CN111013333A - Method for treating hydrogen sulfide in waste gas generated in viscose fiber production - Google Patents
Method for treating hydrogen sulfide in waste gas generated in viscose fiber production Download PDFInfo
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- CN111013333A CN111013333A CN201911349024.7A CN201911349024A CN111013333A CN 111013333 A CN111013333 A CN 111013333A CN 201911349024 A CN201911349024 A CN 201911349024A CN 111013333 A CN111013333 A CN 111013333A
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- waste gas
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- fiber production
- viscose fiber
- absorption liquid
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 76
- 239000002912 waste gas Substances 0.000 title claims abstract description 73
- 229920000297 Rayon Polymers 0.000 title claims abstract description 58
- 238000007380 fibre production Methods 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000010521 absorption reaction Methods 0.000 claims abstract description 114
- 239000007788 liquid Substances 0.000 claims abstract description 80
- 230000008929 regeneration Effects 0.000 claims abstract description 45
- 238000011069 regeneration method Methods 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 239000011874 heated mixture Substances 0.000 claims abstract description 5
- 239000013067 intermediate product Substances 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 239000000543 intermediate Substances 0.000 claims abstract description 3
- 238000011084 recovery Methods 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 46
- 239000002608 ionic liquid Substances 0.000 claims description 27
- 238000003795 desorption Methods 0.000 claims description 25
- 239000002250 absorbent Substances 0.000 claims description 18
- 230000002745 absorbent Effects 0.000 claims description 18
- 230000007797 corrosion Effects 0.000 claims description 9
- 238000005260 corrosion Methods 0.000 claims description 9
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 8
- 239000012190 activator Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 238000009987 spinning Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 239000002994 raw material Substances 0.000 description 11
- 238000000746 purification Methods 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000000979 retarding effect Effects 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
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1425—Regeneration of liquid absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
- B01D53/1468—Removing hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/304—Hydrogen sulfide
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
Discloses a method for treating hydrogen sulfide in waste gas generated in viscose fiber production, belonging to the technical field of spinning. Which comprises the following steps: obtaining production waste gas from a viscose fiber production plant; the waste gas containing H2After the absorption tower of the S absorption liquid, H is obtained2S absorption liquid and H removal2S; said compound containing H2Absorbing heat of the absorbing liquid of S by a heat exchanger to obtain heated H-containing liquid2An absorption liquid of S; said heated mixture containing H2The absorption liquid of S is regenerated and desorbed by a regeneration tower to obtain H2S recovery of intermediates and regeneration of H2S absorption liquid; said H2S, cooling and gas-liquid separating the recovered intermediate product to obtain recovered H2S and condensed water; the recovered H2S is sent to H2S, storing a tank; the condensed water is sent to a regeneration tower. It has the advantages of low investment, safe operation, low cost and H tolerance2Good S treatment effect and H2The S removal rate is more than or equal to 95 percent and is suitable for low H2And (5) treating the viscose waste gas with the S concentration.
Description
Technical Field
The invention relates to the technical field of spinning, in particular to a method for treating hydrogen sulfide in waste gas generated in viscose fiber production.
Background
The excellent use properties of viscose fibres and the ready availability and reproducibility of the main raw material cellulose determine that it will be highly desirable for a long time, but in the production of viscose fibres, large amounts of hydrogen sulphide (H) are produced2S) and carbon disulfide (CS)2) The waste gas causes serious pollution to the environment. The efficient and economic treatment of waste gas is always a technical problem in the viscose industry. At present, the viscose fiber production waste gas is mainly treated by adopting alkali washing H of German Lurgi (Lurgi) company2S plus active carbon adsorption of CS2The two technologies are large in investment and high in operation cost, especially the low-concentration waste gas treatment cost is higher, and the purpose of treating the odor of an enterprise cannot be achieved, so that the production of the enterprise often causes dissatisfaction of residents around a plant area, and even a plurality of viscose filament yarn enterprises directly discharge the waste gas without treating the waste gas; alkali washing H2Sodium hydrosulfide produced as a byproduct in the S method belongs to hazardous chemicals and brings certain potential safety hazard.
