CN1162203C - Physical process for removing sulfur and carbon by solvent - Google Patents
Physical process for removing sulfur and carbon by solvent Download PDFInfo
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- CN1162203C CN1162203C CNB011272600A CN01127260A CN1162203C CN 1162203 C CN1162203 C CN 1162203C CN B011272600 A CNB011272600 A CN B011272600A CN 01127260 A CN01127260 A CN 01127260A CN 1162203 C CN1162203 C CN 1162203C
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Abstract
The present invention belongs to the field of gas separation engineering. A novel physical absorption solvent is adopted, a main body of the physical absorption solvent is polyethylene glycol dimethyl ether CH<3>O (c<2>H<4>O) <x>CH<3>, and constituent requires X=2 and X=3, <=13%, X=4, X=5 and X=6,>=73%, X=7 and X=8, <=12%. An activating agent is a heterocyclic compound, when in use, the solution is allowed to contain water with a quantity of smaller than 10%(wt). An absorption temperature is-5 to 40 DEG C, and the absorbent pressure is 1.4 to 6.0Mpa. Compared with other technologies, the present invention has the advantages of low energy consumption, high purifying rate, strong capability for absorbing acid gas, desulfurization with selectivity, no corrosion of the solvent, less investment, less volatilization loss of the solvent, stable solvent, asepsis, no taste, short process and convenient operation. The present invention has a wide application range, and is especially suitable for purification of ammonia synthesis gas of sulfide and high carbon dioxide content, methanol synthesis gas and oxo synthesis gas by using coal as a raw material. The present invention is also suitable for eliminating acid gas in natural gas, oil field gas, refinery gas and city gas, and has obvious economical and social benefits.
Description
Technical field: the invention belongs to gas delivery engineering field, specifically is the energy-efficient physical absorption method about sulfide and carbonic acid gas in the removing process gas.
Background technology: carbonic acid gas and sulfide remove in all needing unstripped gas in the industry such as, oxo process synthetic in ammonia synthesis, methyl alcohol, hydrogen manufacturing, Sweet natural gas, to satisfy the requirement of back operation.Sophisticated purifying method is a lot of on the current industrial, can be divided into chemical absorption, physical absorption, physical chemistry and absorb three class methods.In general, the investment and the process cost of physical absorption process are lower, needn't adopt steam regeneration, need not settle a large amount of heat-exchange equipments and large-scale cooling system.And when unstripped gas was formed with other processing condition fluctuation, the physical absorption device had bigger adaptability and turndown ratio.
Technology related to the present invention mainly contains:
1, Kohl, A.L., and Riesenfield, F.C., " Gas Purification ", Third Edition, Gulf PublishingCompany, 1979, the Rectisol technology (cold methanol method) of strange (Lurgi) company in the German Shandong that 748-756,773-779, these books and newspapers have led.Gas such as carbonic acid gas, sulfide has very big solubleness in low-temp methanol, in case step-down, these gas dissolvedes are easily overflowed from methanol solution again.Also reported the Fei Luoer solvent technology of U.S. Fei Luoer (Fluor) company exploitation in the book.It is great amount of carbon dioxide in the physical absorption solvent removal Sweet natural gas with the propylene carbonate.Further being in the synthesis ammonia plant of raw material with the Sweet natural gas, removed carbonic acid gas in the conversion gas afterwards with propylene carbonate.
2, US 3,737,392,1973, remove the used solvent composition of sour gas from gaseous mixture.This patent is declared by U.S. Ah Leadd B.V (Allied Chemical Corporation).The Sai Lekesuo that is declared (Selexol) technology is with Polyethylene glycol dimethyl ether [CH
3O (C
2H
4O)
XCH
3] be solvent, in the formula: X=3,4～9% are roughly formed in X=3～9, homologue; X=4,22～24%; X=5,24～28%; X=6,20～22%; X=7,13～15%; X=8,6～8%; X=9,2～4%.This method is used for removing sour gas such as the contained hydrogen sulfide of gaseous mixture (as Sweet natural gas), carbonic acid gas.
3, US 4,044,100,1977, separating acid gas component from gaseous mixture.Proposed to remove the technology of sour gas in the gaseous mixture with poly-alkane glycol dialkyl ether and diisopropanolamine (DIPA) mixed solvent.Under selected acceptance condition, mixed solvent keeps homogeneous phase.The mixed solvent that has absorbed sour gas can be recycled after regeneration.
