CN1167084A - Technology for refining ammonia - Google Patents
Technology for refining ammonia Download PDFInfo
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- CN1167084A CN1167084A CN 96104976 CN96104976A CN1167084A CN 1167084 A CN1167084 A CN 1167084A CN 96104976 CN96104976 CN 96104976 CN 96104976 A CN96104976 A CN 96104976A CN 1167084 A CN1167084 A CN 1167084A
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- ammonia
- hydrogen sulfide
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Abstract
The combined technological process consisting of washing,c rystallizing, adsorption and fine desulfurization for refining ammonia is characterized by adding concetrated ammonia liquor washing process before the existent processes of "crystallizing adsorption and fine desulfurization". The stripped gas ammonia is passed through fractional condensation and cooled to below 40 deg.C to make its hydrogen sulfide and water content be about 1%(w), then is fed into crystallizing tank and adsorption tower so as to further remove the impurities of sulfur and water, etc., finally passed through fine desulfurization to obtain high-pure liquid ammonia product whose purity is up to 99.8% and hydrogen sulfide content is less than Ippm. Said invented process is stable, low in energy consumption, free from secondary pollution, and can be continuously operated.
Description
The present invention relates to technology for refining ammonia, be particularly useful for the moisture gas ammonia of impurity that waits of sulfur-bearing that the sewage from oil refinery stripping comes out and reclaim refining.
In the gas ammonia that the sewage stripper plant reclaims, contain oil, water, hydrogen sulfide, phenol and other organic compound and solid dust.Ammonia purified task is to improve purity, reduces impurity, especially will reduce hydrogen sulfide content.
In the existing technology for refining ammonia, strong aqua circulation cleaning method is the moisture gas ammonia process of the sulfur-bearing washing tower that stripping is come out, and with recycle pump strong aqua is beaten to cat head, and impurity such as the hydrogen sulfide in the ammonia of absorption below 10 ℃, water are to reach refining purpose.German Patent DD255720, U.S. Pat 4060591 adopt strong aqua circulation cleaning-liquefied ammonia washing method refining, get liquefied ammonia purity and be higher than 99.5%, hydrogen sulfide content can be controlled in below the 10ppm, but Production Flow Chart complexity, used moving equipment is many, operational difficulty, the energy consumption height, hydrogen sulfide stripping is complete inadequately.
Crystallization-the absorption of prior art-smart doctor treatment is that the moisture gas ammonia of sulfur-bearing that stripping comes out is sloughed most of hydrogen sulfide and water through the liquefied ammonia crystallisation by cooling earlier, again through r-Al
2O
3Or activated carbon adsorption, compression, refining then, with further desorption hydrogen sulfide wherein.64 pages of the 9th phases of " refining of petroleum and chemical industry " nineteen ninety-five have reported that laboratory using crystallization-fine desulfurizing technology makes with extra care gas ammonia, and the liquefied ammonia hydrogen sulfide content of gained can be controlled in below the 10ppm.The shortcoming of this technology is that hydrogen sulfide, water-content are still higher, and quality is understable, and it is high that purity is owed; Enter sulfur-bearing moisture higher (～1%) in the gas ammonia of crystallizer, hydrogen sulfide and water to gather speed fast, switch and flushing cycle is lacked, complex operation, labour intensity is big; Hydrogen sulfide content after the crystallization in the gas ammonia is higher, and growth in time and increasing; The sorbent material load is big, and the time that bed is penetrated is short, and regeneration is frequent.
Purpose of the present invention is intended to overcome the deficiencies in the prior art and a kind of technology for refining ammonia of providing, claims " washing-crystallization-absorption-smart desulfurization " ammonia makes with extra care process integration.