Disclosure of Invention
In view of the above, the present invention provides a method for treating hydrogen sulfide in waste gas from viscose fiber production, which has the advantages of low investment, safe operation, low cost and H component content2Good S treatment effect and H2The S removal rate is more than or equal to 95 percent and is suitable for low H2And the treatment of the viscose waste gas with the S concentration is more practical.
In order to achieve the purpose, the technical scheme of the method for treating the hydrogen sulfide in the waste gas generated in the viscose fiber production provided by the invention is as follows:
the method for treating hydrogen sulfide in waste gas generated in viscose fiber production comprises the following steps:
obtaining production waste gas from a viscose fiber production plant;
the waste gas containing H2After the absorption tower of the S absorption liquid, H is obtained2S absorption liquid and H removal2S;
said compound containing H2The absorption liquid of S absorbs heat through the heat exchangerTo obtain a heated mixture containing H2An absorption liquid of S;
said heated mixture containing H2The absorption liquid of S is regenerated and desorbed by a regeneration tower to obtain H2S recovery of intermediates and regeneration of H2S absorption liquid;
said H2S, cooling and gas-liquid separating the recovered intermediate product to obtain recovered H2S and condensed water;
the recovered H2S is sent to H2S, storing a tank;
the condensed water is sent to a regeneration tower.
The method for treating hydrogen sulfide in waste gas generated in viscose fiber production provided by the invention can be further realized by adopting the following technical measures.
Preferably, in the absorption column, the H is2And spraying the S absorption liquid from the upper part of the absorption tower.
Preferably, the heated mixture contains H2When the absorption liquid of S enters the regeneration tower, the absorption liquid enters from the upper part of the regeneration tower, and H2S recycling intermediate products are discharged from the upper part of the regeneration tower.
As a preference, the first and second liquid crystal compositions are,
the temperature range of the waste gas generated in the viscose fiber production is 20-60 ℃;
h of waste gas generated in production of viscose fibers2The S content value range is 100-12000 mg/m3。
Preferably, said H is2S absorption liquid is composed of H2S absorbent, water, a small amount of activator, corrosion inhibitor and antioxidant; wherein,
the concentration of the absorbent is 0.5-5.0 mol/L, the concentration of the activator is 0.02-0.15 mol/L, the concentration of the corrosion inhibitor is 0.1-0.2 wt%, the concentration of the antioxidant is 0.1-0.2 wt%, and the balance is water.
Preferably, the H in the off-gas in the absorption tower2S is sprayed from the upper part of the absorption tower2The absorption temperature of the S absorption liquid ranges from 30 ℃ to 50 ℃.
Preferably, the absorption H is2The absorption liquid after S enters from the bottom of the absorption tower through a pumpThe heat exchanger absorbs heat and then enters the regeneration tower from the upper part of the regeneration tower for regeneration and desorption H2The desorption temperature of S is 75-100 ℃.
Preferably, said H is2S absorbent is ionic liquid, which is in the H2The concentration range of the S absorption liquid is 0.5-5.0 mol/L.
Preferably, the ionic liquid is represented by the following structure:
[(R1-)(R2-)N-R3-NH2 +-R4]A-or [ (-R)5-)N-R3-NH2 +-R4]A-；
Wherein,
R1-、R2-: an alkyl group having 1 to 6 carbon atoms;
R4-: an alkyl group having 1 to 4 carbon atoms;
R1-、R2-、R4-: the three are different, the same or any two of the three are the same;
-R3-: an alkylene group having 2 to 6 carbon atoms;
-R5-: an alkylene group having 3 to 8 carbon atoms;
-R3-、-R5-: the two are different or the same;
A-：CH3COO-、BF4 -、PF6 -one kind of (1).
Preferably, the removal of H is carried out2And (4) sending the waste gas of the S into a waste gas flue for treatment to obtain clean gas.