4, CN 85,103,897,1985, and the efficient physical method that removes sulfide and carbonic acid gas from the gas mixture of acid gas-containing released in article, adopt to consist of CH
3O (C
2H
4O)
XCH
3Polyalcohol ether is made absorption agent, X=2 wherein, 2～5%; X=3,18～19%; X=4,28～30%; X=5,23～26%; X=6,18～20%.This method is compared with other physics method, and it is low to have energy consumption, the degree of purification height, and characteristics such as selectivity is good, and flow process is simple, and solvent is nontoxic, does not have corrosion, and is stable can be used for the purification of synthetic ammonia and hydrogen feedstock gas, town gas, Sweet natural gas etc., to obtain energy-saving effect preferably.
Summary of the invention: the present invention compares with existing external Selexol technology, domestic polyalcohol ether technology, and the solvent difference has better mass transfer and separation performance.Used activator is neutral heterocyclic compound, according to the broad acid-base theory, it contains-molecular structure of a kind of like this hard base group of C=O, help the absorption of hard acidic gases such as carbonic acid gas, hydrogen sulfide, improved receptivity, determined the operational condition different with other technology.See table 1 for details.
Table 1
| Selexol technology | Polyalcohol ether technology | The present invention | |
| Absorption pressure MPa | 3.5～10.5 | 2.0 | 1.4～6.0 |
| Activating component in the solvent | Do not have | Do not have | Have |
| Absorb the sour gas ability | 1.0 | 1.1 | 1.2 |
| Use solvent comprises water amount Wt% | ＜3 | ＜8 | ＜10 |
| Gas drawings tolerance | 1.0 | 0.9 | 0.8 |
The present invention adopts a kind of novel physical lyosorption, and its target is that (1) increases CO
2, H
2The receptivity of S, COS etc.; Absorb when (2) reducing all gases; (3) internal circulating load of minimizing solvent; (4) improve mass-transfer efficiency; (5) reduce the solvent expense.
The present invention is achieved in that the solvent main body is Polyethylene glycol dimethyl ether CH
3O (C
2H
4O)
XCH
3, composition requirement X=2 and X=3 ,≤13%; X=4, X=5 and X=6, 〉=73%; X=7 and X=8 ,≤12%, activator is a kind of heterocyclic compound, during use, allows that solution contains the water yield less than 10% (wt).
Absorption temperature of the present invention-5～40 ℃, absorption pressure 1.4～6.0MPa.Unstripped gas advances tower from the bottom, absorption tower, with by cat head spray and under solvent, counter current contact in packing layer.Sour gas in the unstripped gas is removed, and purified gas is discharged by cat head, and rich solution is discharged in the bottom, absorption tower.Through one-level or what vacuum flashing, flash liquid is squeezed into regenerator column, proposes regeneration by rare gas element (air, nitrogen etc.) or steam gas.Resurgent gases is discharged system by cat head.Lean solution after the regeneration is gone out by tower bottom flow, squeezes into the top, absorption tower by solution pump, recycles.When purification was less demanding, flash liquid can directly be squeezed into the absorption tower and recycle, and leaves out gas and puies forward regeneration step.
The present invention can remove carbonic acid gas, remove carbonic acid gas after removing sulfide and carbonic acid gas, first selectively removing sulfide simultaneously.
Unstripped gas of the present invention can be ammonia synthesis gas, methyl methanol syngas, oxo-synthesis gas, hydrogen feedstock gas, Sweet natural gas, oil field gas, refinery gas or town gas etc.
Main economic and technical indices of the present invention: after cleaning by solvent of the present invention, the process gas carbonated is less than 0.1%, and hydrogen sulfide is less than 1ppm, and the sulphur carbonoxide is less than 1ppm, confession urea (or other) use carbon dioxide purity greater than 98.5%, solvent consumption is less than 0.2Kg/TNH
3, power consumption can be less than 80KWH/TNH
3The degree of purification height, energy consumption is low, remarkable benefit.
