CN102408100B - Sodium sulfhydrate product with concentration of 22% and low content of carnallite produced from viscose fiber waste gas - Google Patents
Sodium sulfhydrate product with concentration of 22% and low content of carnallite produced from viscose fiber waste gas Download PDFInfo
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- CN102408100B CN102408100B CN201110218352.0A CN201110218352A CN102408100B CN 102408100 B CN102408100 B CN 102408100B CN 201110218352 A CN201110218352 A CN 201110218352A CN 102408100 B CN102408100 B CN 102408100B
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Abstract
The invention develops a production process and device for reducing carnallite in a sodium sulfhydrate product with a concentration of 22% and a product. According to the invention, the content of carnallite in sodium sulfhydrate with a concentration of 22% is decreased from 9% to below 6%, consumption of NaOH is reduced, burden to subsequent production is alleviated, and economic benefits in the industrial production of viscose fibers are improved.
Description
Technical field
The present invention relates to viscose fibre industry process gas and administer the new technology in field, particularly for reducing the method for carnallite in the 22%NaHS product producing in hydrogen sulfide tail gas removal process and producing the product obtaining by the method.
Background technology
In viscose fibre industry production process, conventionally all will use carbon disulfide as raw material, after after chemical reaction, it can produce hydrogen sulfide (H
2s) waste gas and carbon disulfide waste gas.Hydrogen sulfide, carbon disulfide are all hypertoxic gas, and directly discharge meeting causes serious pollution to air.The method of existing improvement hydrogen sulfide tail gas has: the one, and catalytic desulfuriation, is that mix waste gas is contacted with catalyst liquid phase, makes hydrogen sulfide change Sulfur into and is eliminated.But due to catalyst source less, expensive, too high being difficult to of operating cost promote; The 2nd, combustion method, this method has strict demand to the concentration of each component in waste gas, requires the concentration of hydrogen sulfide, carbon disulfide more than 5 grams/cubic metre, oxygen content requires lower than 6%, otherwise easily blast, operating safety factor is low, and still has part sulfur dioxide (SO2) emissions to cause secondary pollution in atmosphere; The 3rd, microbial biochemical method is administered, and because microorganism fungus kind is difficult, cultivates, easily makes a variation, and it is low that it removes hydrogen sulfide efficiency, and power cost is high; The 4th, the mode that adopts NaOH to absorb, i.e. H
2after S reacts with NaOH, generate NaHS (NaHS), guarantee that toxic emission is up to standard, its reaction equation is: H
2s+2NaOH → Na
2s+2H
2o (1); Na
2s+H
2s → 2NaHS (2).The method that Ge great viscose glue factory (as Tangshan three friends, Jiangxi Sai get Li, the refined U.S. in Shandong etc.) generally adopts the 4th kind of method, alkali to absorb is at present administered hydrogen sulfide tail gas.
But in viscose rayon plant gas except containing hydrogen sulfide, also contain other impurity, therefore can be with certain impurity in reacted sodium hydrosulfide, and also aqueous slkali is when recycle, in absorbing hydrogen sulphide, also can react with airborne CO2, produce a large amount of Na
2cO
3, its reaction equation is: 2NaOH+CO
2=Na
2cO3+H
2o (3).This part be take sodium carbonate and is that main carnallite makes in 70%NaHS process and remove with centrifuge is separated at 22%NaHS, as refuse, disposes.In general, in 22% NaHS, the content of sodium carbonate maintains 9% left and right.If monthly produce 1000 tons of 22% NaHSs, i.e. 220 tons of NaHSs, 157.14 tons, theoretical consumption caustic soda; 90 tons, sodium carbonate, 67.92 tons, caustic soda of consumption, two are added 225.06 tons, consumption caustic soda, and wherein having 30% consumption is that we are undesirable.If carbonate content reduces by 1% in each ton of 22%NaHS finished product, just can consume less 0.022 ton, 32% caustic soda, not only reduce the burden that alkaline consumption has also reduced centrifuge in producing 70%NaHS process simultaneously.
Summary of the invention
Technical problem solved by the invention is to have overcome above-mentioned defect, develop production technology, equipment and the product of carnallite in a set of reduction by 22% NaHS product, the content of carnallite in 22% NaHS is reduced to below 6% by 9%, the consumption that has reduced NaOH also reduces the burden of subsequent production, improves the economic benefit that viscose fibre industry is produced.