The method for treating hydrogen sulfide in waste gas generated in viscose fiber production can be applied to waste gas treatment of newly-built viscose fiber production enterprises, can also be used for carrying out technical upgrading and reconstruction on waste gas treatment of the existing viscose fiber production enterprises, can also be used for additionally carrying out waste gas treatment on viscose filament yarn enterprises which do not carry out waste gas treatment, and can be used for treating recovered H generated in waste gas generated in viscose fiber production by treating the waste gas2S is sent into H2S storage tank for preparing adhesiveRaw material sulfuric acid and condensed water produced in the production of the viscose are sent into a regeneration tower for recycling, and H is removed2The waste gas of S has little harm to the environment. Compared with the existing waste gas treatment technology, the method can greatly reduce investment, reduce operation cost, reduce the influence on the environment, does not produce secondary pollution, and has higher safety, thereby promoting the sustainable long-term development of enterprises.
Drawings
Fig. 1 is a flow chart of a substance change process in a process of a method for treating hydrogen sulfide in waste gas generated in viscose fiber production according to an embodiment of the present invention.
Detailed Description
The invention aims to solve the problems in the prior art and provides a method for treating hydrogen sulfide in waste gas generated in viscose fiber production, which has the advantages of low investment, safe operation, low cost and H pair2Good S treatment effect and H2The S removal rate is more than or equal to 95 percent and is suitable for low H2And the treatment of the viscose waste gas with the S concentration is more practical.
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description will be given of the method for treating hydrogen sulfide in waste gas from viscose fiber production according to the present invention with reference to the accompanying drawings and preferred embodiments, and the detailed description thereof. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the features, structures, or characteristics of one or more embodiments may be combined in any suitable manner.
The term "and/or" herein is merely an association describing an associated object, meaning that three relationships may exist, e.g., a and/or B, with the specific understanding that: both a and B may be included, a may be present alone, or B may be present alone, and any of the three cases can be provided.
Referring to FIG. 1, in the following description, "feed gas" refers to exhaust gas collected from a viscose fiber production plant; "purge gas" means H in the exhaust gas2S is sprayed from the upper part of the absorption tower2S absorption liquid absorbs and removes H2The waste gas after S; "in raw gas H2The removal rate of S is expressed as H in viscose waste gas2S treatment effect, H in raw material gas2Removal rate (%) of S was 100 (H in raw material gas)2S content-H in purified gas2S content)/H in feed gas2The S content.
Example 1:
at a temperature of 20 ℃ H2The S content is 4675mg/m3Is continuously fed into an absorption tower where H in the feed gas is2S is sprayed from the upper part of the absorption tower2S is absorbed by an absorption liquid containing 1.5mol/L of ionic liquid [ (CH)3-)(CH3CH2CH2CH2-)N-CH2CH2CH2-NH2 +-CH2CH3]CH3COO-The absorption temperature is 30 ℃, and H is removed2The purified gas after S is sent into a waste gas flue for other treatment; absorption of H2The absorption liquid (rich liquid) after S enters a lean-rich liquid heat exchanger from the bottom of the absorption tower through a pump, absorbs heat and then enters a regeneration tower from the upper part of the regeneration tower to be regenerated and desorbed H2S, desorption temperature is 85 ℃, desorption H2The absorption liquid (barren solution) after S flows out from the bottom of the regeneration tower, enters the upper part of the absorption tower after heat exchange of a pump, a barren and rich solution heat exchanger and a barren solution cooler, and absorbs H again2S, the absorption liquid circulates back and forth to form continuous absorption and desorption H2S; desorbed H2S is cooled by a condenser, condensed water is separated by a gas-liquid separator and then is sent to H2S, a storage tank for preparing raw material sulfuric acid for viscose fiber production; and sending the condensed water separated from the gas-liquid separator to a regeneration tower. H in the purified gas was measured at any time point after 0.5H of the treatment run2The S content is 77mg/m3In the feed gas H2The removal rate of S was 98.4%.
Example 2:
the other example is the same as example 1, except that the ionic liquid in the absorbent solution is [ (CH)3-)(CH3CH2CH2CH2-)N-CH2CH2CH2-NH2 +-CH2CH3]PF6 -. Purification of H from gas2The S content is 96mg/m3In the feed gas H2The removal rate of S was 97.9%.
