CN104190209A - Treatment method of tail gas generated by preparation process of sodium hydrosulfite - Google Patents
Treatment method of tail gas generated by preparation process of sodium hydrosulfite Download PDFInfo
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- CN104190209A CN104190209A CN201410389944.2A CN201410389944A CN104190209A CN 104190209 A CN104190209 A CN 104190209A CN 201410389944 A CN201410389944 A CN 201410389944A CN 104190209 A CN104190209 A CN 104190209A
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Abstract
The invention belongs to the technical field of waste gas treatment and in particular relates to a treatment method of tail gas generated by the preparation process of sodium hydrosulfite. The treatment method comprises the steps of introducing fine methanol into tail gas to absorb sulfur dioxide, methyl alcohol and methyl formate in the tail gas; then absorbing sulfur dioxide and carbon dioxide in tail gas through an alkaline liquid, and finally, feeding the tail gas into a combustion furnace or a boiler, carrying out treatment on the tail gas with a high temperature combustion method, so as to remove organic gases such as ethyl mercaptan, methyl mercaptan, dimethyl sulfide, and ethyl thioether in the tail gas. According to the method, the tail gas absorbed by methyl alcohol and the alkaline liquid is completely combusted in the combustion furnace or the boiler, so that organic gases such as ethyl mercaptan can be removed, the technological defect caused by a situation that a hydrogen peroxide or potassium permanganate liquid is used for absorbing ethyl mercaptan and other organic gases and the disadvantages of environment pollution, high cost and the like caused by the technological defect can be overcome, the process is simple, the conception is skillful, and the organic gases such as ethyl mercaptan can be removed by a direct combustion method, and therefore, the treatment method has good creation value and economic value.
Description
Technical field
The invention belongs to technical field of waste gas treatment, relate in particular to the processing method that produces tail gas in a kind of sodium hydrosulfite preparation process.
Background technology
The patent No. has been that ZL200910235226.9's disclose in " in sodium hydrosulfite preparation process waste gas produced processing method ", and " temperature of use is that 0 DEG C～10 DEG C, the oxidant of concentration 5%～15% absorb, to remove the ethyl mercaptan in waste gas.The hydrogen peroxide that the oxidant using is concentration 5%～15% or the liquor potassic permanganate of concentration 1%～20% ".
But, find in practice, not only there is an ethyl mercaptan because waste gas produced in sodium hydrosulfite preparation process, also has micro-methyl mercaptan, methyl sulfide, the organic gas such as ethyl sulfide, the hydrogen peroxide that the oxidant using is concentration 5%～15%, itself has special odor hydrogen peroxide, unstable, thereby cause hydrogen peroxide to the ethyl mercaptan in sodium hydrosulfite tail gas, methyl mercaptan, methyl sulfide, the organic gas assimilation effects such as ethyl sulfide are poor, hydrogen peroxide consumption is large, the waste water producing is many, and be difficult to process, therefore cause sodium hydrosulfite production cost high, in sodium hydrosulfite discharging waste gas, peculiar smell is difficult to stably reaching standard processing, surrounding enviroment are caused to larger impact.If the liquor potassic permanganate that the oxidant using is in addition 1%～20%, itself has unstability, and along with the rising stability of temperature reduces, thereby cause liquor potassic permanganate poor to organic gas assimilation effects such as the ethyl mercaptan in sodium hydrosulfite tail gas, methyl mercaptan, methyl sulfide, ethyl sulfides, liquor potassic permanganate consumption is large, in the waste water producing, containing manganese dioxide is difficult to process, therefore cause sodium hydrosulfite production cost high, in sodium hydrosulfite discharging waste gas, peculiar smell is difficult to stably reaching standard processing, and surrounding enviroment are caused to larger impact.
Summary of the invention
The present invention is directed to the deficiency that above-mentioned prior art exists, the processing method that produces tail gas in a kind of environmental protection, sodium hydrosulfite preparation process with low cost is provided.
