CN103772250B - Recycling method of sulfur-containing mixed waste gas in viscose fiber production - Google Patents
Recycling method of sulfur-containing mixed waste gas in viscose fiber production Download PDFInfo
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- CN103772250B CN103772250B CN201410002204.9A CN201410002204A CN103772250B CN 103772250 B CN103772250 B CN 103772250B CN 201410002204 A CN201410002204 A CN 201410002204A CN 103772250 B CN103772250 B CN 103772250B
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000007789 gas Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 38
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 37
- 239000011593 sulfur Substances 0.000 title claims abstract description 37
- 229920000297 Rayon Polymers 0.000 title claims abstract description 34
- 238000007380 fibre production Methods 0.000 title abstract description 11
- 239000010812 mixed waste Substances 0.000 title abstract 3
- 238000004064 recycling Methods 0.000 title description 4
- 239000002912 waste gas Substances 0.000 claims abstract description 57
- 238000010521 absorption reaction Methods 0.000 claims abstract description 40
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 239000000835 fiber Substances 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 69
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 46
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 42
- 239000002253 acid Substances 0.000 claims description 40
- 239000003513 alkali Substances 0.000 claims description 38
- 238000009833 condensation Methods 0.000 claims description 36
- 230000005494 condensation Effects 0.000 claims description 36
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 34
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 28
- 239000005864 Sulphur Substances 0.000 claims description 27
- 238000011084 recovery Methods 0.000 claims description 22
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 20
- 229920002488 Hemicellulose Polymers 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 14
- 239000000920 calcium hydroxide Substances 0.000 claims description 14
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 14
- 239000000084 colloidal system Substances 0.000 claims description 14
- 239000001117 sulphuric acid Substances 0.000 claims description 14
- 235000011149 sulphuric acid Nutrition 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- MYFXBBAEXORJNB-UHFFFAOYSA-N calcium cyanamide Chemical compound [Ca+2].[N-]=C=[N-] MYFXBBAEXORJNB-UHFFFAOYSA-N 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- 239000007921 spray Substances 0.000 abstract description 6
- 229920002678 cellulose Polymers 0.000 abstract description 4
- 239000001913 cellulose Substances 0.000 abstract description 3
- 239000002910 solid waste Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 19
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 10
- 239000002699 waste material Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 235000010265 sodium sulphite Nutrition 0.000 description 5
- 239000007787 solid Substances 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 235000010980 cellulose Nutrition 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000010795 gaseous waste Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- Treating Waste Gases (AREA)
Abstract
The invention relates to a method for recovering and treating sulfur-containing mixed waste gas in viscose fiber production, and belongs to the technical field of treatment of sulfur-containing waste gas in viscose fiber production. The invention provides a new technical route aiming at the waste gas treatment condition of the existing viscose fiber production enterprises, which comprises the steps of pretreating low-concentration sulfur-containing waste gas, selectively absorbing the sulfur-containing waste gas by adopting a spray absorption technology, and treating absorption liquid to finally obtain a product with higher cost performance. The technical route has high industrialization degree, and the content of the cellulose in the production process of viscose fiber industry is lowConcentration H2S and CS2The mixed waste gas composed of a large amount of air and a small amount of solid waste substances can be effectively treated in time, and meanwhile, certain economic and social benefits can be obtained, so that the method has good technical feasibility and economic feasibility, and can meet the requirements of social sustainable development.
Description
Technical field
The present invention relates to a kind of recovery and treatment method of sulphur-containing exhaust gas, more particularly, the present invention relates to the recovery and treatment method of sulfur-bearing mix waste gas in the production of a kind of viscose fiber, belong to the processing technology field of sulphur-containing exhaust gas in viscose fiber production.