Example 3:
the other example is the same as example 1, except that the ionic liquid in the absorbent solution is [ (CH)3-)(CH3CH2CH2CH2-)N-CH2CH2CH2-NH2 +-CH2CH3]BF4 -. Purification of H from gas2The S content is 89mg/m3In the feed gas H2The removal rate of S was 98.1%.
Example 4:
the temperature is 35 ℃, H2The S content is 2805mg/m3Is continuously fed into an absorption tower where H in the feed gas is2S is sprayed from the upper part of the absorption tower2S is absorbed by an absorption liquid containing 2.1mol/L of ionic liquid [ (CH)3CH2CH2CH2-)(CH3CH2CH2CH2-)N-CH2CH2-NH2 +-CH2CH2CH2CH3]CH3COO-The absorption temperature is 40 ℃, and H is removed2The purified gas after S is sent into a waste gas flue for other treatment; absorption of H2The absorption liquid (rich liquid) after S enters a lean-rich liquid heat exchanger from the bottom of the absorption tower through a pump, absorbs heat and then enters a regeneration tower from the upper part of the regeneration tower to be regenerated and desorbed H2S, desorption temperature is 90 ℃, desorption H2The absorption liquid (barren solution) after S flows out from the bottom of the regeneration tower, enters the upper part of the absorption tower after heat exchange of a pump, a barren and rich solution heat exchanger and a barren solution cooler, and absorbs H again2S, the absorption liquid circulates back and forth to form continuous absorption and desorption H2S; desorbed H2S is cooled by a condenser, condensed water is separated by a gas-liquid separator and then is sent to H2S, a storage tank for preparing raw material sulfuric acid for viscose fiber production; and sending the condensed water separated from the gas-liquid separator to a regeneration tower. After 0.5h of treatment operationMeasurement of H in purified gas at any time2The S content is 17mg/m3In the feed gas H2The removal rate of S was 99.4%.
Example 5:
the other example is the same as example 4 except that the ionic liquid in the absorbent solution is [ (CH)3CH2-)(CH3CH2CH2CH2CH2CH2-)N-CH2CH2CH2CH2CH2CH2-NH2 +-CH3]CH3COO-. Purification of H from gas2The S content is 51mg/m3In the feed gas H2The removal rate of S was 98.2%.
Example 6:
the other example is the same as example 4 except that the ionic liquid in the absorbent solution is [ (-CH)2CH2CH2-)N-CH2CH2CH2-NH2 +-CH2CH2CH3]CH3COO-. Purification of H from gas2The S content is 32mg/m3In the feed gas H2The removal rate of S was 98.9%.
Example 7:
the other example is the same as example 4 except that the ionic liquid in the absorbent solution is [ (-CH)2CH2CH2CH2CH2CH2CH2CH2-)N-CH2CH2-NH2 +-CH2CH3]CH3COO-Purification of H from gas2The S content is 13mg/m3In the feed gas H2The removal rate of S was 99.5%.
Example 8:
the other example is the same as example 4 except that the ionic liquid in the absorbent solution is [ (-CH)2CH2CH2-)N-CH2CH2CH2-NH2 +-CH2CH2CH3]PF6 -. Purification of H from gas2The S content is 73mg/m3In the feed gas H2Removal of SThe removal rate was 97.4%.
Example 9:
the other example is the same as example 4 except that the ionic liquid in the absorbent solution is [ (-CH)2CH2CH2-)N-CH2CH2CH2-NH2 +-CH2CH2CH3]BF4 -. Purification of H from gas2The S content is 60mg/m3In the feed gas H2The removal rate of S was 97.9%.
