CN102660331A - Pressure swing adsorption and vacuum desulphurization process for coke oven gas - Google Patents
Pressure swing adsorption and vacuum desulphurization process for coke oven gas Download PDFInfo
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- CN102660331A CN102660331A CN2012101731113A CN201210173111A CN102660331A CN 102660331 A CN102660331 A CN 102660331A CN 2012101731113 A CN2012101731113 A CN 2012101731113A CN 201210173111 A CN201210173111 A CN 201210173111A CN 102660331 A CN102660331 A CN 102660331A
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Abstract
The invention relates to a pressure swing adsorption and vacuum desulphurization process for coke oven gas. The process is low in energy consumption, simple for productive operation, high in productivity, and long in service life of adsorbent. The process includes subjecting raw gas to compression, freeze separation, tar removal, purification, evacuated desulphurization and decarburization, compressive finish desulphurization and purification. Heavy components in the raw gas are removed in the freeze separation and tar removal procedures, so that normal operation of the adsorbent in subsequent procedures is guaranteed. Double purification is adopted to remove the heavy components in the raw gas and control dew-point temperature and water content. Evacuation is adopted in the desulphurization and decarburization procedure, so that the heavy components are removed thoroughly. The process has the advantages that operation is simple, productivity is high, energy consumption is low, the service life of the adsorbent is long, economic benefit is high, and practical value is high.
Description
Technical field
The invention belongs to the pressure swing adsorption process gas separation technique field, relate in particular to that a kind of energy consumption is low, safe, the sorbent material life-span is long and the coke-oven gas transformation absorption completely of regenerating vacuumizes sulfur removal technology.
Background technology
The coke-oven gas recycling is great techno-economic policy of country, to improve the level of resources utilization, develop a circular economy, building a conservation-minded society has crucial meaning.But, contain a large amount of sulphur in the coke-oven gas, wherein mainly be that the form with hydrogen sulfide exists.If the hydrogen sulfide burning perhaps directly is discharged in the atmosphere and pollutes the environment, so reality aborning, handle coke oven gas desulfurization.
Coke oven gas desulfurization method commonly used at present has wet desulphurization, dry desulfurization and transformation adsorption desulfurize, but dry desulfurization treatment capacity precision little, desulfurization is low, discard the sweetening agent difficult treatment, be not suitable for the higher coke-oven gas of sulfide content; The doctor solution of wet desulphurization is expensive, investment is big, doctor solution toxicity is big, to equipment material have relatively high expectations, discarded doctor solution difficult treatment, be prone to cause secondary pollution; The transformation adsorption desulfurize is then often because virgin gas purifies not thorough before getting into the transformation sweetener; Especially the water content in the virgin gas is bigger; After getting into the transformation desulfurizer; Moisture content in the virgin gas is prone to generate elemental sulfur with hydrogen sulfide generation reduction reaction and stops up sorbent material, influences adsorption effect, causes desulfurization not thorough; In addition, because hydrogen sulfide has very strong polarity, the time of hydrogen sulfide desorb is longer in the existing processes; The time that in adsorption tower, stops is longer; In adsorption tower, react easily, cause the adsorbent reactivation difficulty, the work-ing life of sorbent material is shorter; Equipment running cost is bigger, has increased burden to enterprise operation.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art and provide that a kind of energy consumption is low, safe, sorbent material long service life and the coke-oven gas transformation absorption completely of regenerating vacuumizes sulfur removal technology.
The objective of the invention is to realize like this:
A kind of coke-oven gas transformation absorption vacuumizes sulfur removal technology, and it may further comprise the steps:
Step 1, compression: through compressor pressurizes, make the pressure of virgin gas reach 0.58Mpa in coke-oven gas;
Step 4, purification: the virgin gas after step 3 processing is sent into the oil removing tower of first step TSA device and the pretreater of second stage TSA device successively; Carry out twice purification; Essence removes tar, benzene, naphthalene and other heavy constituent impurity and the partial vulcanization hydrogen in the virgin gas after step 3 is handled; The outlet virgin gas dew-point temperature of wherein controlling first step TSA device is that-45 ~-35 ℃, the outlet virgin gas dew-point temperature of the 2nd TSA device are-60 ~-50 ℃, controls in the outlet virgin gas of the 2nd TSA device moisture content simultaneously below 25ppm;
Step 5, vacuumize desulfurization and decarburization: the virgin gas after step 4 is handled feeds the PSA-S/R device; Adopt vacuum pump that PSA-S/R device adsorption tower is vacuumized simultaneously; Pressure in the PSA-S/R device adsorption tower was reached in 30 seconds-0.085Mpa; And kept at least 120 seconds, and removed HCN, C in the virgin gas
2, CO
2, H
2S, NH
3, NO, organosulfur and most of CH
4, CO, N
2, obtain work in-process gas;
Step 6, compress smart desulfurization: the work in-process air pressure that step 5 is obtained contracts, and pressure reaches 1.30Mpa and gets into the fine desulfurization process by dry device, the hydrogen sulfide of trace is removed fully, and further remove the CH in the work in-process gas
4, CO, N
2
Step 7, purification: the work in-process gas that obtains after the smart desulfurization of step 6 compression is fed the PSA device for producing hydrogen, obtain hydrogen, and hydrogen is purified, make hydrogen purity reach 99.99%.