In order to reach above-mentioned technical purpose, the technical solution used in the present invention is:
A 22% NaHS product that utilizes the low carnallite content of viscose rayon waste gas production, in wherein said 22% NaHS product, carbonate content is below 6%.
The preparation method of above-mentioned 22% NaHS product, adopt the hydrogen sulfide tail gas in alkali liquor absorption viscose fibre industry waste gas, generate NaHS, focus on: by 22% sodium hydrosulfide obtaining after the alkali liquor absorption through in alkaline bath for the first time through alkaline bath for the second time, make NaHS partly generate vulcanized sodium, concentration of lye in alkaline bath is for the second time reduced, turn back to again the first alkaline bath, repeat above-mentioned alkaline cleaning procedure, finally by alkaline bath for the third time, export 22% NaHS product of low carnallite content, alkali lye in the 3rd alkaline bath turns back in the second alkaline bath and reuses simultaneously, wherein the flux of alkaline liquor in alkaline cleaning procedure is 200-400m
3/ h, initial concentration of lye is 250-260g/L.Continuous operations between described three alkaline baths.
For described preparation method's equipment, comprise for the first time alkaline bath, alkaline bath, alkaline bath, NaHS storage tank, alkali surge-tank and scrubbing tower for the third time for the second time, for the first time alkaline bath, alkaline bath, UNICOM continuously between alkaline bath for the third time for the second time; Alkaline bath is connected hydrogen sulfide tail gas conveyance conduit for the first time, and is controlled and be switched to NaHS storage tank by alkali cleaning pump and valve; NaHS storage tank is switched to alkaline bath for the second time by pump, and alkaline bath is switched to alkaline bath for the first time by alkali cleaning pump for the second time; Alkali surge-tank is switched to alkaline bath for the third time by alkali transfer pump, and alkaline bath is switched to alkaline bath for the second time by alkali cleaning pump for the third time; After alkaline bath, connect scrubbing tower for the third time.
Inventor finds through research:
1, through assay, find, sodium carbonate is mainly the generation in reaction (1), and caustic soda is converted into after vulcanized sodium completely, and when reaction (2), (in tank, solution is Na
2s, NaHS mixture, NaOH total overall reaction is complete) content of sodium carbonate in solution increase not obvious, in conjunction with above situation, by blocking or reducing the CO containing in caustic soda and dirty gas
2neutralization reaction, just can reach the generation that reduces sodium carbonate, also can reduce the consumption of caustic soda simultaneously.From three large workshops, send into CO in the dirty gas in waste gas workshop
2amount number be bad control.Only from caustic soda aspect, set about.
When 2, alkali cleaning moves, in the generative process of NaHS, be through reaction (1), (2) front latter two reaction; In (1) reaction is carried out, before the NaOH in tank does not neutralize completely and generates Na2S, NaHS can not generate, and NaHS and NaOH are incompatible in solution.HS-+OH-=S
-2+ H
2o, and in reaction (2) process, Na
2the S aqueous solution and CO
2the speed of contact carbonating is very slow, in alkali cleaning workshop section, forms NaHS in the short time (in 8～12 hours), and the salt changing into is less.
3, waste gas finished product 22%NaHS solution is pumped in secondary alkaline bath and (for material being sent into alkali cleaning for the third time, also considered, but because alkali cleaning pump for the third time only approaches when qualified and just moves at alkali cleaning material for the first time, running time is shorter, if do not circulate after displacement, the easy crystallization of sodium sulfide solution causes fluctuation of service, as continuous operation alkali cleaning for the third time, can increase power consumption, put aside) to mix by a certain percentage with the 250g/L alkali lye from alkali surge-tank, part generates Na
2s:NaHS+NaOH=Na
2s+H
2o, the NaOH content in the solution of secondary alkaline bath reduces.By the continuous groove that falls, operate, the material NaOH content that pumps into an alkaline bath from secondary alkaline bath is also reduced simultaneously, can be with changing into Na than the present short remaining NaOH of time chien shih in circular flow
2s, the rise time of shortening NaHS, reduces and synchronously carries out neutralization reaction generation Na
2cO
3, the utilization rate of raising liquid caustic soda.
