variable-frequency variable-voltage of the present invention absorption.
The specific embodiment
Below in conjunction with Fig. 1, describe embodiments of the present invention in detail.
As shown in Figure 1, technological process of the present invention is: by the de-tank degree of depth essence of furnace gas → cyclone dust removal → electric precipitation → dry → cooling → essence dehydration out of the fluidized bed furnace of roasting pyrite, deoxidation with carbon dioxide removal → transformation absorption realize nitrogen and sulfur dioxide separated → compression → condensation → gas-liquid separation → cooling → acquisition liquid SO2.
Embodiment 1:
Gentle low temperature cooling, purifying in by the furnace gas out of the fluidized bed furnace by roasting pyrite after high-temperature residual heat boiler recovery waste heat, cyclone dust removal and electric precipitation, dedusting and sulfur trioxide, dry and cooling, now, furnace gas temperature is 35 ℃, containing sulfur dioxide mass ratio, be 12%, CO 2and O 2content lower than 1%, N2, be 87%; Through the filter for refined sulfuric acid furnace gas of 200 order polytetrafluoroethylene (PTFE) materials, remove grit and the iron rust of carrying secretly in gaseous mixture again, then through loading the de-tank absorption of essence of combination carbon molecular sieve, remove minor amount of water, the O mixing in furnace gas 2and CO 2, now, the reduced water content in mixing furnace gas is to 2.1mg/kg, and the content of sulfur dioxide is about 12.5%, N 2content be about 87.5%; Then the compression of band frequency converter compressor, is 0.13MPa with the exhaust pressure of frequency converter compressor, and delivery temperature is 35 ℃ of normal temperature; Furnace gas enters in adsorption tower from adsorption tower bottom afterwards, and the adsorbent absorption sulfur dioxide on adsorbent bed is realized the separated of nitrogen and sulfur dioxide; Be adsorbed the sulfur dioxide depressurization desorption of agent absorption, by vavuum pump, extract and send into surge tank, again high concentration sulfur dioxide is obtained to liquid sulfur dioxide with pressurization or freezing, the gas-liquid mixture that contains liquid and gaseous sulfur dioxide enters gas-liquid separator and carries out gas-liquid separation, liquid sulfur dioxide after separation is drained in steel cylinder to be collected, and the purity of liquid sulfur dioxide is 98.6%; Adsorbent obtains holomorphosis simultaneously; After adsorbent bed vacuumizing, then use that from adsorption tower, to eject the nitrogen that purity is 98.5%, pressure is 0.11MPa be 0.10MPa to the adsorbent bed reverse adsorptive pressure that boosts to, adsorbent bedly just start to enter next sorption cycle process.Separated a small amount of SO is not liquefied 2again enter band frequency converter compressor, compress, the cyclic process of cooling and gas-liquid separation, liquid sulfur dioxide wherein is constantly separated, bottling confession is industrial.The N that is 98.5% by tower top purity out 2enter bottle after surge tank stand-by.
The composition of the adsorbent of the de-tank of essence of described loading combination carbon molecular sieve is: from the bottom up, the bottom is silochrom, and the second layer is Kiselgel A, and the 3rd layer is sodium bentonite, and the 4th layer is 13X molecular sieve, and the superiors are carbon molecular sieves.
Described adsorbent on adsorbent bed is that to take the active carbon that natural pond slag makes be basis, adds sludge carbon material, Ludox, mass ratio and be the liquid paraffin of 1 ﹕ 5 and bicarbonate mixture, sodium bentonite, and mediation forms.
The preparation method of described natural pond slag active carbon is: the natural pond slag after methane-generating pit fermentation, through cleaning, filtration, removal of impurities, soaks through liquor zinci chloridi, then embathes by deionized water, equal extrusion dehydration after above-mentioned every step; Then dry or dry, microwave irradiation charing, naturally cooling after, dry efflorescence after rinsed with deionized water, obtain described natural pond slag active carbon.
The preparation method of described sludge carbon material is: marsh gas fermentation pool mud drains through screening precipitation, and liquor zinci chloridi soaks, and drains post-drying, and microwave irradiation charing is dried after rinsed with deionized water, and efflorescence, obtains described sludge carbon material.