Background technology
In production process of viscose fiber, can produce a large amount of containing dithiocarbonic anhydride (CS
2) and hydrogen sulfide (H
2s) waste gas, hydrogen sulfide content is generally below 5%.Hydrogen sulfide is lower due to concentration, generally adopts three kinds for the treatment of processs:
1, alkali absorb method: employing highly basic (sodium hydroxide, sodium carbonate etc.) produces Sodium sulfhydrate after absorbing low concentration hydrogen sulphide waste gas or sodium sulphite puts goods on the market, this is the technology that current most domestic viscose fiber manufacturer adopts, although the waste gas after this technology can make process reaches discharging standards, owing to there being more CO in waste gas
2and CS
2, make the quality product that obtains lower, be worth not high, the product of production is difficult to the acquisition direct economic benefit that puts goods on the market;
2, combustion method produces sulfuric acid: this technology belongs to advanced foreign technology, and will adopt the special-purpose catalyst of external price costliness in treating processes, production cost is higher, and sulfuric acid internal price is very low, and working cost is high, and inapplicable domestic existing situation;
3, biochemical process: can reach emission standard after this method process, this technology also belongs to advanced foreign technology, because the special mushroom survival time is limited, processing cost is higher, does not also put it at home.
It is CN1058960 that State Intellectual Property Office discloses a publication number in 1992.2.26, and the patent of invention that name is called " method from stink damp direct synthesizing thiourea ", which discloses with plant gas H
2s is the method that raw material is directly processed into high value Chemicals thiocarbamide, breaks traditional barium sulphide and sulfuric acid or hydrochloric acid reaction and prepares H
2s prepare again thiocarbamide complex process, investment is many, cost is high, have the operational path that industrial gaseous waste waste residue is discharged, the present invention, as application refinery, can replace Crouse's sulphur recovery and produce sulphur, and change the product thiocarbamide that productive value equals sulphur decades of times into, bring great economic benefit.
From above-mentioned patent, in petroleum chemical industry, the hydrogen sulfide waste gas of generation directly can be processed into the Chemicals thiocarbamide of high value.But the sulphur-containing exhaust gas of the other industries such as the sulphur-containing exhaust gas in viscose fiber production and petrochemical complex has very large difference on composition and content, the sulphur-containing exhaust gas of petroleum chemical industry is mainly based on organic composition, inorganic components is auxiliary, and inorganic components is mainly based on hydrogen sulfide; And the sulphur-containing exhaust gas of viscose fiber industry is mainly inorganics, mainly containing nitric sulfid (CS
2) and hydrogen sulfide (H
2s), this waste gas has lower concentration (lower than 5%), low-purity (except H in waste gas
2s, CS
2beyond large quantity of air, also containing dithiocarbonic anhydride and tiny fibre dust, sulfur-bearing class material), high humidity (packed moisture is greater than 80%) there is the character of certain temperature (40-50 DEG C).So recovery processing technique hydrogen sulfide waste gas being converted into thiocarbamide in the industries such as existing petrochemical complex can not be applicable to the recycling of sulfur-bearing mix waste gas in viscose fiber production, produces thiocarbamide.And sulfur-bearing mix waste gas change into thiocarbamide and recycles in viscose fiber will being produced, need to solve following problems:
1, the problem of interference component in sulphur-containing exhaust gas is solved;
2, the enrichment problem of low concentration hydrogen sulphide gas is solved;
3, the problem of waste gas, waste water and waste residue how is fully utilized.
Aforementioned patent " method from stink damp direct synthesizing thiourea ", the hydrogen sulfide waste gas concentration of its process is higher, and volume fraction is more than 20%, and xanthation hydrogen exhaust gas volume mark is 0.05-5%, and concentration of hydrogen sulfide is lower, and intervention composition is more (as CS
2, CO
2, sulphur class material).
Summary of the invention
The present invention is intended to solve the problem that in above-mentioned prior art, how lower concentration sulfur-bearing mix waste gas processes, provide the recovery and treatment method of sulfur-bearing mix waste gas in the production of a kind of viscose fiber, sulfur-bearing mix waste gas process in viscose fiber can being produced, and be converted into thiocarbamide, reach the recycling object of waste gas.