Adopt method and apparatus provided by the invention, the finished product 22% NaHS carbonate content in waste gas workshop has dropped to 6% left and right, greatly reduces the consumption of caustic soda, has alleviated the burden of NaHS workshop except carnallite.
Accompanying drawing explanation
Fig. 1 is equipment schematic diagram of the present invention.
The specific embodiment
For further illustrating the present invention, illustrate with the following Examples:
Embodiment 1:
A kind of Preparation equipment (as shown in Figure 1) that utilizes 22% NaHS product of the low carnallite content that viscose rayon waste gas produces, comprise alkaline bath 1, alkaline bath 2, alkaline bath 3, NaHS storage tank 4, alkali surge-tank 5 and scrubbing tower 6, for the first time alkaline bath 1, alkaline bath 2, connection continuously between alkaline bath 3 for the third time for the second time for the third time for the second time for the first time; Alkaline bath 1 is connected hydrogen sulfide tail gas conveyance conduit for the first time, and is controlled and be switched to NaHS storage tank 4 by alkali cleaning pump 7 and valve; NaHS storage tank 4 is switched to alkaline bath 2 for the second time by pump 8, and alkaline bath 2 is switched to alkaline bath 1 for the first time by alkali cleaning pump 9 for the second time; Alkali surge-tank 5 is switched to alkaline bath 3 for the third time by alkali transfer pump 10, and alkaline bath 3 is switched to alkaline bath 2 for the second time by alkali cleaning pump 11 for the third time; The rear connection scrubbing tower 6 of alkaline bath 3 for the third time.Preparation method is: adopt sodium hydroxide lye to absorb the hydrogen sulfide tail gas in viscose fibre industry waste gas, generate NaHS, by 22% sodium hydrosulfide obtaining after the alkali liquor absorption through in alkaline bath 1 for the first time through alkaline bath 2 for the second time, make NaHS partly generate vulcanized sodium, concentration of lye in alkaline bath 2 is for the second time reduced, turn back to again the first alkaline bath 1, repeat above-mentioned alkaline cleaning procedure, finally by alkaline bath 3 outputs for the third time, obtain 22% NaHS product of low carnallite content, alkali lye in the 3rd alkaline bath turns back in the second alkaline bath and reuses simultaneously, wherein the flux of alkaline liquor in alkaline cleaning procedure is identical, the dirty throughput 40000m in workshop
3/ h, wherein H 2 S-containing gas concentration 6.2g/m
3, initial alkali cleaning concentration 255g/L, flux of alkaline liquor 200m
3/ h, 22% NaHS storage tank capacity of returns 5m
3/ h, with this understanding, the content 5.6% of sodium carbonate in the 22% NaHS product obtaining.
Embodiment 2:
Preparation equipment is with embodiment 1.
Preparation method is: adopt sodium hydroxide lye to absorb the hydrogen sulfide tail gas in viscose fibre industry waste gas, generate NaHS, by 22% sodium hydrosulfide obtaining after the alkali liquor absorption through in alkaline bath 1 for the first time again through alkaline bath 2 for the second time, make NaHS partly generate vulcanized sodium, concentration of lye in alkaline bath 2 is for the second time reduced, turn back to again the first alkaline bath 1, repeat above-mentioned alkaline cleaning procedure, finally by alkaline bath 3 outputs for the third time, obtain 22% NaHS product of low carnallite content; Wherein the flow in alkaline cleaning procedure is identical, the dirty throughput 80000m in workshop
3/ h, wherein H 2 S-containing gas concentration 6.8g/m
3, initial alkali cleaning concentration 260g/L, flux of alkaline liquor 300m
3/ h, 22% NaHS storage tank capacity of returns 10m
3/ h, with this understanding, the content 5.5% of sodium carbonate in the 22% NaHS product obtaining.
Above-described embodiment is described the preferred embodiment of the present invention; not scope of the present invention is limited; design under the prerequisite of spirit not departing from the present invention; various distortion and improvement that the common engineers and technicians in this area make technical scheme of the present invention, all should fall in the definite protection domain of claims of the present invention.