Description of drawings: accompanying drawing 1 is the embodiment of the invention 1 a flow process simplified schematic diagram; Accompanying drawing 2 is the embodiment of the invention 2 flow process simplified schematic diagram; Accompanying drawing 3 is the embodiment of the invention 3 flow process simplified schematic diagram.In the accompanying drawing 1, the 1-absorption tower; The 2-flash drum; The 3-regenerator column; The 4-storage tank; The 5-solvent pump.In the accompanying drawing 3, the 1-thionizer; 2, the 14-water cooler; 3-flashed vapour compressor; 4,18, the 22-turbine; 5,8,13,20, the 24-pump; 6-desulfurization high pressure flash groove; 7-, 10,12, the 15-interchanger; 9-desulfurization low-pressure flashing tank; 11-desulfurization regeneration tower; The 16-separator; The 17-decarbonizing tower; The 19-ammonia cooler; 20-decarburization high pressure flash groove; 23-decarburization low-pressure flashing tank; 25-decarbonization gas stripper.
Embodiment: the embodiment of the invention is described in detail below in conjunction with accompanying drawing.
Embodiment 1 (seeing process flow sheet shown in the accompanying drawing 1)
Conversion gas by certain nitrogen fertilizer plant sends here advances tower from the bottom, absorption tower, with by cat head spray and under solvent, counter current contact in packing layer.Sour gas in the unstripped gas is removed, and purified gas is discharged by cat head.Rich solution is discharged in the bottom, absorption tower, decompression, and to the flash drum flash distillation, flashed vapour emptying.Flash liquid is pressed onto the section of separating often at regenerator column top automatically by statical head, separate the most of carbonic acid gas of sucking-off after, import the stripping section of regenerator column by upflow tube, with the air of sending into by tower bottom counter current contact in packing section.Gas stripping gas is discharged by tower top, and the lean solution after the regeneration is gone into solvent feed tank by tower bottom flow, squeezes into the top, absorption tower by solution pump, recycles.
Major equipment is as follows:
Absorption tower: Φ 38 * 2.5, H～3000, stainless steel, packed height is 1800mm, interior dress Φ 6 * 6 porcelain Raschig rings.
Gas stripping column: Φ 51 * 3.5, H～4100, stainless steel, packed height is 2500mm, interior dress Φ 8 * 8 porcelain Raschig rings.
The conversion atmospheric pressure is 1.7MPa, and temperature is a normal temperature, and tolerance is 160～400L/H, and main component is H
250～55%, N
214～18%, CO
224～28%, CO～3%, H
2S 2～10mg/Nm
3Solvent is polyalcohol ether process solvent and solvent of the present invention, and liquid measure is 7～8L/H.This model trial in fact also is a lateral flow assay.
Test-results shows that with polyalcohol ether solvent phase ratio, this solvent removal sour gas ability improves more than 10%, and available gas loss, solution circulated amount, absorption tower packed height, solvent input amount, investment cost and decarburization energy consumption are all descended, and see table 2 for details.
Table 2
| The polyalcohol ether solvent | This solvent | Relatively | |
| Absorb CO 2Ability | 1 | 1.087～1.175 | Improve 8.7～17.5% |
| CO 2Degree of purification % | 2.52～9.70 | 1.38～8.44 | Improve 13～45% |
| H 2、N 2Loss | 1 | 0.87 | Reduce 13% |
| The solution circulated amount | 1 | 0.87 | Reduce 13% |
| The absorption tower height | 1 | 0.77 | Reduce 23% |
| The solvent input amount | 1 | 0.87 | Reduce 13% |
| The investment total expenses | 1 | 0.90～0.92 | Reduce 8～10% |
| Decarburization energy consumption | 1 | 0.903 | Reduce 9.7% |
Embodiment 2, (seeing process flow sheet shown in the accompanying drawing 2)
Present embodiment is the process that removes carbonic acid gas.
Become the degassing and (pressure 1.6MPa, 40 ℃ of temperature, contain CO
228%) mixes with the high gas that dodges, enter gas heat exchanger E101, cooled off, and after advancing tower gas separating device V101 and separating water of condensation, enter decarbonizing tower T101 by low pressure flash gas and decarbonization gas.In tower, the carbonic acid gas in the air-flow is absorbed, and leaves decarbonizing tower from cat head, and at this moment, the decarbonization gas carbonated by gas heat exchanger E101, advances tower gas with cooling less than 0.2%, goes subsequent handling then.