In order to realize foregoing invention object, its concrete technical scheme is as follows:
A recovery and treatment method for sulfur-bearing mix waste gas in viscose fiber production, is characterized in that: comprise following processing step:
A, the sulfur-bearing mix waste gas that produces in production process of viscose fiber to be reclaimed after dithiocarbonic anhydride through condensation, be sent to alkali sprinkling system and carry out alkali spray-absorption;
B, when in alkali spray-absorption liquid, sodium sulfide content is more than 20%, absorption liquid can be used for next step reaction;
Drip acid solution in C, the absorption liquid that obtains in step B, carry out acid out, the gas of precipitation reclaims dithiocarbonic anhydride again by graphite condenser, makes hydrogen sulfide content in the noncondensable gas obtained reach more than 65%;
D, use milk of lime carry out spray-absorption to the hydrogen sulfide in the noncondensable gas obtained in step C, after calcium sulfhydrate concentration in milk of lime reaches the requirement of producing thiocarbamide, by absorption liquid and lime nitrogen Reactive Synthesis thiocarbamide.
The present invention is in steps A and C, and it is adopt graphite condenser to carry out condensation recovery that dithiocarbonic anhydride is reclaimed in described condensation.
In step, described condensation is reclaimed dithiocarbonic anhydride and is specially in the present invention: first adopt normal-temperature water and sulfur-bearing mix waste gas to carry out heat exchange, make the temperature of sulfur-bearing mix waste gas be down to 50-60 DEG C, then carries out condensation recovery dithiocarbonic anhydride with the refrigerated water of 5-8 DEG C.
The present invention in step, the alkali lye of the described alkali lye carrying out the employing of alkali spray-absorption to be NaOH concentration be 30-250g/L, hemicellulose concentration 40-150g/L.
The present invention is in step C, and the described acid solution of carrying out acid out is sulfuric acid content is≤20g/L, and fines content is 0.05-0.1g/L, and colloid sulphur and sulfide content are the mix acid liquor of the sulphuric acid soln of 0.1-0.5g/L and the vitriol oil of 98%.
Above-mentioned sulfuric acid content is≤20g/L, and fines content is 0.05-0.1g/L, and colloid sulphur and sulfide content are the usage ratio of the sulphuric acid soln of 0.1-0.5g/L and the vitriol oil of 98% is 1:1-6.
In step D, the concentration of described milk of lime is 10-30% in the present invention.
The Advantageous Effects that the present invention brings:
1, the present invention is intended to solve the problem that in prior art, how lower concentration sulfur-bearing mix waste gas processes, provide a kind of method utilizing the low concentration hydrogen sulphide waste gas in viscose fiber production to produce thiocarbamide, sulfur-bearing mix waste gas process in viscose fiber can being produced, and be converted into thiocarbamide, reach the recycling object of waste gas.The present invention proposes to adopt the waste gas produced in viscose fiber enterprise production process to produce the method for thiocarbamide, obtain the Thio Urea product that marketable value is higher, effectively administer viscose glue enterprise waste gas, effective utilization has been carried out to the salkali waste spent acid in viscose glue enterprise production process simultaneously, make viscose glue enterprise in waste gas pollution control and treatment process, obtain certain economic benefit, there is very high market popularization value.
2, the present invention is directed to current viscose fiber manufacturing enterprise off gas treatment situation, propose a kind of technical strategies, first pre-treatment is carried out to the sulphur-containing exhaust gas of lower concentration, then spray-absorption technology is adopted optionally to absorb it, subsequently absorption liquid is processed, the product that final acquisition sexual valence is higher.This technological line industrialization level is higher, make in viscose fiber industry production process containing lower concentration H
2s and CS
2, large quantity of air, a small amount of solid waste material the mix waste gas of composition obtain timely and effective process while, also can obtain certain economic and social benefit, there is good technical feasibility and economic feasibility, the needs of social sustainable development can be met.