The object of the present invention is achieved like this: in the prime enriching ammonia scrubbing flow process of existing crystallization-absorption-fine desulfurizing technology flow process.With the gas ammonia that the sewage stripping comes out, reduce to below 40 ℃ through the fractional condensation temperature, hydrogen sulfide, water-content in the gas ammonia are stabilized in about 1% (W), enter washing tower, guarantee the washing tower smooth operation.In washing tower, wash at the gas ammonia to hydrogen sulfide and water-content about 1% (W) below 10 ℃ with strong aqua, make the content of its outlet hydrogen sulfide and water be lower than 200ppm, promptly greatly reduce the hydrogen sulfide and the water concentration of crystallizer inlet.Thus, in the crystallizer sulfide and water to gather speed slow, the concentration of hydrogen sulfide is below 30ppm in the balance liquid phase, the possibility that sulphur hydrogenation ammonium is separated out in the crystallizer liquid phase is minimum simultaneously, only need discharge a small amount of hydrops simply, need not switch and wash.Owing to concentration of hydrogen sulfide in the gas ammonia that enters adsorption tower can be stabilized in the following lower level of 30ppm, the adsorbent bed time that is penetrated was more than 1 year, in a production cycle, need not to switch regeneration, adsorption tower inlet moisture content is low simultaneously, the physical strength loss of sorbent material is little, bed is difficult for hardening, and sorbent material is difficult for inactivation.
The refining process integration of ammonia of the present invention is also removed the entrained micro-sorbent material dust of gas ammonia to the gas ammonia that adsorption tower comes out through fly-ash separator, and remove the liquid that gas ammonia may have through minute flow container, lower the temperature slightly through ammonia compressor compression gas ammonia again, enter the lubricating oil of bringing into when the de-oiling jar removes compression; Gas ammonia after the de-oiling enters smart digester bottom, under 90-130 ℃ of condition trace hydrogen sulfide is further removed, after water cooler gets the high purity liquid ammonia product.
Adopt " washing-crystallization-absorption-smart desulfurization " of the present invention ammonia to make with extra care process integration, the purity of gained liquefied ammonia can be up to 99.8%, and concentration of hydrogen sulfide can be guaranteed below 1ppm; The hydrogen sulfide of crystallizer, water load need not to switch and flushing for a short time; The adsorption tower switching regeneration period is long, and adsorbent bed being difficult for hardens, and sorbent material is difficult for inactivation, and regeneration times is few, long service life; Produce continuously steadily, energy consumption is low, non-secondary pollution.
Accompanying drawing is the refining joint process figure of " washing-crystallization-absorption-smart desulfurization " of the present invention ammonia.
Below in conjunction with embodiment technical scheme of the present invention is done further statement.
See accompanying drawing.The moisture gas ammonia of the sulfur-bearing that stripping comes out from sewage, be chilled to through the 1st grade of water cooler (1) and enter the 1st grade of separator (2) about 80 ℃, the liquid phase part that condensation separation is got off is as the adsorption liquid of aminoacid stripping tower, and part is as the absorption liquid of hydrogen sulfide stripping tower, and a small amount of phlegma returns raw material sewage jar; Gas ammonia after the separation is chilled to below 40 ℃ through the 2nd grade of water cooler (3), separates through the 2nd grade of separator (4) again, and liquid phase is returned raw material sewage jar.
Gas ammonia after the dehydration and an amount of liquefied ammonia mixing postcooling enter strong aqua washing tower (5) bottom.With strong aqua recycle pump (6) with strong aqua beat to washing tower (5) cat head as washing composition, gas ammonia is counter current contact with it, washing removes most hydrogen sulfide and water in the gas ammonia.Washing tower (5) tower top temperature is controlled at and is lower than 10 ℃, and the poly-sulfur-bearing strong aqua of washing tower (5) tower prodelta clay flows back to raw material sewage jar.
Sulfur-bearing gas ammonia after the washing is dispersed in the liquefied ammonia of crystallizer (7) through sparger equably from compressing into into crystallizer (7) bottom, fully contacts with liquefied ammonia, and exchange of substance takes place, and utilizes liquefied ammonia self gasification and lowers the temperature.The reaction of ammonia and hydrogen sulfide generates sulphur hydrogenation ammonium at low temperatures, and most of hydrogen sulfide is fixed in the liquid phase and is removed.Factors such as the service temperature of the decreasing ratio of hydrogen sulfide and crystallizer (7) gas ammonia inlet concentration of hydrogen sulfide, crystallizer (7), liquid level are relevant.The temperature of crystallizer (7) is controlled at below 0 ℃; Liquid level by automatic regulating valve crystallization control jar (7) is at 20-50%.