Rich solution goes out from the decarbonizing tower underflow, step-down flash distillation in high pressure flash groove V104, and the high gas that dodges mixes with the change degassing, and through nitrogen-hydrogen compressor compression, reentry system.The high liquid that dodges enters low-pressure flashing tank V105, further step-down, flash distillation.Low to dodge gas mainly be carbonic acid gas, after E101 cools off into tower gas, can make multiple use.The low liquid that dodges is got to gas stripping column T102 top by rich solution pump P102, contacts with gas exhaust circulation of vital energy in the wrong direction stream, and solution obtains regeneration, through lean pump P101, ammonia cooler E102, sends into decarbonizing tower, is reused for absorbing carbon dioxide.Gas exhaust gas is supplied with by gas blower C101,, is entered bottom the gas stripping column by the stripper overhead cooling of dropping a hint at air-cooler E103, and gas exhaust gas and by the carbonic acid gas of desorb together leaves emptying behind air-cooler from stripper overhead.
If water content is too high in the solution, can extracts partial solvent and dewater.
Embodiment 3, (seeing process flow sheet shown in the accompanying drawing 3)
Present embodiment is first selectively removing hydrogen sulfide, then, removes the process of carbonic acid gas again.
Conversion gas (pressure 3.3MPa, 38 ℃ of temperature, contains H
2S 1～3g/Nm
3, COS 1.6ppm, CO
244%) with flashed vapour, enter the lean solution counter current contact under thionizer 1 bottom and the overhead streams, absorb whole H
2S, COS and portion C O
2, go out the sweet gas of desulfurization cat head, contain H
2S＜1ppm send decarbonization system.
The rich solution of discharging at the bottom of the thionizer, through hydraulic turbine 4 recovered energies, the 1.2MPa that reduces pressure (a) enters desulfurization high pressure flash groove 6, and the high gas (with decarbonization) that dodges returns thionizer, with recover hydrogen through 3 pressurizations of flashed vapour compressor.High lean solution heat exchange in poor rich liquid heat exchanger 7 of dodging after liquid is regenerated with heat enters desulfurization low-pressure flashing tank 9, and the pressure-controlling of lower flash slot is about 0.7MPa (a), and the low gas (with resurgent gases) that dodges is sent to sulphur recovery plant through regeneration condensate cooler 14.Low lean solution of dodging after liquid is regenerated with heat, heat exchange in poor rich liquid heat exchanger 10 enters regenerator column 11 tops.Solution, is driven out of the residual amount hydrogen sulfide in the solution with conversion gas hot digestion by conversion gas boiling device 12 at the bottom of the regenerator column, obtains the higher regeneration lean solution of poor degree.Lean solution is through poor rich liquid heat exchanger 10, lean pump 8, and poor rich liquid heat exchanger 7 by 5 superchargings of desulfurization high-pressure pump, and cool off in lean solution water cooler 2 by water coolant, and finally lean solution is entered the thionizer top with 38 ℃, has finished solution circulated.The resurgent gases of regenerator column packing section is through the eddy flow plate on tower top, and the phlegma washing cooling with trim the top of column goes out regenerator column, enters resurgent gases condensate cooler 14, is sent to sulphur recovery plant at last.The phlegma that separates is squeezed into the washing section of regeneration overhead with backflow liquid pump 13.
Sweet gas enters gas heat exchanger 15, by decarburization low pressure flash gas and decarbonization gas cooling, and the solvent mist that in advancing tower gas separating device 16, separates water of condensation and carry secretly, enter decarbonizing tower 17.In tower, the carbonic acid gas in the air-flow is absorbed, and leaves decarbonizing tower from cat head.At this moment, decarbonization gas carbonated～0.1%, by interchanger 15, after tower gas is advanced in cooling, the demethanization device.