Compressor in the described step 1 is a spiral-lobe compressor.
The heavy constituent impurity that the subzero fractionation of described step 2 removes comprises high-carbon hydrocarbon, naphthalene, benzene.
The cold carrier of the ice maker that described step 2 subzero fractionation is used is a terepthaloyl moietie.
The filler that described step 3 is removed the oil removing tower in the tar is a coke, and whole oil removing tower is one deck filler.
The tar that removes of described step 3 is meant the tar in the virgin gas behind step 2 subzero fractionation is removed at least 80%.
The present invention compared with prior art has following advantage:
1) coke-oven gas transformation of the present invention absorption vacuumizes and subzero fractionation is set in the sulfur removal technology and removes the tar operation, wherein the subzero fractionation operation can well remove naphthalene in the virgin gas, benzene, etc. heavy constituent impurity, guaranteed the works better of sorbent material in the subsequent handling; Remove the tar operation and adopt the oil removing tower, and the filler of oil removing tower is coke, can well remove the oily components such as tar in the virgin gas like this, can remove 80% tar, guaranteed the works better of sorbent material in the subsequent handling;
2) coke-oven gas transformation of the present invention absorption vacuumizes in the sulfur removal technology virgin gas is provided with two-step purification, thoroughly removes heavy constituent impurity such as tar in the virgin gas, benzene, naphthalene, water; Effectively protected the sorbent material of subsequent processing; And the dew-point temperature that control purifies the back virgin gas is that-60 ~-50 ℃, water content are below 25ppm; Reduced the moisture that gets into subsequent processing like this; And then avoided moisture and hydrogen sulfide generation reduction reaction to generate elemental sulfur and stopped up sorbent material, make the better effects if of absorption more thorough, adsorbent reactivation is complete; And then make the longer service life of sorbent material, the effectively lower operation cost of enterprise;
3) coke-oven gas transformation absorption of the present invention vacuumizes in the sulfur removal technology and on the PSA-S/R device, is communicated with vacuum pump; The PSA-S/R device is vacuumized; Make the strong hydrogen sulfide molecule desorb at short notice of polarity like this, reduce hydrogen sulfide time that in device, stops and the probability that redox reaction takes place, reduce the generation of elemental sulfur; And then avoided stopping up sorbent material because of hydrogen sulfide generation reduction reaction generates elemental sulfur; Make the regeneration of sorbent material more complete, and then make the longer service life of sorbent material, the effectively lower operation cost of enterprise;
In addition, coke-oven gas transformation of the present invention absorption vacuumize sulfur removal technology also have simple to operate, production efficiency is high, advantage of low energy consumption, has very high economic benefit and practical value.
Description of drawings
Fig. 1 vacuumizes the process flow sheet of sulfur removal technology for coke-oven gas transformation absorption of the present invention.
Fig. 2 vacuumizes the frame diagram of sulfur removal technology for coke-oven gas transformation absorption of the present invention.
Among the figure: 1, compressor 2, ice maker 3, oil removing tower 4, first step TSA device 5, second stage TSA device 6, PSA-S/R device 7, fine desulfurization process by dry device 8, PSA device for producing hydrogen 9, vacuum pump.
Embodiment
Combine specific embodiment that the present invention is further specified at present.
