CN103920363A - Method and device for treating sulfurous industrial waste gas - Google Patents
Method and device for treating sulfurous industrial waste gas Download PDFInfo
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- CN103920363A CN103920363A CN201410136944.1A CN201410136944A CN103920363A CN 103920363 A CN103920363 A CN 103920363A CN 201410136944 A CN201410136944 A CN 201410136944A CN 103920363 A CN103920363 A CN 103920363A
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- waste gas
- carbon disulfide
- industrial waste
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- hydrogen sulfide
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Abstract
The invention belongs to the fields of chemical industry and environment protection, relates to a method and a device for treating industrial waste gas, and particularly relates to a method and a device for treating waste gas of viscose production enterprises. More specifically, the method comprises the step of cooling carbon-disulfide-containing gas before adsorbing carbon disulfide (activated carbon adsorption, for example). By virtue of the method or the device, carbon disulfide and even hydrogen sulfide can be efficiently removed (or recovered); besides, the adsorption rate of activated carbon to carbon disulfide can be enhanced and the adsorption activity of the activated carbon can be maintained. In addition, the freezing phenomenon in condensing equipment (condenser) after desorption is reduced. The method and the device do not need big transformation on the original recovering system (a viscose production enterprise waste gas recovering system for example), so that the economic cost of the enterprise is reduced.
Description
Technical field
The invention belongs to chemical industry and field of Environment Protection, relate to a kind of industrial waste gas processing method and device, particularly, relate to a kind of viscose rayon manufacturing enterprise's waste gas processing method (recovery method) and device.
Background technology
CS
2and H
2s is pollutant common in industrial gas emission, can produce comparatively serious harm to environment and biological health.CS in waste gas
2and H
2s can also recycle.
Viscose rayon manufacturing enterprise waste gas major pollutants are H
2s, CS
2.General " the three grades of alkali cleaning+active carbon adsorption " method that adopts recycles technology waste gas at present.As shown in Figure 1, its technological process is also summarized as follows in " alkali cleaning-charcoal absorption " technological process:
Use air-introduced machine will be containing H
2s, CS
2viscose rayon manufacturing enterprise waste gas by three grades of caustic wash towers, in caustic wash tower, spray NaOH solution (normal temperature), process the H in waste gas
2s, the two reaction generates NaHS, can discharge outer selling, for the production of NaHS tablet.
Waste gas through alkali cleaning is carried out to demist processing.Be not limited to theoretical restriction, the object of demist is mainly the water droplet producing while removing alkali cleaning spray, can use the conventional methods such as cyclonic separation, nonwoven, sintered metal filtration, wherein simple with cyclonic separation method.
Gas after demist is sent to adsorption tower absorption CS
2, the active carbon desorb according to a conventional method (carrying out desorption with high steam after nitrogen filled protection) of having adsorbed carbon disulfide.After absorption, remaining tail gas drains into 120m toxin expelling tower high altitude discharge.
The H of viscose rayon enterprise
2s, CS
2discharge, carries out " emission standard for odor pollutants " (GB14554-93) secondary standard limit value in table 2; H
2s:21kg/h; CS
2: 97kg/h.Through above-mentioned " alkali cleaning-charcoal absorption " technique, H
2s discharge can reach discharge standard substantially, but in practice, finds CS
2even be also difficult to reach the desired 97kg/h of this standard through active carbon adsorption.
In addition part CS in alkaline cleaning procedure,
2can condensation sneak in NaHS solution, in the time making tablet retort solution, overflow, can form secondary pollution to atmosphere.Carbon disulfide is poisonous, also can cause direct threat to operating personnel healthy.In addition carbon disulfide also can bring the unsafe factors such as burning, blast.
At present, this area is needed particularly treatment process and the device of the carbon disulfide in viscose rayon manufacturing enterprise waste gas of a kind of effective removal industrial waste gas badly.