Rich solution goes out from the decarbonizing tower underflow, through hydraulic turbine 18, and recovery part energy, flash distillation in high pressure flash groove 21 then.Decarbonization mixes with the high gas that dodges of desulfurization, through the flashed vapour compressor pressurizes, returns thionizer, with recover hydrogen.The high liquid that dodges enters low-pressure flashing tank 23 through hydraulic turbine 22, further continues flash distillation under lower pressure.Gas concentration lwevel is sent to urea plant more than 98.5% in the low sudden strain of a muscle gas.The low liquid that dodges is delivered to gas stripping column 25 tops by pump 24, when flowing through packing layer downwards, is carried nitrogen gas by gas and proposes regeneration.Gas is carried nitrogen from air separation facility, after passing through all packing layers, in company with the carbonic acid gas emptying together that is put forward by gas.Lean solution after the regeneration increases pressure head through lean pump 20, by ammonia cooler 19, is cooled to-5 ℃ by liquefied ammonia, enters decarbonizing tower, is reused for absorbing carbon dioxide.
Claims (5)
1, a kind of physical solvent desulfurization and decarburization technology is characterized in that absorption agent is with Polyethylene glycol dimethyl ether [CH
3O (C
2H
4O)
XCH
3, wherein X=2 and X=3 ,≤13%; X=4, X=5 and X=6, 〉=73%; X=7 and X=8 ,≤12% ,] be main body, with contain-the neutral heterocyclic compound of the molecular structure of a kind of like this hard base group of C=O is an activator, during use, allows that solution contains the water yield less than 10% (wt); Absorption temperature-5～40 ℃; Absorption pressure 1.4～6.0Mpa.
2, a kind of physical solvent desulfurization and decarburization technology as claimed in claim 1 is characterized in that removing carbonic acid gas.
3, a kind of physical solvent desulfurization and decarburization technology as claimed in claim 1 is characterized in that removing simultaneously sulfide and carbonic acid gas.
4, a kind of physical solvent desulfurization and decarburization technology as claimed in claim 1 is characterized in that removing carbonic acid gas behind the first selectively removing sulfide.
5, a kind of as claim 1 or 2 or 3 or 4 described physical solvent desulfurization and decarburization technology, it is characterized in that unstripped gas is ammonia synthesis gas, methyl methanol syngas, oxo-synthesis gas, hydrogen feedstock gas, Sweet natural gas, oil field gas, refinery gas or town gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011272600A CN1162203C (en) | 2001-09-26 | 2001-09-26 | Physical process for removing sulfur and carbon by solvent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011272600A CN1162203C (en) | 2001-09-26 | 2001-09-26 | Physical process for removing sulfur and carbon by solvent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1356158A CN1356158A (en) | 2002-07-03 |
| CN1162203C true CN1162203C (en) | 2004-08-18 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100384510C (en) * | 2003-12-09 | 2008-04-30 | 南化集团研究院 | Method for removing sulfides and carbon dioxide by high pressure |
| CN100415345C (en) * | 2005-07-12 | 2008-09-03 | 南京理工大学 | Preparation of composite acid gas absorbent |
| CN101492616B (en) * | 2008-12-12 | 2012-12-19 | 兖矿鲁南化肥厂 | Desulfurization and decarburization integrated absorption process for polyglycol dimethyl ether |
| CN101659420B (en) * | 2009-08-07 | 2012-02-15 | 上海国际化建工程咨询公司 | Method and device for drying and purifying ammonia synthetic fresh gas |
| CN102397739B (en) * | 2011-11-11 | 2012-12-26 | 南通正拓气体有限公司 | Technology for preparing hydrogen and carbon dioxide by purifying and refining biological butanol fermentation tail gas and purification plant thereof |
| CN103432890B (en) * | 2013-09-10 | 2015-12-09 | 北京博源恒升高科技有限公司 | Modified poly (ethylene glycol) removes the method for SOx in gas |
| CN104495965A (en) * | 2014-12-30 | 2015-04-08 | 中国天辰工程有限公司 | Process for treating low-temperature condensate at conversion section |
| CN106334412A (en) * | 2015-07-14 | 2017-01-18 | 北京化工大学苏州（相城）研究院 | Skid-mounted carbon dioxide gas absorption method and apparatus applicable to offshore platform |
| CN107754559B (en) * | 2016-08-19 | 2020-10-20 | 中国石油化工股份有限公司 | Alcohol ether composite solvent for gas separation and method |
| CN111003690A (en) * | 2019-11-27 | 2020-04-14 | 浙江天禄环境科技有限公司 | Decarburization process of synthesis gas |
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