As depicted in figs. 1 and 2, a kind of coke-oven gas transformation absorption vacuumizes sulfur removal technology, and it may further comprise the steps:
Step 1, compression: through compressor 1 pressurization, make the pressure of virgin gas reach 0.58Mpa in coke-oven gas;
Step 4, purification: the virgin gas after step 3 processing is sent into the oil removing tower of first step TSA device 4 and the pretreater of second stage TSA device 5 successively; Carry out twice purification; Essence removes tar, benzene, naphthalene and other heavy constituent impurity and the partial vulcanization hydrogen in the virgin gas after step 3 is handled; The outlet virgin gas dew-point temperature of wherein controlling first step TSA device 4 is that-45 ~-35 ℃, the outlet virgin gas dew-point temperature of the 2nd TSA device 5 are-60 ~-50 ℃, controls in the outlet virgin gas of the 2nd TSA device 5 moisture content simultaneously below 25ppm;
Step 5, vacuumize desulfurization and decarburization: the virgin gas after step 4 is handled feeds PSA-S/R device 6; Adopt the adsorption tower of 9 pairs of PSA-S/R devices 6 of vacuum pump to vacuumize simultaneously; The interior pressure of adsorption tower of PSA-S/R device 6 was reached in 30 seconds-0.085Mpa; And kept at least 120 seconds, and removed HCN, C in the virgin gas
2, CO
2, H
2S, NH
3, NO, organosulfur and most of CH
4, CO, N
2, obtain work in-process gas;
Step 6, compress smart desulfurization: the work in-process gas that step 5 is obtained compresses with reciprocating compressor, and pressure reaches 1.30Mpa and gets into fine desulfurization process by dry device 7, the hydrogen sulfide of trace is removed fully, and further remove the CH in the work in-process gas
4, CO, N
2
Step 7, purification: the work in-process gas that obtains after the smart desulfurization of step 6 compression is fed PSA device for producing hydrogen 8, obtain hydrogen, and hydrogen is purified, make hydrogen purity reach 99.99%.
Compressor 1 in the described step 1 is a spiral-lobe compressor.
The heavy constituent impurity that the subzero fractionation of described step 2 removes comprises high-carbon hydrocarbon, naphthalene, benzene.
The cold carrier of the ice maker 2 that described step 2 subzero fractionation is used is a terepthaloyl moietie.
The filler that described step 3 is removed the oil removing tower 3 in the tar is a coke, and whole oil removing tower 3 is one deck filler.
The tar that removes of described step 3 is meant the tar in the virgin gas behind step 2 subzero fractionation is removed at least 80%.
Coke-oven gas transformation of the present invention absorption vacuumizes in the sulfur removal technology virgin gas is provided with two-step purification, thoroughly removes heavy constituent impurity such as tar in the virgin gas, benzene, naphthalene, water; Effectively protected the sorbent material of subsequent processing; And the dew-point temperature that control purifies the back virgin gas be-60 ~-50 ℃, water content below 25ppm, reduced getting into the moisture of subsequent processing like this, and then avoided moisture and hydrogen sulfide generation reduction reaction generation elemental sulfur obstruction sorbent material; Coke-oven gas transformation absorption of the present invention vacuumizes sulfur removal technology and on the PSA-S/R device, is communicated with vacuum pump, and the PSA-S/R device is vacuumized, and makes the strong hydrogen sulfide molecule desorb at short notice of polarity like this; Reduce hydrogen sulfide time that in device, stops and the probability that redox reaction takes place; Reduce the generation of elemental sulfur, make the better effects if of absorption more thorough, the regeneration of sorbent material is complete; And then make the longer service life of sorbent material, the effectively lower operation cost of enterprise;
In addition; Coke-oven gas transformation of the present invention absorption vacuumize sulfur removal technology also have simple to operate, production efficiency is high, advantage of low energy consumption; Have very high economic benefit and practical value, use coke-oven gas transformation absorption of the present invention to vacuumize sulfur removal technology production hydrogen and can improve throughput 50% ~ 58%.
