CN102453566A - Purified gas dehydration technology applied in natural gas with high sulfur content - Google Patents
Purified gas dehydration technology applied in natural gas with high sulfur content Download PDFInfo
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- CN102453566A CN102453566A CN2010105193411A CN201010519341A CN102453566A CN 102453566 A CN102453566 A CN 102453566A CN 2010105193411 A CN2010105193411 A CN 2010105193411A CN 201010519341 A CN201010519341 A CN 201010519341A CN 102453566 A CN102453566 A CN 102453566A
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Abstract
The invention discloses a purified gas dehydration technology applied in natural gas with high sulfur content. The purified gas dehydration technology applied in natural gas with high sulfur content contains steps of: removing moisture from wet purified gas, regenerating a dehydration solution and the like. The invention can be used to effectively dehydrate purified gas and reduce dehydration cost, and requires simple processes.
Description
Technical field
The present invention relates to a kind of purified gas dewatering process that is applied to high sulfur-containing natural gas.
Background technology
Removing of gas H2S generally can be divided into dry method and wet method two big classes.Wet method comprises absorption process and wet oxidation process, and its desulfurization load is high, but ubiquity shortcomings such as power consumption is big, equipment volume is huge, working cost is high, control condition harshness.Dry method comprises iron oxide process, zinc oxide method, activated carbon method, sieve method etc., and dry method is applicable to low sulfurous gas processing, is widely used so that its technology is simple, easy to operate, desulfurization precision is high, energy consumption is low.Existing sulfur removal technology mainly contains following several kinds:
Absorption process: absorption process comprises chemical absorption method, physical absorption method and physical chemistry absorption process.
(1) chemical absorption method: chemical absorption method comprises amine method, improvement hydramine method, hot salt of wormwood method etc.The amine method be used for removing use in the existing method of multiple unwanted component that industrial gasses comprise H2S more general a kind of.This method solvent for use is generally the alkanol amine.Monoethanolamine MEA BASF (MEA) is the strongest at various amine neutral and alkalis, both can remove H
2S can remove CO again
2, degree of purification reaches several ppm, but regeneration needs considerable energy.Diethylolamine (DEA) can be used for containing in the virgin gas occasion of COS, though the molecular weight of DEA is bigger, owing to can adapt to the load of the above MEA of twice, thereby its application is still economical.Also have trolamine (TEA), diglycolamine (DGA), HSDB 338 (DIPA) and methyldiethanolamine (MDEA) in this kind solvent.The MDEA method, is proved and has to H2S advantages such as good selection removes ability and anti-degradation property is strong, reaction heat is lower, corrosion tendency is little, vp is lower just through industrial amplification test at early fifties.But it is higher owing to the solvent price at that time; Be not very urgent objectively to the requirement of selectively removing H2S in addition; So slowly fail to promote; Up between recent two decades, just developed rapidly, this method is noticeable with its potential energy-saving effect at present, uses MDEA can virgin gas be handled the sulfur-bearing standard that reaches purified gas.
In recent years, the alkanolamine doctor treatment has been done many improvement, particularly evident is to have improved the alkanolamine doctor solution, in alkanolamine solution, adds alcohol, boric acid or N-Methyl pyrrolidone or N-methyl-3-morpholone mai, removes H simultaneously to improve
2S, CO
2, sour gas such as COS effectiveness.These technology promptly are improvement hydramine methods, are also quite paid close attention to.
(2) physical absorption method: the physical absorption method comprises cold methanol method, N-base pyrrolidone method, polyglycol dimethyl ether process, tbp method, N-methyl ε-Ji Neixianan method etc.
Cold methanol method (Rectisol method) is a solvent with the low-temp methanol, is mainly used in ammonia factory or Methanol Plant purification synthetic gas and before the natural gas liquids deep cooling, purifying before liquefied ammonia washing.Remove H2S and CO2, NH3, HCN, colloidal materials, higher hydrocarbon and other materials in the virgin gas that this method can be produced by gasification, also can be by reforming gas, the gas removal H2S, COS and the CO2 that particularly produce by hydrocarbon partial oxidation.One of advantage of cold methanol method also is that solvent method is common, promptly under the high condition of partial pressure, can obtain the high solvent load.The main drawback of this method is to absorb heavy hydrocarbons.