Crystallizer (7) comes out to contain the gas ammonia of a small amount of hydrogen sulfide through adsorption tower (8), is lower than 20 ℃ of hydrogen sulfide, water, phenol, oil and other impurity in the following adsorb ammonia with activated carbon adsorbent in temperature.
The gas ammonia that adsorption tower (8) comes out contains a small amount of sorbent material dust, particularly during shutting down.For preventing of the wearing and tearing of superfine sorbent material dust, remove the entrained micro-sorbent material dust of gas ammonia through fly-ash separator (9) to ammonia compressor.
Gas ammonia after the dedusting is removed the liquid that gas ammonia may have through a minute flow container (10), in case the ammonia compressor feed liquor.Gas ammonia after the desulfurization is compressed to about 1.5MPa through screw rod ammonia compressor (11) again, and the gas ammonia after the compression enters the lubricating oil of bringing into when de-oiling jar (12) removes compression through cooling slightly, to protect the purity of liquefied ammonia.
Gas ammonia after the de-oiling enters smart de-oiling jar (13) bottom, by the effect of smart devulcanization catalyzer, trace hydrogen sulfide is further removed under 90-130 ℃ of condition.This reactor can also remove micro-hydrogen, phenol and other impurity in the deammoniation simultaneously.
Gas ammonia after the smart desulfurization, through liquefied ammonia water cooler (14) cooling, ammonia tank (15) gets the high purity liquid ammonia product.
Following table is listed the composition of the raw material of present embodiment, main intermediate stream and product.As seen through of the present invention " washing-crystallization-absorption-smart desulfurization " behind the refining process integration of ammonia, the purity of ammonia is up to more than 99.8%, and hydrogen sulfide content is lower than 1ppm, and water, oil, discharge opeing 10 30 at the bottom of gas ammonia＜80 500 96.5～2%～2.0 washing tower inlet gas ammonias＜40 470 98.0～1%～1.0 scrubber overhead gas ammonias, 10 470 99.2 100ppm＜0.8 scrubbing tower after grade separation of phenol content also reduce greatly. project logistics title temperature ℃ flow kg/h ammonia content % hydrogen sulfide water content % raw material ammonia aqueous vapor 110 3500～45～5% 1st～33 3%＜5 crystallizing tanks outlet gas ammonia, 0 500 99.5＜30ppm＜0.5 adsorption tower outlet gas ammonia, 20 500 99.7＜10ppm＜0.3 smart desulfurization entrance gas ammonia 90-130 500 99.8＜1ppm＜0.2 product liquefied ammonia＜45 450 99.8＜1ppm＜0.2
Claims (7)
1. the one kind refining process integration of " washing-crystallization-absorption-smart desulfurization " ammonia, comprise crystallization-absorption-smart desulfurization flow process, it is characterized in that the gas ammonia that the sewage stripping is come out reduces to below 40 ℃ through the fractional condensation temperature, make hydrogen sulfide, water-content in the gas ammonia enter strong aqua washing tower (5) at 1% time; In washing tower (5), the gas ammonia that enters is being washed below 10 ℃ with strong aqua, make its outlet hydrogen sulfide and water-content be lower than 200ppm, enter crystallizer (7).
2. by the refining process integration of the described ammonia of claim 1, it is characterized in that the moisture gas ammonia of sulfur-bearing that stripping comes out is chilled to through the 1st grade of water cooler (1) enters the 1st grade of separator (2) under 80 ℃, gas ammonia after the separation is chilled to below 40 ℃ through the 2nd grade of water cooler (3), separate through the 2nd grade of separator (4) again, enter strong aqua washing tower (5).
3. by the refining process integration of the described ammonia of claim 1, it is characterized in that crystallizer (7) temperature is controlled at below 0 ℃.