3, dithiocarbonic anhydride is reclaimed in the condensation of steps A of the present invention, first be that the dithiocarbonic anhydride in waste gas is reclaimed, next is remove portion solid matter, then is the preliminary concentration realizing sulfurous gas, and this step has and is beneficial to the purification of subsequent step available gas and the advantage of enrichment.
4, in steps A of the present invention and step C, condensation is reclaimed dithiocarbonic anhydride and is preferably adopted graphite condenser, and it is highly suitable for the condensation process of phase transformation, and corrosion resistance nature is fine.Condensation is reclaimed in the process of dithiocarbonic anhydride does not have High Temperature High Pressure, does not need the equipment of other high cost withstand high temperatures high pressure.In condensation process, dithiocarbonic anhydride becomes liquid state from gaseous state, and dithiocarbonic anhydride is good organic solvent, and the sour gas hydrogen sulfide containing higher concentration in waste gas, graphite has good tolerance to these two kinds of materials, and whole technological process cost is reduced.
5, the present invention is preferred in step, condensation is reclaimed dithiocarbonic anhydride process and is specially: first adopt normal-temperature water and sulfur-bearing mix waste gas to carry out heat exchange, make the temperature of sulfur-bearing mix waste gas be down to 50-60 DEG C, then carry out condensation recovery dithiocarbonic anhydride with the refrigerated water of 5-8 DEG C.Above-mentioned condensation at twice, effectively can save the consumption of refrigerated water, reduces production cost.
6, the present invention is preferred in step, the alkali lye of the alkali lye carrying out the employing of alkali spray-absorption to be NaOH concentration be 30-250g/L, hemicellulose concentration 40-150g/L.Above-mentioned alkali lye is the alkali lye of sodium hydroxide and hemicellulose composition, and the squeezing waste lye during viscose fiber namely can be used to produce, to reduce production cost, realizes the lower concentration CS in waste gas
2hemicellulose class substance reaction in the squeezing waste lye produced with viscose fiber and the effect removed, eliminate the CS in mix waste gas further
2, CO
2, solid matter in portion gas, enrichment has been carried out to gas, has reached the H in sulphur-containing exhaust gas
2s and air, CS
2deng other separating substances, purification, concentrated object, make hemicellulose class material in squeezing salkali waste through precipitate and separate simultaneously, in gas solid matter also can be precipitated out because of hemicellulose, cellulose adsorption in salkali waste, the hemicellulose class material be precipitated out and other solid matters are utilized as fuel, reach the object of waste gas, wastewater utilization.
7, the present invention is preferred in step C, and the described acid solution of carrying out acid out is sulfuric acid content is≤20g/L, and fines content is 0.05-0.1g/L, and colloid sulphur and sulfide content are the mix acid liquor of the sulphuric acid soln of 0.1-0.5g/L and the vitriol oil of 98%.Further, above-mentioned sulfuric acid content is≤20g/L, and fines content is 0.05-0.1g/L, and colloid sulphur and sulfide content are the usage ratio of the sulphuric acid soln of 0.1-0.5g/L and the vitriol oil of 98% is 1:1-6.The acid solution that the present invention carries out acid out is the acid solution being mixed with sulfuric acid and hemicellulose, spent acid solution during viscose fiber can be used to produce, reduce cost, by adding acid solution in absorption liquid, a large amount of Mierocrystalline celluloses that can make to dissolve in salkali waste, hemicellulose are separated out, and greatly reduce the intractability of waste liquid, and the Mierocrystalline cellulose of separating out, hemicellulose can be reclaimed by common filtering technique, may be used for combustion heat supplying, also can refine purification, for the manufacture of other high value-added product.