Summary of the invention
The inventor is through deep research and performing creative labour, obtain a kind ofly can effectively removing the particularly process of the carbon disulfide in viscose rayon manufacturing enterprise waste gas of industrial waste gas, and the inventor is surprised to find, use method of the present invention, (recovery) carbon disulfide not only can be removed efficiently, and the adsorption rate of active carbon to carbon disulfide and the adsorption activity of maintenance active carbon can be improved.Described method has also further improved removal (recovery) efficiency of hydrogen sulfide.Following invention is provided thus:
One aspect of the present invention relates to a kind of method of removing or reclaim carbon disulfide from industrial waste gas, is included in carbon disulfide is adsorbed to (for example charcoal absorption) before, to the step of processing of lowering the temperature containing the gas of carbon disulfide.
According to the method described in any one of the present invention, wherein, described cooling is treated to the gas containing carbon disulfide is cooled to 1 DEG C-20 DEG C, 2 DEG C-15 DEG C, 3 DEG C-12 DEG C, 1 DEG C-10 DEG C, 1 DEG C-4 DEG C, 4 DEG C-10 DEG C, 4 DEG C-6 DEG C; The temperature range forming between any two of 1 DEG C, 2 DEG C, 3 DEG C, 4 DEG C, 5 DEG C, 6 DEG C, 7 DEG C, 8 DEG C, 9 DEG C, 10 DEG C, 11 DEG C or 12 DEG C or these concrete numerical value.
According to the method described in any one of the present invention, wherein, described cooling is processed by chilled water (0-15 DEG C) condensation and is realized; Preferably, described cooling was processed before carbon disulfide is adsorbed; More preferably, before carbon disulfide is adsorbed and after demist.
Be not limited to theoretical restriction, in enterprise, condensed water is generally divided into three kinds: normal-temperature water (by season and be roughly from different places 18 DEG C-25 DEG C), chilled water (being roughly 0 DEG C-15 DEG C), cryogenic refrigeration water (below 0 DEG C).Wherein, normal-temperature water is general in line or use by air cool cycles, and chilled water is to add that with refrigerator heat exchanger realizes, and cryogenic refrigeration water is general direct to freeze by freezing unit.The inventor finds by research, and normal-temperature water can not achieve the goal, and cryogenic refrigeration water can cause that condenser freezes, block system, adopts the effect of chilled water best.
In one embodiment of the invention, after demist, before absorption, increase by one 1 DEG C-10 DEG C or 4 DEG C of-10 DEG C of chilled water condensing units, waste gas is carried out to condensation.
The inventor is surprised to find, and processes by cooling, can effectively improve removal or the organic efficiency of carbon disulfide.
The inventor is also surprised to find, and processes by cooling, can also improve the adsorption rate of active carbon to carbon disulfide and maintain the adsorption activity of active carbon.In addition, also reduced the icing phenomenon in condensing plant (condenser).
Be not limited to theoretical restriction, the CS that can make in waste gas is processed in cooling
2before entering activated carbon adsorber, waste gas under condensation, reduces as far as possible CS in waste gas
2concentration, alleviates the load of charcoal absorption, can make after demist simultaneously remaining steam also as much as possible condensation get off, further reduce the water vapour content in waste gas, avoid the activity of active carbon to be destroyed by steam.And because charcoal absorption is exothermic reaction, the waste gas of lower temperature enters adsorption tower and is conducive to active carbon and more thoroughly adsorbs the carbon disulfide in waste gas.In addition, adopt 1 DEG C-10 DEG C or 4 DEG C-10 DEG C, can ensure that maximum possible reduces CS in waste gas
2when concentration and vapor content, steam can not freeze in condenser, causes system jams.The carbon disulfide that in chilled water condensing unit, condensation is got off and water reclaim after entering the decker of active carbon desorption system.
According to the method described in any one of the present invention, wherein, described industrial waste gas also comprises hydrogen sulfide; Particularly, described industrial waste gas is the waste gas of producing viscose rayon discharge.
According to the method described in any one of the present invention, before it is also included in described cooling processing and/or demist, remove or reclaim the step of hydrogen sulfide; Particularly, for waste gas being carried out to for example three grades of alkali cleanings of alkali cleaning; More specifically, use NaOH solution to carry out alkali cleaning.