Embodiment 2:
By the fluidized bed furnace by roasting pyrite out containing the furnace gas of sulfur dioxide through high-temperature residual heat boiler recovery waste heat, middle temperature cooling, purifying after cyclone dust removal and electric precipitation and low temperature cooling, purifying, dedusting and except sulfur trioxide, dry and cooling, now, furnace gas temperature is 40 ℃, containing sulfur dioxide, be 7%, CO 2and O 2content lower than 1%, N 2be 92%; Minor amount of water, the O mixing in furnace gas removed in the grit of carrying secretly in the filter for refined sulfuric acid furnace gas removal gaseous mixture of 200 order polytetrafluoroethylene (PTFE) materials again and iron rust, the de-tank absorption of essence 2and CO 2, now, the reduced water content in mixing furnace gas is to 3.2mg/kg, and the content that the content of sulfur dioxide is about 7.5%, N2 is about 92.5%; Then the compression of band frequency converter compressor, exhaust pressure with frequency converter compressor is 0.55MPa, and delivery temperature is 41 ℃ of left and right of normal temperature, at the bottom of adsorption tower, enters the adsorbent bed of adsorption tower, adsorbent absorption sulfur dioxide, realizes the separated of nitrogen and sulfur dioxide.Be adsorbed the sulfur dioxide depressurization desorption adsorbing in agent, vavuum pump by frequency converter extracts, enter surge tank, again high concentration sulfur dioxide is obtained to liquid sulfur dioxide with pressurization or freezing, the gas-liquid mixed gas that contains liquid sulfur dioxide and gaseous sulfur dioxide enters gas-liquid separator and carries out gas-liquid separation, sulfur dioxide after separation is drained in steel cylinder to be collected, and the purity of liquid sulfur dioxide is 99.5%.Adsorbent obtains holomorphosis simultaneously.After vacuumizing, then use that from adsorption tower, to eject the nitrogen that purity is 99.8%, pressure is 0.53MPa be 0.50MPa to the adsorbent bed reverse adsorptive pressure that boosts to, adsorbent bedly just start to enter next sorption cycle process.Separated a small amount of SO is not liquefied 2circulation enters band frequency converter compressor again, compresses, the cyclic process of cooling and gas-liquid separation, and liquid sulfur dioxide wherein is constantly separated, and bottling confession is industrial.By tower top N2 purity out, be 99.8% to enter surge tank, bottling, for industrial.
All the other are with embodiment 1.

Claims (7)

1. nitrogen in roasting pyrite furnace gas and the method for sulfur dioxide are reclaimed in variable-frequency variable-voltage absorption, it is characterized in that processing step is as follows:
(1) by the fluidized bed furnace of the roasting pyrite furnace gas containing sulfur dioxide out after waste heat recovery cooling, cyclone dust removal and the electric precipitation of high-temperature residual heat boiler in temperature purify and low temperature purification, dedusting, except sulfur trioxide, dry and cooling, now, furnace gas temperature is 35 ℃～40 ℃, containing sulfur dioxide, be 7%～12%, CO 2and O 2content lower than 1%, N 2be 87%～92%;
(2) furnace gas after step (1) purge drying removes through the filter for refined sulfuric acid furnace gas of polytetrafluoroethylene (PTFE) material grit and the iron rust of carrying secretly in furnace gas again;
(3) adsorbent that step (2) gained furnace gas combines the de-tank of essence of carbon molecular sieve by loading is removed micro-water, the O in furnace gas 2and CO 2, now, the reduced water content in furnace gas is to 2.1mg/kg～3.2mg/kg, and the content of sulfur dioxide is 7.5%～12.5%, N 2content be 87.5%～92.5%;
(4) step (3) gained furnace gas enters surge tank, and the compression through with frequency converter compressor enters adsorption tower at the bottom of adsorption tower, and the sulfur dioxide in furnace gas is adsorbed the adsorbent absorption on agent bed, realizes nitrogen separated with sulfur dioxide; The sulfur dioxide being adsorbed, after depressurization desorption, by the vavuum pump suction surge tank of frequency converter, obtains liquid sulfur dioxide with pressurization or freezing; Containing the gas-liquid mixture of liquid sulfur dioxide and gaseous sulfur dioxide, enter gas-liquid separator and carry out gas-liquid separation, gained liquid sulfur dioxide is drained into be collected stand-byly in steel cylinder, and its purity is 98.6%～99.5%; Adsorbent obtains holomorphosis simultaneously; After adsorbent bed being evacuated, using and ejecting from adsorption tower the nitrogen that purity is 98.5%～99.8%, pressure is 0.11MPa～0.53MPa is 0.10MPa～0.50MPa to the adsorbent bed reverse adsorptive pressure that boosts to, and adsorbent bedly just starts to enter next sorption cycle process;
(5) the separated a small amount of SO2 that is not liquefied loops that step (4) is compressed or cooling, gas-liquid separation, and sulfur dioxide wherein is constantly separated;
(6) by adsorption tower tower top nitrogen gas purity out, be 98.5%～99.8%, enter surge tank, then it be stand-by to bottle.