8, the present invention is preferred in step D, and the concentration of described milk of lime is 10-30%.The hydrogen sulfide purity obtained in prior art is very high, impurity is few, the interference be subject in the process of reacting with milk of lime is less, only need through negative pressure absorbing, and viscose fiber produce in sulphur-containing exhaust gas in foreign gas many, content is high, in noncondensable gas described in step D, foreign gas content is higher, and adopt the milk of lime that present invention optimizes concentration, spray spray and bubble absorption are carried out to noncondensable gas, ensure that the abundant absorption to hydrogen sulfide in noncondensable gas, make the gas energy qualified discharge after absorption, also can prevent from impacting thiocarbamide production during the concentration generation larger fluctuation of hydrogen sulfide in noncondensable gas.
Embodiment
embodiment 1
A recovery and treatment method for sulfur-bearing mix waste gas in viscose fiber production, comprises following processing step:
A, the sulfur-bearing mix waste gas that produces in production process of viscose fiber to be reclaimed after dithiocarbonic anhydride through condensation, be sent to alkali sprinkling system and carry out alkali spray-absorption;
B, when in alkali spray-absorption liquid, sodium sulfide content is more than 20%, absorption liquid can be used for next step reaction;
Drip acid solution in C, the absorption liquid that obtains in step B, carry out acid out, the gas of precipitation reclaims dithiocarbonic anhydride again by condensation, makes hydrogen sulfide content in the noncondensable gas obtained reach more than 65%;
D, use milk of lime carry out spray-absorption to the hydrogen sulfide in the noncondensable gas obtained in step C, after calcium sulfhydrate concentration in milk of lime reaches the requirement of producing thiocarbamide, by absorption liquid and lime nitrogen Reactive Synthesis thiocarbamide.
embodiment 2
On the basis of embodiment 1, preferred:
The present invention is in steps A and C, and it is adopt graphite condenser to carry out condensation recovery that dithiocarbonic anhydride is reclaimed in described condensation.
In step, described condensation is reclaimed dithiocarbonic anhydride and is specially in the present invention: first adopt normal-temperature water and sulfur-bearing mix waste gas to carry out heat exchange, make the temperature of sulfur-bearing mix waste gas be down to 50 DEG C, then carries out condensation recovery dithiocarbonic anhydride with the refrigerated water of 5 DEG C.
The present invention in step, the alkali lye of the described alkali lye carrying out the employing of alkali spray-absorption to be NaOH concentration be 30g/L, hemicellulose concentration 40g/L.
The present invention is in step C, and the described acid solution of carrying out acid out is sulfuric acid content is≤20g/L, and fines content is 0.05g/L, and colloid sulphur and sulfide content are the mix acid liquor of the sulphuric acid soln of 0.1g/L and the vitriol oil of 98%.
Above-mentioned sulfuric acid content is≤20g/L, and fines content is 0.05g/L, and colloid sulphur and sulfide content are the usage ratio of the sulphuric acid soln of 0.1g/L and the vitriol oil of 98% is 1:1.
In step D, the concentration of described milk of lime is 10% in the present invention.
embodiment 3
On the basis of embodiment 1, preferred:
The present invention is in steps A and C, and it is adopt graphite condenser to carry out condensation recovery that dithiocarbonic anhydride is reclaimed in described condensation.
In step, described condensation is reclaimed dithiocarbonic anhydride and is specially in the present invention: first adopt normal-temperature water and sulfur-bearing mix waste gas to carry out heat exchange, make the temperature of sulfur-bearing mix waste gas be down to 60 DEG C, then carries out condensation recovery dithiocarbonic anhydride with the refrigerated water of 8 DEG C.
The present invention in step, the alkali lye of the described alkali lye carrying out the employing of alkali spray-absorption to be NaOH concentration be 250g/L, hemicellulose concentration 150g/L.
The present invention is in step C, and the described acid solution of carrying out acid out is sulfuric acid content is≤20g/L, and fines content is 0.1g/L, and colloid sulphur and sulfide content are the mix acid liquor of the sulphuric acid soln of 0.5g/L and the vitriol oil of 98%.
Above-mentioned sulfuric acid content is≤20g/L, and fines content is 0.1g/L, and colloid sulphur and sulfide content are the usage ratio of the sulphuric acid soln of 0.5g/L and the vitriol oil of 98% is 1:6.