The technical scheme that the present invention solves the problems of the technologies described above is as follows: in a kind of sodium hydrosulfite preparation process, produce the processing method of tail gas, step is as follows:
(1) first sodium hydrosulfite tail gas passed in Methanol Wash Column, with temperature be the refined methanol countercurrent washing of-20 DEG C～10 DEG C, to absorb sulfur dioxide, methyl alcohol and the methyl formate in tail gas; In the time of methyl alcohol absorption liquid pH value≤4.5, the refined methanol more renewing is as cleaning solution, to ensure the assimilation effect of sulfur dioxide, methyl alcohol and methyl formate in tail gas; Wherein, the methyl alcohol absorption liquid of pH value≤4.5 is for sodium hydrosulfite batching, to reduce the production cost of sodium hydrosulfite;
(2) tail gas after methanol wash enters in alkaline solution scrubbing tower, with temperature be the alkaline solution countercurrent washing that-5 DEG C～10 DEG C, concentration are 5wt%～20wt%, to absorb sulfur dioxide and the carbon dioxide in tail gas; In the time of alkaline solution pH value≤7.5, the alkaline solution more renewing is as cleaning solution, to ensure sulfur dioxide and the carbon dioxide absorption effect in tail gas; Wherein, the alkaline solution of pH value≤7.5 is for reacting by-product anhydrous sodium sulfite or anhydrous potassium sulfite with sodium hydrosulfite synthesis mother liquid;
(3) finally tail gas is sent in combustion furnace or boiler, make ethyl mercaptan, methyl mercaptan, methyl sulfide, ethyl sulfide and the completing combustion under hot conditions of other organic gas in sodium hydrosulfite tail gas, to remove ethyl mercaptan, methyl mercaptan, methyl sulfide, ethyl sulfide and other organic gas in sodium hydrosulfite tail gas, to reach the object of thorough elimination sodium hydrosulfite tail gas peculiar smell.
Wherein, the alkaline solution described in step (2) is sodium hydroxide solution or potassium hydroxide solution;
Ignition temperature described in step (3) is 450 DEG C～1100 DEG C, and furnace pressure is-0.005MPa～-0.02MPa.
Know-why of the present invention:
The reaction of ethyl mercaptan high-temp combustion:
The reaction of methyl mercaptan high-temp combustion:
The reaction of methyl sulfide high-temp combustion:
The reaction of ethyl sulfide high-temp combustion:
The invention has the beneficial effects as follows: the tail gas in the present invention after methyl alcohol and alkali liquor absorption, completing combustion in combustion furnace or boiler, remove the organic gas such as ethyl mercaptan, methyl mercaptan, methyl sulfide, ethyl sulfide, solved and used hydrogen peroxide or liquor potassic permanganate to absorb the defective workmanship of the organic gas such as ethyl mercaptan and the shortcoming such as environmental pollution, high cost of bringing; And technique of the present invention is simple, be skillfully constructed, adopt direct combustion method to remove the organic gas such as ethyl mercaptan, methyl mercaptan, methyl sulfide, ethyl sulfide, can thoroughly remove the organic gas such as ethyl mercaptan in sodium hydrosulfite tail gas, methyl mercaptan, methyl sulfide, ethyl sulfide, the gas such as CO2, SO2 that burning produces is after the PROCESS FOR TREATMENT such as desulfurization in flue gas treating process, gas reaches discharging standards, solve and in background technology, had the problem that in sodium hydrosulfite discharging waste gas, peculiar smell is difficult to stably reaching standard processing, possessed the good creation of value and economic worth.
Detailed description of the invention
Below in conjunction with example, principle of the present invention and feature are described, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment 1
A processing method that produces tail gas in sodium hydrosulfite preparation process, step is as follows:
(1) first sodium hydrosulfite tail gas passed in Methanol Wash Column, with temperature be the refined methanol countercurrent washing of-20 DEG C, absorb sulfur dioxide, methyl alcohol and the methyl formate in tail gas to absorb sodium hydrosulfite; In the time that methyl alcohol absorption liquid pH value is 4.5, the refined methanol more renewing is as cleaning solution, to ensure the assimilation effect of sulfur dioxide, methyl alcohol and methyl formate in tail gas; Wherein, the methyl alcohol absorption liquid that pH value is 4.5 is prepared burden for sodium hydrosulfite;
(2) tail gas after methanol wash enters in alkaline solution scrubbing tower, with temperature be the sodium hydroxide solution countercurrent washing that-5 DEG C, concentration are 5wt%, to absorb sulfur dioxide and the carbon dioxide in tail gas; In the time that alkaline solution pH value is 7.5, the alkaline solution more renewing is as cleaning solution, to ensure sulfur dioxide and the carbon dioxide absorption effect in tail gas; Wherein, the alkaline solution that pH value is 7.5 is for reacting by-product anhydrous sodium sulfite with sodium hydrosulfite synthesis mother liquid;
(3) finally tail gas is sent in combustion furnace by closed conduit, adopt high-temperature combustion method processing, make the organic gas such as ethyl mercaptan in sodium hydrosulfite tail gas, methyl mercaptan, methyl sulfide, ethyl sulfide fire box temperature be 450 DEG C, furnace pressure be-carry out completing combustion under the condition of 0.005MPa, with organic gas such as the ethyl mercaptan in removal sodium hydrosulfite tail gas, methyl mercaptan, methyl sulfide, ethyl sulfides, reach the object of thorough elimination sodium hydrosulfite tail gas peculiar smell.