Example 10:
at a temperature of 60 ℃ H2The S content is 100mg/m3Is continuously fed into an absorption tower where H in the feed gas is2S is sprayed from the upper part of the absorption tower2S is absorbed by an absorption liquid containing 3.0mol/L of ionic liquid [ (CH)3CH2CH2CH2-)(CH3CH2CH2CH2-)N-CH2CH2-NH2 +-CH2CH2CH2CH3]CH3COO-The absorption temperature is 50 ℃, and H is removed2The purified gas after S is sent into a waste gas flue for other treatment; absorption of H2The absorption liquid (rich liquid) after S enters a lean-rich liquid heat exchanger from the bottom of the absorption tower through a pump, absorbs heat and then enters a regeneration tower from the upper part of the regeneration tower to be regenerated and desorbed H2S, desorption temperature of 75 ℃, desorption H2The absorption liquid (barren solution) after S flows out from the bottom of the regeneration tower, enters the upper part of the absorption tower after heat exchange of a pump, a barren and rich solution heat exchanger and a barren solution cooler, and absorbs H again2S, the absorption liquid circulates back and forth to form continuous absorption and desorption H2S; desorbed H2S is cooled by a condenser, condensed water is separated by a gas-liquid separator and then is sent to H2S, a storage tank for preparing raw material sulfuric acid for viscose fiber production; and sending the condensed water separated from the gas-liquid separator to a regeneration tower. H in the purified gas was measured at any time point after 45min of the treatment operation2The S content is 5mg/m3In the feed gas H2The removal rate of S was 95.0%.
Practice ofExample 11:
the temperature is 45 ℃ and H2The S content is 12000mg/m3Is continuously fed into an absorption tower where H in the feed gas is2S is sprayed from the upper part of the absorption tower2S is absorbed by an absorption liquid containing 5.0mol/L of ionic liquid [ (CH)3CH2CH2CH2-)(CH3CH2CH2CH2-)N-CH2CH2-NH2 +-CH2CH2CH2CH3]CH3COO-The absorption temperature is 45 ℃, and H is removed2The purified gas after S is sent into a waste gas flue for other treatment; absorption of H2The absorption liquid (rich liquid) after S enters a lean-rich liquid heat exchanger from the bottom of the absorption tower through a pump, absorbs heat and then enters a regeneration tower from the upper part of the regeneration tower to be regenerated and desorbed H2S, desorption temperature of 100 ℃, desorption H2The absorption liquid (barren solution) after S flows out from the bottom of the regeneration tower, enters the upper part of the absorption tower after heat exchange of a pump, a barren and rich solution heat exchanger and a barren solution cooler, and absorbs H again2S, the absorption liquid circulates back and forth to form continuous absorption and desorption H2S; desorbed H2S is cooled by a condenser, condensed water is separated by a gas-liquid separator and then is sent to H2S, a storage tank for preparing raw material sulfuric acid for viscose fiber production; and sending the condensed water separated from the gas-liquid separator to a regeneration tower. H in the purified gas was measured at any time point after 45min of the treatment operation2The S content is 85mg/m3In the feed gas H2The removal rate of S was 99.3%.
Example 12:
the temperature is 30 ℃, H2The S content is 169mg/m3Is continuously fed into an absorption tower where H in the feed gas is2S is sprayed from the upper part of the absorption tower2S is absorbed by an absorption liquid containing 0.5mol/L of ionic liquid [ (CH)3CH2CH2CH2-)(CH3CH2CH2CH2-)N-CH2CH2-NH2 +-CH2CH2CH2CH3]BF4 -The absorption temperature is 30 ℃, and H is removed2The purified gas after S is sent into a waste gas flue for other treatment; absorption of H2The absorption liquid (rich liquid) after S enters a lean-rich liquid heat exchanger from the bottom of the absorption tower through a pump, absorbs heat and then enters a regeneration tower from the upper part of the regeneration tower to be regenerated and desorbed H2S, desorption temperature of 100 ℃, desorption H2The absorption liquid (barren solution) after S flows out from the bottom of the regeneration tower, enters the upper part of the absorption tower after heat exchange of a pump, a barren and rich solution heat exchanger and a barren solution cooler, and absorbs H again2S, the absorption liquid circulates back and forth to form continuous absorption and desorption H2S; desorbed H2S is cooled by a condenser, condensed water is separated by a gas-liquid separator and then is sent to H2S, a storage tank for preparing raw material sulfuric acid for viscose fiber production; and sending the condensed water separated from the gas-liquid separator to a regeneration tower. H in the purified gas was measured at any time point after 45min of the treatment operation2The S content is 8mg/m3In the feed gas H2The removal rate of S was 95.3%.