In step D, the concentration of described milk of lime is 30% in the present invention.
embodiment 4
On the basis of embodiment 1, preferred:
The present invention is in steps A and C, and it is adopt graphite condenser to carry out condensation recovery that dithiocarbonic anhydride is reclaimed in described condensation.
In step, described condensation is reclaimed dithiocarbonic anhydride and is specially in the present invention: first adopt normal-temperature water and sulfur-bearing mix waste gas to carry out heat exchange, make the temperature of sulfur-bearing mix waste gas be down to 55 DEG C, then carries out condensation recovery dithiocarbonic anhydride with the refrigerated water of 6.5 DEG C.
The present invention in step, the alkali lye of the described alkali lye carrying out the employing of alkali spray-absorption to be NaOH concentration be 140g/L, hemicellulose concentration 95g/L.
The present invention is in step C, and the described acid solution of carrying out acid out is sulfuric acid content is≤20g/L, and fines content is 0.075g/L, and colloid sulphur and sulfide content are the mix acid liquor of the sulphuric acid soln of 0.3g/L and the vitriol oil of 98%.
Above-mentioned sulfuric acid content is≤20g/L, and fines content is 0.075g/L, and colloid sulphur and sulfide content are the usage ratio of the sulphuric acid soln of 0.3g/L and the vitriol oil of 98% is 1:3.5.
In step D, the concentration of described milk of lime is 20% in the present invention.
embodiment 5
On the basis of embodiment 1, preferred:
The present invention is in steps A and C, and it is adopt graphite condenser to carry out condensation recovery that dithiocarbonic anhydride is reclaimed in described condensation.
In step, described condensation is reclaimed dithiocarbonic anhydride and is specially in the present invention: first adopt normal-temperature water and sulfur-bearing mix waste gas to carry out heat exchange, make the temperature of sulfur-bearing mix waste gas be down to 58 DEG C, then carries out condensation recovery dithiocarbonic anhydride with the refrigerated water of 6 DEG C.
The present invention in step, the alkali lye of the described alkali lye carrying out the employing of alkali spray-absorption to be NaOH concentration be 60g/L, hemicellulose concentration 130g/L.
The present invention is in step C, and the described acid solution of carrying out acid out is sulfuric acid content is≤20g/L, and fines content is 0.09g/L, and colloid sulphur and sulfide content are the mix acid liquor of the sulphuric acid soln of 0.2g/L and the vitriol oil of 98%.
Above-mentioned sulfuric acid content is≤20g/L, and fines content is 0.09g/L, and colloid sulphur and sulfide content are the usage ratio of the sulphuric acid soln of 0.2g/L and the vitriol oil of 98% is 1:5.
In step D, the concentration of described milk of lime is 17% in the present invention.
embodiment 6
In the alkali spray of steps A of the present invention:
According to the volume of alkali sprayed tank storage tank, disposablely pump into alkali lye, then by the form of spray, alkali lye is constantly circulated between storage tank and top jet nozzle bottom sprayed tank, alkali lye absorbs the sulfur-bearing mix waste gas delivered in sprayed tank in the process of circulation, hydrogen sulfide in sulfur-bearing mix waste gas and alkaline reaction generate sodium sulphite, determine when spray terminates by the content (described in step B) detecting sodium sulphite.
In the acid out of step C of the present invention:
The composition of absorption liquid is comparatively complicated, be not easy to calculate the concrete consumption of acid and the time of acid out, absorption liquid with acid carry out reaction release hydrogen sulfide time, absorption liquid has obvious color and change of state, when just starting, absorption liquid is amber transparent liquid, after acid adding, sodium sulphite in absorption liquid understands the releasing hydrogen sulfide that first react with acid, and after sodium sulphite has reacted, the hemicellulose be dissolved in absorption liquid can generate white thing hard to tolerate with acid-respons, now absorption liquid starts to become muddy, color graduates into white, is now reaction end, stops acid adding.