Embodiment 2
A processing method that produces tail gas in sodium hydrosulfite preparation process, step is as follows:
(1) first sodium hydrosulfite tail gas passed in Methanol Wash Column, with temperature be the refined methanol countercurrent washing of 0 DEG C, absorb sulfur dioxide, methyl alcohol and the methyl formate in tail gas to absorb sodium hydrosulfite; In the time that methyl alcohol absorption liquid pH value is 4.3, the refined methanol more renewing is as cleaning solution, to ensure the assimilation effect of sulfur dioxide, methyl alcohol and methyl formate in tail gas; Wherein, the methyl alcohol absorption liquid that pH value is 4.3 is prepared burden for sodium hydrosulfite;
(2) tail gas after methanol wash enters in alkaline solution scrubbing tower, with temperature be the potassium hydroxide solution countercurrent washing that 5 DEG C, concentration are 10wt%, to absorb sulfur dioxide and the carbon dioxide in tail gas; In the time that alkaline solution pH value is 7.3, the alkaline solution more renewing is as cleaning solution, to ensure sulfur dioxide and the carbon dioxide absorption effect in tail gas; Wherein, the alkaline solution that pH value is 7.3 is for reacting by-product anhydrous potassium sulfite with sodium hydrosulfite synthesis mother liquid;
(3) finally tail gas is sent in boiler by closed conduit, adopt high-temperature combustion method processing, make the organic gas such as ethyl mercaptan in sodium hydrosulfite tail gas, methyl mercaptan, methyl sulfide, ethyl sulfide fire box temperature be 850 DEG C, furnace pressure be-carry out completing combustion under the condition of 0.01MPa, with organic gas such as the ethyl mercaptan in removal sodium hydrosulfite tail gas, methyl mercaptan, methyl sulfide, ethyl sulfides, reach the object of thorough elimination sodium hydrosulfite tail gas peculiar smell.
Embodiment 3
A processing method that produces tail gas in sodium hydrosulfite preparation process, step is as follows:
(1) first sodium hydrosulfite tail gas passed in Methanol Wash Column, with temperature be the refined methanol countercurrent washing of 5 DEG C, absorb sulfur dioxide, methyl alcohol and the methyl formate in tail gas to absorb sodium hydrosulfite methyl alcohol; In the time that methyl alcohol absorption liquid pH value is 4.0, the refined methanol more renewing is as cleaning solution, to ensure the assimilation effect of sulfur dioxide, methyl alcohol and methyl formate in tail gas; Wherein, the methyl alcohol absorption liquid that pH value is 4.0 is prepared burden for sodium hydrosulfite;
(2) tail gas after methanol wash enters in alkaline solution scrubbing tower, with temperature be the sodium hydroxide solution countercurrent washing that 10 DEG C, concentration are 15wt%, to absorb sulfur dioxide and the carbon dioxide in tail gas; In the time that alkaline solution pH value is 7.0, the alkaline solution more renewing is as cleaning solution, to ensure sulfur dioxide and the carbon dioxide absorption effect in tail gas; Wherein, the alkaline solution that pH value is 7.0 is for reacting by-product anhydrous sodium sulfite with sodium hydrosulfite synthesis mother liquid;
(3) finally tail gas is sent in combustion furnace by closed conduit, adopt high-temperature combustion method processing, make the organic gas such as ethyl mercaptan in sodium hydrosulfite tail gas, methyl mercaptan, methyl sulfide, ethyl sulfide fire box temperature be 950 DEG C, furnace pressure be-carry out completing combustion under the condition of 0.005MPa, with organic gas such as the ethyl mercaptan in removal sodium hydrosulfite tail gas, methyl mercaptan, methyl sulfide, ethyl sulfides, reach the object of thorough elimination sodium hydrosulfite tail gas peculiar smell.