N methylpyrrolidone process (Purisol method) adopts the physical solvent N-Methyl pyrrolidone, and the H2S content after the processing can be reduced to the defeated standard of coincidence tube.This method is used for carbon steel equipment, does not have obviously corrosion.
Polyglycol dimethyl ether process (Selexol method) is used for removing the H2S and the CO2 of gas.The application of this method in industry still is limited to low relatively H2S load gas (2.29g/m3) so far.It is little that its advantage is that solvent does not have the burn into loss, and shortcoming is to absorb heavy hydrocarbons.
The absorbing medium that tbp method (24tasolvan method) is used is tbp (TBP), and TBP can be with the gas processing that contains H2S to reaching the defeated standard of pipe, but organic sulfide removal thing also.
N-methyl ε-Ji Neixianan method (NMC method) is suitable for removing the organosulfur in the gas, particularly mercaptan most, but industrial application is still immature.
(3) chemistry-physical absorption method: chemistry-physical absorption method is the method with chemical absorber and physical absorbent combined utilization, is commonly used with sulfolane process at present.This method is that U.S. Shell oil company developed in phase early 1960s, is used for selexol process mostly.Tetramethylene sulfone doctor treatment solvent for use generally is made up of DIPA, tetramethylene sulfone and water.Tetramethylene sulfone is all stable to water, acid, alkali, oxygen etc., and volatility is little, and is nontoxic.Experiment shows that tetramethylene sulfone concentration is high in the solution, be suitable for removing COS, otherwise low tetramethylene sulfone concentration then is suitable for removing H2S.Sulfolane process is a kind of newer sulfur method, obviously surpasses the ability of ethanolamine solutions commonly used, and flow of process air is very effective when high pressure and acidic components concentration are high especially.
Wet oxidation process
(1) arsyl technology
1. arsenic alkaline process (Thylox method)
Adopting arsenical basic soln to remove the method for hydrogen sulfide in the gas, is a kind of method with the longest history in the wet oxidation process, once is widely used in desulfurization in the various virgin gass.This method in the 1950's by the industriallization of U.S. Koppers company, washing lotion is made up of K2CO3 or Na2CO3 and As2O3, is thiooxidant with arsenate or thioarseniate, staple is Na4As2S5O2.This method removes hydrogen sulfide and produces effect very much, can produce the gas of sulfide hydrogen＜5mg/m3 (mark).But along with environmental requirement is strict, arsenic is highly toxic substance, and therefore, the arsenic alkaline process is replaced by some other sulfur method at present, seldom uses in the industry.
2. Giammarco-Vetrocoke process (G-V method)
This method is the improvement to arsyl technology; Purposes according to H2S in the gas and CO2 concentration and CO2; Can be divided into low pH (pH=7.5) and two kinds of flow process hydrogen sulfide of high pH (pH=9.0) and arsenite reaction generation thioarseniate; By the arsenate oxidation, obtain thioarseniate and arsenite simultaneously again, catalyst for oxidation reaction is a quinhydrones.In the G-V method, must carry out aftertreatment to remove arsenite.This method range of application is wider, and absorption temperature is from normal temperature to 150 ℃, and pressure can be handled the dense gas of CO2 from the normal pressure to 7.4MPa.Purify the H2S content＜1mg/m3 (mark) in the gas of back, the sulfur capacity of solution high (0.5～8kg/m3)
(2) vanadium base sulfur removal technology: be also referred to as the Strentford method, domestic title ADA method.This method the earliest by English North Western Gas Board (being British Gas company) and Clayton Aniline company at present in exploitation the 1950's, after be applied to the desulfurization of all gases.China also is applied to this method desulfurization such as coke(oven)gas, coal gas in late 1960s, is one of maximum sulfur method of present domestic application.This technology is with the basic catalyzer of vanadium as desulfurization, and employing anthraquinone-2, and 7-diacid sodium (ADA) is as the regeneration oxygen carrier of going back the ortho states vanadium, and washing lotion is made medium by carbonate.The technological problems of this method is: the sulfur granules that (1) suspends reclaims difficulty, is prone to cause filter stoppage; (2) by product increases the pharmaceutical chemicals consumption; (3) sulphur is of poor quality; (4) CS2, CO2 and mercaptan are worked hardly; (5) harmful waste liquid difficult treatment possibly cause secondary pollution; (6) the gas pungency is big.For overcoming Stretford method technological problems, developed Sulfolin technology, this method was in industriallization in 1985.Sulfolin technology adds a kind of organic nitrogen compound in solution, to overcome the generation of salt in the Stretford method solution.