The method for treating hydrogen sulfide in waste gas generated in viscose fiber production can be applied to waste gas treatment of newly-built viscose fiber production enterprises, can also be used for carrying out technical upgrading and reconstruction on waste gas treatment of the existing viscose fiber production enterprises, can also be used for additionally carrying out waste gas treatment on viscose filament yarn enterprises which do not carry out waste gas treatment, and can be used for treating recovered H generated in waste gas generated in viscose fiber production2S is sent into H2S storage tank for storing sulfuric acid used as raw material for viscose fiber production, and sending condensed water into regeneration tower for recycling to remove H2The waste gas of S has little harm to the environment. Compared with the existing waste gas treatment technology, the method can greatly reduce investment, reduce operation cost, reduce the influence on the environment, does not produce secondary pollution, and has higher safety, thereby promoting the sustainable long-term development of enterprises.
Wherein, the ionic liquid is H2The S absorbent has low vapor pressure, almost no volatilization and good thermal stability, so that the S absorbent can not cause raw material loss and secondary pollution in the using process. The ionic liquid [ (R) with a specific structure of the invention1-)(R2-)N-R3-NH2 +-R4]A-Or [ (-R)5-)N-R3-NH2 +-R4]A-R of which1-、R2-、-R3-、R4-、-R5All are lower alkyl or alkylene, A-Is represented by CH3COO-、BF4 -And PF6 -The ionic liquid with the specific structure can be prepared by the acid-base neutralization reaction of amine corresponding to the cation of the ionic liquid with the specific structure and acid corresponding to the anion, so that the preparation method is simple and the cost is low. Typically, primary, secondary amines are reacted with H2S has strong interaction and desorbs H2S is high in temperature and high in desorption energy consumption, and tertiary amine is weak in alkalinity and reacts with H2S has relatively weak interaction with H2S has higher absorption capacity, so the ionic liquid with the specific structure contains tertiary amine groups, and can ensure H2Efficient absorption and low desorption temperatures of S; meanwhile, tertiary amine groups with specific structures can be avoided from reacting with H in the absorption process2S reacts to form a stable ionic liquid structure to reduce H2Absorption efficiency of S absorbent and H2The desorption rate of S. The cation raw material of the ionic liquid with the specific structure contains secondary amine groups with the specific structure, so that the ionic liquid is easy to form and stable in structure, and the ionic liquid has high heat resistance; at the same time, the active proton H on the cation makes the secondary amine group less basic, with H2S interaction is weakened, and absorbed H can be desorbed at lower temperature2S。
In particular, the ionic liquid provided by the invention is H2S absorbent, ion liquid to H2The S has large absorption capacity, high absorption efficiency and good regeneration desorption performance, thereby being suitable for different H in a wider range2The treatment of the viscose waste gas with S concentration is especially suitable for low H which is not suitable for other technical methods2And (4) treating the viscose waste gas with the concentration of S. The ionic liquid with a specific structure has stable performance, can be recycled and can be recycledIn the process, the H is only obtained by the difference of the temperatures of the absorption liquid flowing through the absorption tower and the regeneration tower2S absorption and desorption, low desorption temperature and low energy consumption, so the method of the invention is adopted to treat H in the viscose waste gas2S, the process and the equipment are simple, the investment is low, and the operation cost is low.