According to the method described in any one of the present invention, wherein, the temperature of described NaOH solution be >=25 DEG C, >=30 DEG C, >=35 DEG C, >=45 DEG C, 30 DEG C-65 DEG C, 35 DEG C-60 DEG C, 40 DEG C-55 DEG C, 40 DEG C-52 DEG C, 40 DEG C-50 DEG C, 45 DEG C-55 DEG C, 45 DEG C-52 DEG C, 45 DEG C-50 DEG C; Preferably, be 47 DEG C-55 DEG C, 47 DEG C-52 DEG C, 47 DEG C-50 DEG C; Preferably, be the temperature range forming between 45 DEG C, 46 DEG C, 47 DEG C, 48 DEG C, 49 DEG C, 50 DEG C, 51 DEG C, 52 DEG C, 53 DEG C, 54 DEG C or 55 DEG C or these concrete numerical value any two.
The inventor is surprised to find, with said temperature particularly preferably the NaOH solution of temperature carry out alkali cleaning, can effectively improve removal or the organic efficiency of hydrogen sulfide.Be not limited to theoretical restriction, under said temperature, can accelerate NaOH and H
2the reaction speed of S, reduces the H in tail gas or waste gas
2s content; In addition, can also prevent CS
2condensation, forms secondary pollution in order to avoid process when NaHS solution is made tablet.
The inventor also found through experiments, and higher NaOH solution temperature (for example, higher than 55 DEG C) is although can further reduce H in tail gas
2s content, but CS in tail gas
2content can not reach " emission standard for odor pollutants " (GB14554-93) in regulation secondary standard limit value 97kg/h.Be not limited to theoretical restriction, one of possible cause is because the EGT after alkali cleaning increases, and has increased the burden of demist and chilled water condensation, part CS in waste gas
2can not be condensed and adsorb.Particularly preferably, NaOH solution temperature is 47 DEG C-50 DEG C.
According to the method described in any one of the present invention, wherein, the concentration of described NaOH solution is 10%-40%; Be preferably 15%-30%; More preferably 18%-25% or 18%-22%; More preferably 18%-20%; Be particularly preferably 18%-19%, for example 18%, 18.5% or 19% or any two of these concrete numerical value between the concentration range that forms.
The inventor obtains the concentration range of above-mentioned NaOH solution through experimental study repeatedly.Be not limited to theoretical restriction, inventor's discovery, if concentration of lye is too low, wherein moisture content is higher, the ultimate density of the NaHS solution that reaction generates is lower; If concentration of lye is too high, after reaction, have remaining NaOH and do not participate in reaction, cause waste, can affect the purity of NaHS simultaneously.
Be not limited to theoretical restriction, the NaHS solution of generation can be made NaHS tablet by steps such as distillation, purifications.Preferably, NaHS solution being heated to 100 DEG C distills.In the time that the concentration of NaHS solution reaches 18%-24%, from the angle of saving heat of evaporation, cost compare is low; Preferably, the concentration of NaHS solution be 18%, 19%, 20%, 21% or 22% or any two of these concrete numerical value between the concentration range that forms.
In one embodiment of the invention, described method as shown in Figure 2.
Another aspect of the present invention relates to a kind of industrial waste gas processing method, comprises the removal described in any one in the present invention or reclaims the method for carbon disulfide; Particularly, described industrial waste gas contains carbon disulfide or carbon disulfide and hydrogen sulfide; Particularly, described industrial waste gas is the waste gas of producing viscose rayon discharge.
Of the present inventionly relate in one aspect to a kind of device of carbon disulfide removed or reclaim from industrial waste gas, it comprises the unit to the processing of lower the temperature containing the gas of carbon disulfide again; Particularly, be chilled water condensing unit.
Of the present inventionly relate in one aspect to again a kind of industrial waste gas that utilizes and produce the method for NaHS, comprise the alkali cleaning step described in any one or three grades of alkali cleaning steps in the present invention; Particularly, industrial waste gas comprises hydrogen sulfide; More specifically, described industrial waste gas is the waste gas of producing viscose rayon discharge.