Embodiment 4
A processing method that produces tail gas in sodium hydrosulfite preparation process, step is as follows:
(1) first sodium hydrosulfite tail gas passed in Methanol Wash Column, with temperature be the refined methanol countercurrent washing of 10 DEG C, absorb sulfur dioxide, methyl alcohol and the methyl formate in tail gas to absorb sodium hydrosulfite methyl alcohol; In the time that methyl alcohol absorption liquid pH value is 3.5, the refined methanol more renewing is as cleaning solution, to ensure the assimilation effect of sulfur dioxide, methyl alcohol and methyl formate in tail gas; Wherein, the methyl alcohol absorption liquid that pH value is 3.5 is prepared burden for sodium hydrosulfite;
(2) tail gas after methanol wash enters in alkaline solution scrubbing tower, with temperature be the potassium hydroxide solution countercurrent washing that 10 DEG C, concentration are 20wt%, to absorb sulfur dioxide and the carbon dioxide in tail gas; In the time that alkaline solution pH value is 6.5, the alkaline solution more renewing is as cleaning solution, to ensure sulfur dioxide and the carbon dioxide absorption effect in tail gas; Wherein, by-product anhydrous potassium sulfite is reacted with sodium hydrosulfite synthesis mother liquid in during the alkaline solution that pH value is 6.5 goes and post;
(3) finally tail gas is sent in boiler by closed conduit, adopt high-temperature combustion method processing, make the organic gas such as ethyl mercaptan in sodium hydrosulfite tail gas, methyl mercaptan, methyl sulfide, ethyl sulfide fire box temperature be 1100 DEG C, furnace pressure be-carry out completing combustion under the condition of 0.02MPa, with organic gas such as the ethyl mercaptan in removal sodium hydrosulfite tail gas, methyl mercaptan, methyl sulfide, ethyl sulfides, reach the object of thorough elimination sodium hydrosulfite tail gas peculiar smell.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any amendment of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (7)
1. a processing method that produces tail gas in sodium hydrosulfite preparation process, is characterized in that step is as follows:
(1) first tail gas being passed into temperature is the refined methanol of-20 DEG C～10 DEG C, and methyl alcohol absorbs sulfur dioxide, methyl alcohol and the methyl formate in tail gas;
(2) be the alkaline solution that-5 DEG C～10 DEG C, concentration are 5wt%～20wt% through excess temperature again, to absorb sulfur dioxide and the carbon dioxide in tail gas;
(3) finally tail gas is sent in combustion furnace or boiler and adopted high-temperature combustion method processing, to remove ethyl mercaptan, methyl mercaptan, methyl sulfide, ethyl sulfide and other organic gas in tail gas.
2. in a kind of sodium hydrosulfite preparation process according to claim 1, produce the processing method of tail gas, it is characterized in that in step (1) that, in the time of methyl alcohol absorption liquid pH value≤4.5, the refined methanol more renewing is as cleaning solution.
3. in a kind of sodium hydrosulfite preparation process according to claim 1 and 2, produce the processing method of tail gas, it is characterized in that the methyl alcohol absorption liquid of pH value≤4.5 in step (1) is for sodium hydrosulfite batching.
4. the processing method that produces tail gas in a kind of sodium hydrosulfite preparation process according to claim 1, is characterized in that the alkaline solution described in step (2) is sodium hydroxide solution or potassium hydroxide solution.
5. in a kind of sodium hydrosulfite preparation process according to claim 1, produce the processing method of tail gas, it is characterized in that in step (2) that, in the time of alkaline solution pH value≤7.5, the alkaline solution more renewing is as cleaning solution.
6. produce according to claim 1 or 5 the processing method of tail gas in a kind of sodium hydrosulfite preparation process, it is characterized in that the alkaline solution of pH value≤7.5 in step (2) is used for reacting by-product anhydrous sodium sulfite or anhydrous potassium sulfite with sodium hydrosulfite synthesis mother liquid.
7. in a kind of sodium hydrosulfite preparation process according to claim 1, produce the processing method of tail gas, it is characterized in that the ignition temperature described in step (3) is 450 DEG C～1100 DEG C, furnace pressure is-0.005MPa～-0.02MPa.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103755048A (en) * | 2013-12-30 | 2014-04-30 | 中盐安徽红四方股份有限公司 | New sodium hydrosulfite wastewater treatment method |
| CN106178873A (en) * | 2016-08-03 | 2016-12-07 | 茂名市广地化工有限公司 | Waste gas processing method in the production of a kind of sodium hydrosulfite and waste gas treatment equipment |
| CN113457379A (en) * | 2020-03-30 | 2021-10-01 | 中石油吉林化工工程有限公司 | Method for reducing organic matter content in methyl methacrylate vacuum pump tail gas |
| CN114534471A (en) * | 2020-11-26 | 2022-05-27 | 中国石油天然气股份有限公司 | Treatment method of tail gas generated by regenerating mercaptan-removing alkali liquor |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN106178873A (en) * | 2016-08-03 | 2016-12-07 | 茂名市广地化工有限公司 | Waste gas processing method in the production of a kind of sodium hydrosulfite and waste gas treatment equipment |
| CN113457379A (en) * | 2020-03-30 | 2021-10-01 | 中石油吉林化工工程有限公司 | Method for reducing organic matter content in methyl methacrylate vacuum pump tail gas |
| CN114534471A (en) * | 2020-11-26 | 2022-05-27 | 中国石油天然气股份有限公司 | Treatment method of tail gas generated by regenerating mercaptan-removing alkali liquor |
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Application publication date: 20141210 |