Furthermore, H2In the S absorption liquid: the concentration of the absorbent is 0.5-5.0 mol/L, the concentration of the activator is 0.02-0.15 mol/L, the concentration of the corrosion inhibitor is 0.1-0.2 wt%, the concentration of the antioxidant is 0.1-0.2 wt%, and the balance is water. The activator is a common surfactant for reducing the surface tension of the aqueous solution; the corrosion inhibitor is a common corrosion inhibitor for preventing or retarding the corrosion of the carbon steel or the stainless steel material by the acidic aqueous solution; the antioxidant is a common antioxidant for preventing or slowing the oxidative degradation of organic matters. Therefore, the components of the activator, corrosion inhibitor and antioxidant are not particularly required.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A method for treating hydrogen sulfide in waste gas generated in viscose fiber production is characterized by comprising the following steps:
obtaining production waste gas from a viscose fiber production plant;
the waste gas containing H2After the absorption tower of the S absorption liquid, H is obtained2S absorption liquid and H removal2S;
said compound containing H2After the absorption liquid of S absorbs heat through the heat exchanger,obtaining a heated product containing H2An absorption liquid of S;
said heated mixture containing H2The absorption liquid of S is regenerated and desorbed by a regeneration tower to obtain H2S recovery of intermediates and regeneration of H2S absorption liquid;
said H2S, cooling and gas-liquid separating the recovered intermediate product to obtain recovered H2S and condensed water;
the recovered H2S is sent to H2S, storing a tank;
the condensed water is sent to a regeneration tower.
2. The method for treating hydrogen sulfide in waste gas generated in viscose fiber production according to claim 1, wherein in the absorption tower, the H is2And spraying the S absorption liquid from the upper part of the absorption tower.
3. Method for treating hydrogen sulfide in waste gas from viscose fiber production according to claim 1, wherein the heated waste gas contains H2When the absorption liquid of S enters the regeneration tower, the absorption liquid enters from the upper part of the regeneration tower, and H2S recycling intermediate products are discharged from the upper part of the regeneration tower.
4. The method for treating hydrogen sulfide in waste gas generated in viscose fiber production according to claim 1,
the temperature range of the waste gas generated in the viscose fiber production is 20-60 ℃;
h of waste gas generated in production of viscose fibers2The S content value range is 100-12000 mg/m3。
5. Method for treating hydrogen sulfide in waste gas from viscose fiber production according to claim 1, wherein H is selected from the group consisting of H, and H2S absorption liquid is composed of H2S absorbent, water, activator, corrosion inhibitor and antioxidant; wherein,
the concentration of the absorbent is 0.5-5.0 mol/L, the concentration of the activator is 0.02-0.15 mol/L, the concentration of the corrosion inhibitor is 0.1-0.2 wt%, the concentration of the antioxidant is 0.1-0.2 wt%, and the balance is water.
6. The method for treating hydrogen sulfide in waste gas generated in viscose fiber production according to claim 2, wherein H in the waste gas generated in the absorption tower is H2S is sprayed from the upper part of the absorption tower2The absorption temperature of the S absorption liquid ranges from 30 ℃ to 50 ℃.
7. Method for treating hydrogen sulfide in waste gas from viscose fiber production according to claim 1, wherein said absorbing H2The absorption liquid after S enters a heat exchanger from the bottom of the absorption tower through a pump, absorbs heat and then enters a regeneration tower from the upper part of the regeneration tower for regeneration and desorption H2The desorption temperature of S is 75-100 ℃.
8. Method for treating hydrogen sulfide in waste gas from viscose fiber production according to claim 5, wherein H is selected from the group consisting of H, and H2S absorbent is ionic liquid, which is in the H2The concentration range of the S absorption liquid is 0.5-5.0 mol/L.
9. The method for treating hydrogen sulfide in waste gas generated in viscose fiber production according to claim 8, wherein the ionic liquid is a substance represented by the following structure:
[(R1-)(R2-)N-R3-NH2 +-R4]A-or [ (-R)5-)N-R3-NH2 +-R4]A-；
Wherein,
R1-、R2-: an alkyl group having 1 to 6 carbon atoms;
R4-: an alkyl group having 1 to 4 carbon atoms;
R1-、R2-、R4-: the three are different, the same or any two of the three are the same;
-R3-: an alkylene group having 2 to 6 carbon atoms;
-R5-: an alkylene group having 3 to 8 carbon atoms;
-R3-、-R5-: the two are different or the same;
A-：CH3COO-、BF4 -、PF6 -one kind of (1).
10. The method for treating hydrogen sulfide in waste gas generated in viscose fiber production according to claim 1, wherein the H is removed2And (4) sending the waste gas of the S into a waste gas flue for treatment to obtain clean gas.
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