In the present invention, described gas or waste gas or industrial waste gas, if not otherwise specified, refer to the waste gas of industrial discharge or pass through and process the gas that does not still meet discharging standards.It is not limited to (for example 25 DEG C, 1 standard atmospheric pressure) under normal temperature and pressure is gaseous state completely, wherein also can contain the solia particle of mist or suspended state.
In one embodiment of the invention, described industrial waste gas contains carbon disulfide and/or hydrogen sulfide.In a specific embodiment of the present invention, described industrial waste gas is the waste gas of producing viscose rayon discharge.
In the present invention, the concentration of described NaOH solution or NaHS solution, if not otherwise specified, is mass percent concentration.
The beneficial effect of the invention
The present invention for example, without the equipment of former recovery system (viscose rayon manufacturing enterprise gas recovery system) is done to very large transformation, do not need more investment, on prior art basis, for example only increase a set of chilled water condensing unit, and change alkali washing process temperature, just can guarantee the CS in waste gas
2discharge reaches 97kg/h below the mark of national regulation, and makes H
2s concentration of emission is lower.
Brief description of the drawings
Fig. 1: the viscose rayon manufacturing enterprise waste-gas treatment process flow schematic diagram adopting at present.
Fig. 2: viscose rayon of the present invention manufacturing enterprise waste-gas treatment process flow schematic diagram.
Detailed description of the invention
Below in conjunction with embodiment, embodiment of the present invention are described in detail, but it will be understood to those of skill in the art that the following example is only for the present invention is described, and should not be considered as limiting scope of the present invention.Unreceipted actual conditions person in embodiment, carries out according to the condition of normal condition or manufacturer's suggestion.The unreceipted person of production firm of agents useful for same or instrument, being can be by the conventional products of commercial acquisition.
comparative example 1: PROCESS FOR TREATMENT viscose rayon of the prior art manufacturing enterprise waste gas
NaOH solution with normal temperature (25 DEG C) 18.5% carries out alkali cleaning, and (as accompanying drawing 1) adsorbed in existing technological process.
With H in methylene blue spectrophotometry toxin expelling tower tail gas
2s content, is 11.2kg/h, lower than " emission standard for odor pollutants " (GB14554-93) the secondary standard limit value 21kg/h in table 2.
But with CS in diethylamine spectrophotometry toxin expelling tower tail gas
2content, is 113.11kg/h, higher than " emission standard for odor pollutants " (GB14554-93) the secondary standard limit value 97kg/h in table 2.
In the time that normal-temperature water is carried out alkali cleaning spray, collect sample, can see that upper strata is the NaHS aqueous solution, the CS that lower floor has condensation to get off
2.The every generation 22%NaHS aqueous solution 100ml 6ml carbon disulfide that can condensation gets off.
embodiment 1: the PROCESS FOR TREATMENT (1) of viscose rayon manufacturing enterprise waste gas
18.5% the NaOH solution with 50 DEG C carries out alkali cleaning, with technique of the present invention (as accompanying drawing 2), first carries out after condensation with 10 DEG C of chilled waters, then makes waste gas enter activated carbon adsorber.
With with comparative example 1 in same method detect H in toxin expelling tower tail gas
2s and CS
2content, is respectively 8.67kg/h and 90.44kg/h, lower than 21kg/h and the 97kg/h of national Specification, and also respectively lower than content 11.2kg/h and 113.11kg/h in comparative example 1.
In the NaHS aqueous solution generating, do not observe carbon disulfide layering.
embodiment 2: the PROCESS FOR TREATMENT (2) of viscose rayon manufacturing enterprise waste gas
18.5% the NaOH solution with 50 DEG C carries out alkali cleaning, with technique of the present invention (as accompanying drawing 2), first carries out after condensation with 4 DEG C of chilled waters, then makes waste gas enter activated carbon adsorber.