(3) iron-based technology
The seventies, U.S. air resource company has developed LO-CAT technology, and this method is typical iron-based technology, in handling processes such as Sweet natural gas, refinery gas, shale retorting gas and synthetic gas, has obtained promoting.Because of adopting iron huge legendary turtle compound, overcome the defective that only adds iron in the past and generate by product, desulfuration efficiency improves greatly.Washing lotion mainly comprises two kinds of huge legendary turtle compounds, a kind of sterilant and a kind of tensio-active agent, and generally between 500～1000ppm, the pH value is between 8～8.5 for concentration of iron, and desulfuration efficiency is kept by adding iron huge legendary turtle compound.
The eighties u s company adopts EDTA to stablize iron, and the centre has also added a kind of hydroxylation sugar, further stabilizing solution.When chelate iron concentration is the 18000ppm use in the mother liquor it is diluted 40 times.This agent of activity is high, and desulfuration efficiency is up to 99.99%, and concentration is low and nontoxic, thereby very popular with users.The LO-CAT system has the following advantages: solid salt generates few; Air capacity and pressure are little; The washing lotion consumption is few; Machine Design is compact.
After sulfur removal technology finished, how the wet purification gas of generation effectively dewatered, and has become problem demanding prompt solution.
Summary of the invention
The objective of the invention is to overcome the shortcoming and defect of above-mentioned prior art, provide a kind of can be effectively to purified gas dewater, flow process is simple, reduce the purified gas dewatering process that is applied to high sulfur-containing natural gas of dehydration cost.
The object of the invention is realized through following technical proposals: be applied to the purified gas dewatering process of high sulfur-containing natural gas, may further comprise the steps:
(a) from the wet purification gas on desulfurization unit absorption tower, the bottom that gets into the dewatering unit absorption tower contacts with dehydrating solution is reverse from bottom to top, thereby sloughs the moisture that contains in the wet purification gas;
(b) dehydrating solution that has absorbed moisture comes out at the bottom of the absorption tower, after the interchanger preheating, gets into flash tank and flashes off the hydrocarbon component in the dehydrating solution, filters through strainer and gets into regenerator column;
(c) in the regenerator column, part moisture becomes steam in the dehydrating solution, leaves system from regeneration overhead, and the dehydrating solution after the regeneration comes out from reboiler, after in interchanger, cooling off with heat exchange, advances to absorb cat head through pumping again, thereby accomplishes the circulation of dehydrating solution.
Said dehydrating solution is poor triglycol.
Said interchanger is poor-rich solution interchanger.
In sum, the invention has the beneficial effects as follows: can be effectively to purified gas dewater, flow process is simple, reduce the dehydration cost.
Embodiment
Below in conjunction with embodiment, the present invention is done further detailed description, but embodiment of the present invention is not limited only to this.
Embodiment:
The purified gas dewatering process that is applied to high sulfur-containing natural gas that the present invention relates to may further comprise the steps:
(a) from the wet purification gas on desulfurization unit absorption tower, the bottom that gets into the dewatering unit absorption tower contacts with dehydrating solution is reverse from bottom to top, thereby sloughs the moisture that contains in the wet purification gas;
(b) dehydrating solution that has absorbed moisture comes out at the bottom of the absorption tower, after the interchanger preheating, gets into flash tank and flashes off the hydrocarbon component in the dehydrating solution, filters through strainer and gets into regenerator column;
(c) in the regenerator column, part moisture becomes steam in the dehydrating solution, leaves system from regeneration overhead, and the dehydrating solution after the regeneration comes out from reboiler, after in interchanger, cooling off with heat exchange, advances to absorb cat head through pumping again, thereby accomplishes the circulation of dehydrating solution.