4, by claim 1 and the refining process integration of 3 described ammonia, it is characterized in that the liquid level of crystallizer (7) is controlled at 20-50%.
5. by the refining process integration of claim 1 and 3,4 described ammonia, it is characterized in that adsorption tower (8) uses activated carbon adsorbent, temperature to be controlled at and be lower than 20 ℃.
6. by the refining process integration of the described ammonia of claim 1, it is characterized in that gas ammonia that adsorption tower (8) comes out through fly-ash separator (9), divide flow container (10), ammonia compressor (11), de-oiling jar (12), enter smart digester (13) then, after cold liquid ammonia but device (14) the high purity liquid ammonia product.
7. by claim 1 and the refining process integration of 6 described ammonia, it is characterized in that the temperature of smart digester (13) is controlled at 90-130 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96104976A CN1047366C (en) | 1996-05-14 | 1996-05-14 | Technology for refining ammonia |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96104976A CN1047366C (en) | 1996-05-14 | 1996-05-14 | Technology for refining ammonia |
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| Publication Number | Publication Date |
|---|---|
| CN1167084A true CN1167084A (en) | 1997-12-10 |
| CN1047366C CN1047366C (en) | 1999-12-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96104976A Expired - Fee Related CN1047366C (en) | 1996-05-14 | 1996-05-14 | Technology for refining ammonia |
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| CN (1) | CN1047366C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298629C (en) * | 2005-02-17 | 2007-02-07 | 昆明理工大学 | Method for recoverying and utilization of pulluted ammonia water of brown coal pressurized gasification |
| CN102464341A (en) * | 2010-11-02 | 2012-05-23 | 住友精化株式会社 | System for purifying ammonia |
| CN104326485A (en) * | 2014-10-12 | 2015-02-04 | 陕西创联工业技术有限公司 | Ammonia refining treatment process |
| CN106395857A (en) * | 2016-08-29 | 2017-02-15 | 北方华锦化学工业集团有限公司 | Liquid ammonia refining decolorization system and method |
| CN109399666A (en) * | 2018-12-14 | 2019-03-01 | 南京新世纪江南环保科技发展有限公司 | A kind of method and device recycling ammonia from acid water |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3054726A (en) * | 1959-10-29 | 1962-09-18 | United States Steel Corp | Method of recovering ammonia from aqueous ammonia vapors by a twostage steam distillation operation |
| US3383173A (en) * | 1965-12-30 | 1968-05-14 | Chevron Res | Ammonia purification |
| DE2527985C3 (en) * | 1975-06-24 | 1981-04-16 | Metallgesellschaft Ag, 6000 Frankfurt | Continuous process for the production of pure ammonia |
| CN1061389A (en) * | 1990-11-12 | 1992-05-27 | 中国人民解放军第七○一八工厂 | The recovery and treatment method of ammonia during bicarbonate of ammonia is produced |
-
1996
- 1996-05-14 CN CN96104976A patent/CN1047366C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298629C (en) * | 2005-02-17 | 2007-02-07 | 昆明理工大学 | Method for recoverying and utilization of pulluted ammonia water of brown coal pressurized gasification |
| CN102464341A (en) * | 2010-11-02 | 2012-05-23 | 住友精化株式会社 | System for purifying ammonia |
| CN102464341B (en) * | 2010-11-02 | 2015-01-21 | 住友精化株式会社 | System for purifying ammonia |
| CN104326485A (en) * | 2014-10-12 | 2015-02-04 | 陕西创联工业技术有限公司 | Ammonia refining treatment process |
| CN106395857A (en) * | 2016-08-29 | 2017-02-15 | 北方华锦化学工业集团有限公司 | Liquid ammonia refining decolorization system and method |
| CN109399666A (en) * | 2018-12-14 | 2019-03-01 | 南京新世纪江南环保科技发展有限公司 | A kind of method and device recycling ammonia from acid water |
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| Publication number | Publication date |
|---|---|
| CN1047366C (en) | 1999-12-15 |
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