With with comparative example 1 in same method detect H in toxin expelling tower tail gas
2s and CS
2content, is respectively 8.75kg/h and 79.83kg/h, lower than 21kg/h and the 97kg/h of national Specification, and H
2s content and embodiment 1 approach, but CS
2content is lower than the 90.44kg/h of embodiment 1.
In the NaHS aqueous solution generating, do not observe carbon disulfide layering.
The result of embodiment 1-2 shows, method of the present invention can make the waste gas of Viscose Fiber Plant discharge reach " emission standard for odor pollutants " requirement (GB14554-93), and is significantly better than the prior art taking comparative example 1 as representative aspect reducing the efficiency of hydrogen sulfide and carbon disulfide in gas discharging.In addition, embodiment 1 and embodiment 2 relatively, illustrate that chilled water temperature is lower, are more conducive to active carbon to CS
2absorption.
the PROCESS FOR TREATMENT (3) of embodiment 3. viscose rayon manufacturing enterprise waste gas
Carry out according to method in the same manner as in Example 1, except the temperature of NaOH solution is 47 DEG C.
H in tail gas
2s content is 8.89kg/h, CS
2content is 90.44kg/h.
In the NaHS aqueous solution generating, do not observe carbon disulfide layering.
embodiment 4: the PROCESS FOR TREATMENT (4) of viscose rayon manufacturing enterprise waste gas
Carry out according to method in the same manner as in Example 2, except the temperature of NaOH solution is 47 DEG C.
H in tail gas
2s content is 8.84kg/h.CS
2content is 79.83kg/h.
In the NaHS aqueous solution generating, do not observe carbon disulfide layering.
The result of comparative example 1,2 and embodiment 3,4 shows, higher NaOH solution temperature can accelerate itself and H
2the reaction of S, reduces H in tail gas
2the content of S, and to CS
2content substantially do not affect.
embodiment 5: the PROCESS FOR TREATMENT (5) of viscose rayon manufacturing enterprise waste gas
Carry out according to method in the same manner as in Example 1, except the temperature of NaOH solution is 25 DEG C of normal temperature.
CS in tail gas
2content is 90.49kg/h, H
2s content is 11.21kg/h.
In the NaHS aqueous solution generating, observe carbon disulfide layering.
embodiment 6: the PROCESS FOR TREATMENT (6) of viscose rayon manufacturing enterprise waste gas
Carry out according to method in the same manner as in Example 2, except the temperature of NaOH solution is 25 DEG C of normal temperature.
CS in tail gas
2content is 79.81, H
2s content is 11.21.
In the NaHS aqueous solution generating, observe carbon disulfide layering.
From the result of embodiment 5 and 6, although CS in tail gas
2content and H
2s content meets standard, but contains carbon disulfide in the NaHS aqueous solution generating, and this has not only affected the purity of NaHS solution, also can in the time that NaHS solution is made tablet, form secondary pollution.
embodiment 7: the PROCESS FOR TREATMENT (7) of viscose rayon manufacturing enterprise waste gas
Carry out according to method in the same manner as in Example 1, except the temperature of NaOH solution is 55 DEG C.
CS in tail gas
2content is 99.89kg/h, H
2s content is 10.71kg/h.
In the NaHS aqueous solution generating, do not observe carbon disulfide layering.
embodiment 8: the PROCESS FOR TREATMENT (8) of viscose rayon manufacturing enterprise waste gas
Carry out according to method in the same manner as in Example 2, except the temperature of NaOH solution is 55 DEG C.
CS in tail gas
2content is 97.81kg/h, H
2s content is 10.71kg/h.
In the NaHS aqueous solution generating, do not observe carbon disulfide layering.
The result of embodiment 7,8 shows, although higher NaOH solution temperature can further reduce H in tail gas
2s content, but CS in tail gas
2content can not reach " emission standard for odor pollutants " (GB14554-93) in table 2 regulation secondary standard limit value 97kg/h.The reason that part is possible is that the EGT after alkali cleaning increases, and has increased the burden of demist and chilled water condensation, part CS in waste gas
2can not be condensed and adsorb.Therefore it is more suitable that the NaOH solution temperature of, getting alkali cleaning is 47 DEG C-50 DEG C.