Claims (3)
1. a method of utilizing viscose rayon waste gas to produce 22% NaHS product of low carnallite content, adopt the hydrogen sulfide tail gas in alkali liquor absorption viscose fibre industry waste gas, generate NaHS, it is characterized in that: by 22% sodium hydrosulfide obtaining after the alkali liquor absorption through in alkaline bath for the first time through alkaline bath for the second time, make NaHS partly generate vulcanized sodium, concentration of lye in alkaline bath is for the second time reduced, turn back to again the first alkaline bath, repeat above-mentioned alkaline cleaning procedure, finally by alkaline bath for the third time, export 22% NaHS product of low carnallite content, alkali lye in the 3rd alkaline bath turns back in the second alkaline bath and reuses simultaneously, wherein the flux of alkaline liquor in alkaline cleaning procedure is 200-400m
3/ h, initial concentration of lye is 250-260g/L.
2. preparation method according to claim 1, is characterized in that: continuous operations between described three alkaline baths.
3. for preparation method's claimed in claim 2 equipment, it is characterized in that: comprise alkaline bath (1), alkaline bath (2), alkaline bath (3), NaHS storage tank (4), alkali surge-tank (5) and scrubbing tower (6), for the first time alkaline bath (1), alkaline bath (2), connection continuously between alkaline bath (3) for the third time for the second time for the third time for the second time for the first time; Alkaline bath (1) is connected hydrogen sulfide tail gas conveyance conduit for the first time, and is controlled and be switched to NaHS storage tank (4) by alkali cleaning pump (7) and valve; NaHS storage tank (4) is switched to alkaline bath (2) for the second time by pump (8), and alkaline bath (2) is switched to alkaline bath (1) for the first time by alkali cleaning pump (9) for the second time; Alkali surge-tank (5) is switched to alkaline bath (3) for the third time by alkali transfer pump (10), and alkaline bath (3) is switched to alkaline bath (2) for the second time by alkali cleaning pump (11) for the third time; After alkaline bath (3), connect for the third time scrubbing tower (6).
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| Application Number | Priority Date | Filing Date | Title |
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| CN201110218352.0A CN102408100B (en) | 2011-08-02 | 2011-08-02 | Sodium sulfhydrate product with concentration of 22% and low content of carnallite produced from viscose fiber waste gas |
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|---|---|---|---|
| CN201110218352.0A CN102408100B (en) | 2011-08-02 | 2011-08-02 | Sodium sulfhydrate product with concentration of 22% and low content of carnallite produced from viscose fiber waste gas |
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| CN102408100B true CN102408100B (en) | 2014-08-20 |
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| CN104826465B (en) * | 2014-02-10 | 2017-05-17 | 中国石油化工股份有限公司 | Multi-stage countercurrent absorption process and system for acidic gas |
| CN104826468B (en) * | 2014-02-10 | 2017-05-31 | 中国石油化工股份有限公司 | A kind of Acidic Gas Treating technique and system |
| CN104826464B (en) * | 2014-02-10 | 2017-05-17 | 中国石油化工股份有限公司 | Novel acidic gas treating process and apparatus |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101530726A (en) * | 2008-04-11 | 2009-09-16 | 玛纳斯澳洋科技有限责任公司 | Method for processing waste gas from the production of viscose chemical fiber |
| CN201643967U (en) * | 2010-03-22 | 2010-11-24 | 江苏蓝之达环境科技股份有限公司 | Industrial waste gas treatment and recycling device |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101530726A (en) * | 2008-04-11 | 2009-09-16 | 玛纳斯澳洋科技有限责任公司 | Method for processing waste gas from the production of viscose chemical fiber |
| CN201643967U (en) * | 2010-03-22 | 2010-11-24 | 江苏蓝之达环境科技股份有限公司 | Industrial waste gas treatment and recycling device |
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Address after: 256500 Binhe Road, Boxing County, Shandong, 333 Patentee after: Shandong Yamei Technology Co., Ltd. Patentee after: Shandong Bohi Industry Co., Ltd. Patentee after: QINGDAO HOHO HUITU ENGINEERING TECHNOLOGY CO., LTD. Address before: 256500 Binhe Road, Boxing County, Shandong, 333 Patentee before: Shandong Yamei Technology Co., Ltd. Patentee before: Shandong Bohi Industry Co., Ltd. Patentee before: Qingdao Bohi Hoho Eng. & Tech. Co., Ltd. |