2. the nitrogen in variable-frequency variable-voltage absorption recovery roasting pyrite furnace gas as claimed in claim 1 and the method for sulfur dioxide, is characterized in that, in described step (2), filter for refined sulfuric acid furnace gas is 200 orders.
3. nitrogen in roasting pyrite furnace gas and the method for sulfur dioxide are reclaimed in variable-frequency variable-voltage as claimed in claim 1 absorption, it is characterized in that the composition that loads the adsorbent of the de-tank of essence that combines carbon molecular sieve in described step (3) is: from the bottom up, the bottom is that quality is the silochrom of adsorbent mass 30%～40%, the second layer is that quality is the Kiselgel A of adsorbent mass 20%～30%, the 3rd layer is that quality is the sodium bentonite of adsorbent mass 10%～20%, the 4th layer is that quality is adsorbent mass 5%～10%13X molecular sieve, the superiors are that quality is the carbon molecular sieve of adsorbent mass 15%～20%, the mass percent summation of above-mentioned each component is 100%.
4. nitrogen in roasting pyrite furnace gas and the method for sulfur dioxide are reclaimed in variable-frequency variable-voltage as claimed in claim 1 absorption, it is characterized in that in described step (4), the pressure at expulsion with frequency converter compressor is 0.13MPa～0.55MPa, delivery temperature is 35 ℃～41 ℃.
5. nitrogen in roasting pyrite furnace gas and the method for sulfur dioxide are reclaimed in variable-frequency variable-voltage as claimed in claim 1 absorption, it is characterized in that adsorbent described in described step (4) is that to take the active carbon that natural pond slag makes be basis, add multiple Compound Supplement, its each component and mass percent thereof are as follows:
The mass percent summation of each component is 100% above.
6. nitrogen in roasting pyrite furnace gas and the method for sulfur dioxide are reclaimed in variable-frequency variable-voltage as claimed in claim 5 absorption, it is characterized in that described natural pond slag active carbon take natural pond slag as raw material, its preparation method is: with the natural pond slag after methane-generating pit fermentation, through cleaning, filtration, removal of impurities and screw extruder or three roller extruders, carry out extrusion dehydration, making its moisture content is 8%～10%; Through mass ratio, be that 10%-20%, temperature are that the liquor zinci chloridi of 30 ℃～40 ℃ soaks 35～40 hours again; Through screw extruder or three roller extruder extrusion dehydrations, dry or dry, making its moisture content is 5%～10%; The microwave irradiation charing that it is 2000W～3000W through irradiation power that gained natural pond slag is placed in the crucible of porcelain or carborundum, exposure time is 20 minutes～30 minutes, naturally after cooling, with after 30 ℃～40 ℃ rinsed with deionized water, dry 25 hours again, efflorescence is 200～400 order attritive powders again, obtains described natural pond slag active carbon.
7. nitrogen in roasting pyrite furnace gas and the method for sulfur dioxide are reclaimed in variable-frequency variable-voltage as claimed in claim 5 absorption, it is characterized in that, described methane tank sludge carbonized material be take marsh gas fermentation pool mud as raw material, its preparation method is: marsh gas fermentation pool mud is after screening precipitation drains, adding mass concentration is 10%-20%, temperature is that the liquor zinci chloridi of 30 ℃～40 ℃ soaks 20 hours, drain rear baking 24h, the microwave irradiation charing that to be placed in the crucible of porcelain or carborundum be 2000W～3000W through irradiation power, exposure time is 10 minutes～20 minutes, with after 30 ℃～40 ℃ rinsed with deionized water, dry 25 hours again, efflorescence becomes 200～400 order attritive powders, obtain described methane tank sludge carbonized material.
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