Although the specific embodiment of the present invention has obtained detailed description, it will be understood to those of skill in the art that.According to disclosed all instructions, can carry out various amendments and replacement to those details, these change all within protection scope of the present invention.Four corner of the present invention is provided by claims and any equivalent thereof.
Claims (10)
1. a method of removing or reclaim carbon disulfide from industrial waste gas, is included in carbon disulfide is adsorbed to (for example charcoal absorption) before, to the step of processing of lowering the temperature containing the gas of carbon disulfide.
2. method according to claim 1, wherein, described cooling is treated to the gas containing carbon disulfide is cooled to 1 DEG C-20 DEG C, 2 DEG C-15 DEG C, 3 DEG C-12 DEG C, 1 DEG C-10 DEG C, 1 DEG C-4 DEG C, 4 DEG C-10 DEG C, 4 DEG C-6 DEG C, 1 DEG C, 2 DEG C, 3 DEG C, 4 DEG C, 5 DEG C, 6 DEG C, 7 DEG C, 8 DEG C, 9 DEG C, 10 DEG C, 11 DEG C or 12 DEG C.
3. method according to claim 1, wherein, described cooling is processed and is realized by chilled water condensation; Preferably, described cooling was processed before carbon disulfide is adsorbed; More preferably, before carbon disulfide is adsorbed and after demist.
4. method according to claim 1, wherein, described industrial waste gas also comprises hydrogen sulfide; Particularly, described industrial waste gas contains carbon disulfide or carbon disulfide and hydrogen sulfide; Particularly, described industrial waste gas is the waste gas of producing viscose rayon discharge.
5. method according to claim 4, its be also included in that described cooling is processed and/demist before, remove or reclaim the step of hydrogen sulfide; Particularly, for waste gas being carried out to for example three grades of alkali cleanings of alkali cleaning; More specifically, use NaOH solution to carry out alkali cleaning.
6. method according to claim 5, wherein, the temperature of described NaOH solution be >=25 DEG C, >=30 DEG C, >=35 DEG C, >=45 DEG C, 30 DEG C-65 DEG C, 35 DEG C-60 DEG C, 40 DEG C-55 DEG C, 40 DEG C-52 DEG C, 40 DEG C-50 DEG C, 45 DEG C-55 DEG C, 45 DEG C-52 DEG C, 45 DEG C-50 DEG C; Preferably, be 47 DEG C-55 DEG C, 47 DEG C-52 DEG C, 47 DEG C-50 DEG C, 45 DEG C, 46 DEG C, 47 DEG C, 48 DEG C, 49 DEG C, 50 DEG C, 51 DEG C, 52 DEG C, 53 DEG C, 54 DEG C or 55 DEG C.
7. method according to claim 5, wherein, the concentration of described NaOH solution is 10%-40%; Be preferably 15%-30%; More preferably 18%-25% or 18%-22%; More preferably 18%-20%; Be particularly preferably 18%-19%, for example 18%, 18.5% or 19%.
8. an industrial waste gas processing method, comprises the removal described in any one in claim 1-7 or reclaims the method for carbon disulfide; Particularly, described industrial waste gas is the waste gas of producing viscose rayon discharge.
9. from industrial waste gas, remove or reclaim a device for carbon disulfide, it comprises the unit of processing that lowers the temperature containing the gas of carbon disulfide; Particularly, be chilled water condensing unit.
10. utilize industrial waste gas to produce a method for NaHS, comprise the alkali cleaning step described in any one or three grades of alkali cleaning steps in claim 5-7; Particularly, industrial waste gas comprises hydrogen sulfide; More specifically, described industrial waste gas is the waste gas of producing viscose rayon discharge.
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| CN107876011A (en) * | 2017-11-07 | 2018-04-06 | 常州布奇纺织有限公司 | A kind of sulfur-bearing industrial waste gas processing method |
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