Claims (6)
1. a coke-oven gas transformation absorption vacuumizes sulfur removal technology, and it is characterized in that: it may further comprise the steps:
Step 1, compression: through compressor pressurizes, make the pressure of virgin gas reach 0.58Mpa in coke-oven gas;
Step 2, subzero fractionation: the virgin gas after step 1 compression is sent into ice maker, make the virgin gas temperature reduce to 0 ~ 5 ℃, remove the heavy constituent impurity in the virgin gas;
Step 3, remove tar: the virgin gas behind step 2 subzero fractionation is sent into the oil removing tower, remove the tar in the virgin gas;
Step 4, purification: the virgin gas after step 3 processing is sent into the oil removing tower of first step TSA device and the pretreater of second stage TSA device successively; Carry out twice purification; Essence removes tar, benzene, naphthalene and other heavy constituent impurity and the partial vulcanization hydrogen in the virgin gas after step 3 is handled; The outlet virgin gas dew-point temperature of wherein controlling first step TSA device is that-45 ~-35 ℃, the outlet virgin gas dew-point temperature of the 2nd TSA device are-60 ~-50 ℃, controls in the outlet virgin gas of the 2nd TSA device moisture content simultaneously below 25ppm;
Step 5, vacuumize desulfurization and decarburization: the virgin gas after step 4 is handled feeds the PSA-S/R device; Adopt vacuum pump that the adsorption tower of PSA-S/R device is vacuumized simultaneously; The interior pressure of adsorption tower of PSA-S/R device was reached in 30 seconds-0.085Mpa; And kept at least 120 seconds, and removed HCN, C in the virgin gas
2, CO
2, H
2S, NH
3, NO, organosulfur and most of CH
4, CO, N
2, obtain work in-process gas;
Step 6, compress smart desulfurization: the work in-process air pressure that step 5 is obtained contracts, and pressure reaches 1.30Mpa and gets into the fine desulfurization process by dry device, the hydrogen sulfide of trace is removed fully, and further remove the CH in the work in-process gas
4, CO, N
2
Step 7, purification: the work in-process gas that obtains after the smart desulfurization of step 6 compression is fed the PSA device for producing hydrogen, obtain hydrogen, and hydrogen is purified, make hydrogen purity reach 99.99%.
2. coke-oven gas transformation absorption as claimed in claim 1 vacuumizes sulfur removal technology, and it is characterized in that: the compressor in the described step 1 is a spiral-lobe compressor.
3. coke-oven gas transformation absorption as claimed in claim 1 vacuumizes sulfur removal technology, and it is characterized in that: the heavy constituent impurity that the subzero fractionation of described step 2 removes comprises high-carbon hydrocarbon, naphthalene, benzene.
4. coke-oven gas transformation absorption as claimed in claim 1 vacuumizes sulfur removal technology, and it is characterized in that: the cold carrier of the ice maker that described step 2 subzero fractionation is used is a terepthaloyl moietie.
5. coke-oven gas transformation absorption as claimed in claim 1 vacuumizes sulfur removal technology, and it is characterized in that: the filler that described step 3 is removed the oil removing tower in the tar is a coke, and whole oil removing tower is one deck filler.
6. coke-oven gas transformation as claimed in claim 1 absorption vacuumizes sulfur removal technology, it is characterized in that: the tar that removes of described step 3 is meant the tar in the virgin gas behind step 2 subzero fractionation is removed 80%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103074113A (en) * | 2013-02-26 | 2013-05-01 | 昆明理工大学 | Method for preparing gas by using biomass and coal |
| CN106179287A (en) * | 2016-08-29 | 2016-12-07 | 中冶焦耐(大连)工程技术有限公司 | Adsorbent reactivation and regeneration off gases processing method during coke-stove gas temp.-changing adsorption desulfurization |
| CN108126475A (en) * | 2017-12-28 | 2018-06-08 | 安徽昊源化工集团有限公司 | A kind of method for improving decarburization hydrogen purity |
| CN111905521A (en) * | 2020-08-18 | 2020-11-10 | 宁波中科远东催化工程技术有限公司 | Coke oven gas desulfurization process and system |
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|---|---|---|---|---|
| CN103074113A (en) * | 2013-02-26 | 2013-05-01 | 昆明理工大学 | Method for preparing gas by using biomass and coal |
| CN106179287A (en) * | 2016-08-29 | 2016-12-07 | 中冶焦耐(大连)工程技术有限公司 | Adsorbent reactivation and regeneration off gases processing method during coke-stove gas temp.-changing adsorption desulfurization |
| CN108126475A (en) * | 2017-12-28 | 2018-06-08 | 安徽昊源化工集团有限公司 | A kind of method for improving decarburization hydrogen purity |
| CN111905521A (en) * | 2020-08-18 | 2020-11-10 | 宁波中科远东催化工程技术有限公司 | Coke oven gas desulfurization process and system |
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Application publication date: 20120912 |