Claims (1)
1. viscose fiber produce in the recovery and treatment method of sulfur-bearing mix waste gas, it is characterized in that: comprise following processing step:
A, the sulfur-bearing mix waste gas that produces in production process of viscose fiber to be reclaimed after dithiocarbonic anhydride through condensation, be sent to alkali sprinkling system and carry out alkali spray-absorption; The alkali lye of the described alkali lye carrying out the employing of alkali spray-absorption to be NaOH concentration be 30-250g/L, hemicellulose concentration 40-150g/L; It is adopt graphite condenser to carry out condensation recovery that dithiocarbonic anhydride is reclaimed in described condensation; Described condensation is reclaimed dithiocarbonic anhydride and is specially: first adopt normal-temperature water and sulfur-bearing mix waste gas to carry out heat exchange, make the temperature of sulfur-bearing mix waste gas be down to 50-60 DEG C, then carries out condensation recovery dithiocarbonic anhydride with the refrigerated water of 5-8 DEG C;
B, when in alkali spray-absorption liquid, sodium sulfide content is more than 20%, absorption liquid can be used for next step reaction;
Drip acid solution in C, the absorption liquid that obtains in step B, carry out acid out, the gas of precipitation reclaims dithiocarbonic anhydride again by graphite condenser, makes hydrogen sulfide content in the noncondensable gas obtained reach more than 65%; The described acid solution of carrying out acid out is sulfuric acid content is≤20g/L, and fines content is 0.05-0.1g/L, and colloid sulphur and sulfide content are the mix acid liquor of the sulphuric acid soln of 0.1-0.5g/L and the vitriol oil of 98%; Described sulfuric acid content is≤20g/L, and fines content is 0.05-0.1g/L, and colloid sulphur and sulfide content are the usage ratio of the sulphuric acid soln of 0.1-0.5g/L and the vitriol oil of 98% is 1:1-6;
D, working concentration are that the milk of lime of 10-30% carries out spray-absorption to the hydrogen sulfide in the noncondensable gas obtained in step C, after calcium sulfhydrate concentration in milk of lime reaches the requirement of producing thiocarbamide, by absorption liquid and lime nitrogen Reactive Synthesis thiocarbamide.
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| CN104436742B (en) * | 2014-10-20 | 2016-05-25 | 宜宾丝丽雅股份有限公司 | CS produced by viscose staple fiber2Recovery process |
| CN104258684B (en) * | 2014-10-20 | 2016-05-25 | 宜宾丝丽雅股份有限公司 | CS produced by viscose staple fiber2Recovery system |
| CN104474875B (en) * | 2014-12-17 | 2016-06-15 | 巨野县鑫源化工有限公司 | Process the method for the waste gas containing hydrogen sulfide, Carbon bisulfide and corresponding device |
| CN105348162A (en) * | 2015-11-20 | 2016-02-24 | 宜宾海翔化工有限责任公司 | Thiourea production technology |
| CN106422729A (en) * | 2016-11-30 | 2017-02-22 | 成都丽雅纤维股份有限公司 | System for treating waste gas in viscose fiber production |
| CN106512651A (en) * | 2016-11-30 | 2017-03-22 | 成都丽雅纤维股份有限公司 | Pre-treating method for treating viscose exhaust gas |
| CN106693647B (en) * | 2016-11-30 | 2020-08-11 | 成都丽雅纤维股份有限公司 | Method for enriching carbon disulfide and hydrogen sulfide in viscose waste gas |
| CN110155957B (en) * | 2019-06-18 | 2022-08-09 | 赛得利（福建）纤维有限公司 | Method for preparing sulfuric acid by using zinc-containing wastewater and NaHS waste liquid in viscose fiber factory |
| CN115745262A (en) * | 2022-11-21 | 2023-03-07 | 中国科学院过程工程研究所 | Desulfurization device and method for sulfur-containing and salt-containing process water |
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