Said dehydrating solution is poor triglycol.
Said interchanger is poor-rich solution interchanger.
The concrete steps of the purified gas dewatering process that the present invention relates to are: from the wet purification gas on desulfurization unit absorption tower; The bottom that gets into the dewatering unit absorption tower contacts with poor triglycol solution is reverse from bottom to top, and the dry gas that comes out from the top, absorption tower can reach the moisture index of I class natural gas makings standard code.The rich glycol liquid that has absorbed moisture comes out at the bottom of the absorption tower, through after poor-rich solution interchanger preheating, gets into flash tank and flashes off the hydrocarbon component in the rich glycol solution, filters through strainer and gets into regenerator column.In regenerator column, part moisture becomes steam in the rich solution, leaves system from regeneration overhead; Poor glycol solution after the regeneration comes out from reboiler; In poor-rich solution interchanger, after cooling off, advance to absorb cat head through pumping again, thereby accomplish the circulation of triglycol solution with the heat exchange of rich glycol solution.
The above only is preferred embodiment of the present invention, is not the present invention is done any pro forma restriction, and every foundation technical spirit of the present invention, any simple modification, equivalent variations to above embodiment did all fall within protection scope of the present invention.
Claims (3)
1. be applied to the purified gas dewatering process of high sulfur-containing natural gas, it is characterized in that, may further comprise the steps:
(a) from the wet purification gas on desulfurization unit absorption tower, the bottom that gets into the dewatering unit absorption tower contacts with dehydrating solution is reverse from bottom to top, thereby sloughs the moisture that contains in the wet purification gas;
(b) dehydrating solution that has absorbed moisture comes out at the bottom of the absorption tower, after the interchanger preheating, gets into flash tank and flashes off the hydrocarbon component in the dehydrating solution, filters through strainer and gets into regenerator column;
(c) in the regenerator column, part moisture becomes steam in the dehydrating solution, leaves system from regeneration overhead, and the dehydrating solution after the regeneration comes out from reboiler, after in interchanger, cooling off with heat exchange, advances to absorb cat head through pumping again, thereby accomplishes the circulation of dehydrating solution.
2. the purified gas dewatering process that is applied to high sulfur-containing natural gas according to claim 1 is characterized in that said dehydrating solution is poor triglycol.
3. the purified gas dewatering process that is applied to high sulfur-containing natural gas according to claim 1 is characterized in that, said interchanger is poor-rich solution interchanger.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103013605A (en) * | 2012-12-26 | 2013-04-03 | 上海华畅环保设备发展有限公司 | Method and device for reducing triethylene glycol consumption in dehydration process of natural gas |
| CN103265985A (en) * | 2013-05-24 | 2013-08-28 | 北京时代桃源环境科技有限公司 | Device for reducing humidity of low-concentration gas and dehumidification method |
| CN104194854A (en) * | 2014-09-23 | 2014-12-10 | 北京化工大学 | Hypergravity-process triglycol natural gas dehydration system and process using system |
| CN107739635A (en) * | 2017-08-31 | 2018-02-27 | 昆山市恒安工业气体有限公司 | A kind of purifying device for natural gas |
-
2010
- 2010-10-18 CN CN2010105193411A patent/CN102453566A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103013605A (en) * | 2012-12-26 | 2013-04-03 | 上海华畅环保设备发展有限公司 | Method and device for reducing triethylene glycol consumption in dehydration process of natural gas |
| CN103265985A (en) * | 2013-05-24 | 2013-08-28 | 北京时代桃源环境科技有限公司 | Device for reducing humidity of low-concentration gas and dehumidification method |
| CN103265985B (en) * | 2013-05-24 | 2014-11-12 | 北京时代桃源环境科技有限公司 | Device for reducing humidity of low-concentration gas and dehumidification method |
| CN104194854A (en) * | 2014-09-23 | 2014-12-10 | 北京化工大学 | Hypergravity-process triglycol natural gas dehydration system and process using system |
| CN107739635A (en) * | 2017-08-31 | 2018-02-27 | 昆山市恒安工业气体有限公司 | A kind of purifying device for natural gas |
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Application publication date: 20120516 |