CN101480560B - Method for processing Claus tail gases by membrane separation - Google Patents

Method for processing Claus tail gases by membrane separation Download PDF

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CN101480560B
CN101480560B CN2008100557965A CN200810055796A CN101480560B CN 101480560 B CN101480560 B CN 101480560B CN 2008100557965 A CN2008100557965 A CN 2008100557965A CN 200810055796 A CN200810055796 A CN 200810055796A CN 101480560 B CN101480560 B CN 101480560B
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nitrogen
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membrane separator
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唐津莲
许友好
汪燮卿
龚剑洪
程从礼
谢朝钢
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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Abstract

The invention relates to a method for treating Claus tail gas by adopting a membrane separator. The Claus tail gas is treated and enters the membrane separator under the condition that the pressure is between 1.0 MPa and 2.5 MPa, preferably between 1.5 MPa and 2.0 MPa, the temperature is between 40 DEG C and 80 DEG C, preferably between 50 DEG C and 60 DEG C, and residual permeable gas containing high-concentration nitrogen and permeable gas concentrating SO2 and H2S are separated out, wherein one part of the permeable gas returns to a Claus device for reclaiming sulphur, while the other part returns to the membrane separator for further reclaiming the nitrogen. Compared with the low-temperature Claus method for reclaiming the sulphur, the invention has the advantages of low equipment investment cost, simple operation, low energy consumption and common nitrogen as a by-product.

Description

A kind of method that adopts film separating treatment Claus tail gases
Technical field
The invention belongs to the refining and utilization of Crouse (Claus) tail gas, more particularly, is a kind of Claus tail gases that separates in membrane separator, produces no sulphur ordinary nitrogen, and recycles the wherein method of sulfurous gas.
Background technology
The tail gas that emits from Cross unit is except containing a small amount of SO 2, H 2S and micro-O 2Outward, major part all is a nitrogen, nitrogen mass fraction 90 weight %, even more than the 95 weight %.Nitrogen is suitable for producing industrial general nitrogen in the Claus tail gas, and its sour gas SO 2, H 2S enters atmosphere, not only environment is caused serious harm, or a kind of very big waste of sulphur resource.
At present, the claus sulphur recovery units tail gas treatment process is broadly divided into low-temperature Claus method, reduction absorption process and catalytic oxidation three major types by its principle, ubiquity device complexity, and operating difficulties is invested defectives such as big.At present most widely used is the low-temperature Claus method, and this method is included in the organic solvent that is added with special catalyst, under the temperature a little more than the sulphur fusing point, makes the H in the tail gas 2S and SO 2Proceed the low temperature liquid phase claus reaction, or under the temperature that is lower than the sulphur dew point, low temperature solid phase claus reaction takes place, as described in patent CN1031194A on solid catalyst.The low-temperature Claus method can not reduce COS and CS in the tail gas 2Content, sulfur recovery rate is on the low side, is about 98.5%~99.5%.
Along with the development of membrane technology, sour gas SO in the industrial tail gas 2, H 2S removes, and also is devoted in recent years to collect to separate with the embrane method that is absorbed in one to absorb processing sulfur-bearing tail gas, removes wherein SO 2, H 2S.The desulfurization of embrane method tail gas, especially embrane method flue gas desulfurization has small investment, and is simple to operate, low power consumption and other advantages.The desulfurization of embrane method tail gas, the main at present doughnut tubular type membrane separator that adopts, its hollow-fibre membrane is the selectivity ventilated membrane, all discloses cellulose hollow fiber gas separation membrane and preparation thereof as CN1199718C, CN1234448C, CN1235669C.SO in the tail gas 2, CO 2Can enter alkaline solution (Na by the selective permeation fenestra 2SO 3Or NaOH), and with its reaction generate NaHSO 3, NaHCO 3, and the N in the flue gas 2, O 2Wait other gases to be trapped in the gas phase, thereby realize flue gas desulfurization, take off CO 2The technological process that the hollow-fibre membrane flue gas removes sour gas is: flue gas enters hollow fiber membrane separator after dedusting, heat exchange, remove SO 2, CO 2Back flue gas is by smoke stack emission, and absorption liquid enters the regeneration of regeneration of absorption solution device and reclaims sulphur or CO 2Doughnut embrane method flue gas desulfurization at present, take off CO 2Be considered to a kind of higher flue gas desulfurization technique of flue gas treatment technology, especially economic benefit that huge commercial application potential is arranged.
For improving desulfuration efficiency, the embrane method desulfurization often combines with other gas separating methods, announced the method for diffusion barrier unit and PSA unit combination separation/recovery of gases as CN1140318C, CN1047632A utilizes the water-soluble, polymeric chelate of polyvalent metal and membrane separation device is removed nitrogen oxide and sulfur oxide from air-flow method, CN1919423A sulphur dioxide-air battery and the application in desulfur technology thereof, CN1297337C ultrasonic wave and doughnut contained liquid membrane are in conjunction with the device and method that removes sulfur dioxide in the gas.
Existing Claus tail gases desulfur technology absorbs the desulfurization ratio with embrane method, equipment investment expense height, and complicated operation, energy consumption is higher; But embrane method absorbs desulfurization absorption liquid easily pollution and regeneration difficulty, is easy to stop up fenestra road desulfurization degree low (desulfurization degree is about 60~90%), has therefore hindered the industrial applications of embrane method tail gas desulfurization, awaits further developing Claus tail gases sulfur recovery new technology.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of method that adopts film separating treatment Claus tail gases, to concentrate the pernicious gas in the Claus tail gases and then to return Cross unit and continue claus reaction recovery sulphur and produce industrial ordinary nitrogen.
The objective of the invention is to realize by following proposal: Claus tail gases is after preliminary treatment, under the preferred 1.5~2.0MPa of pressure 1.0~2.5MPa, 40~80 ℃ of preferred conditions of 50~60 ℃ of temperature, enter membrane separator, isolate and contain oozing residual air and having concentrated SO of nitrogen-rich gas 2, H 2The infiltration gas of S wherein permeates gas and partly returns Cross unit recovery sulphur, and another part returns membrane separator and further reclaims wherein nitrogen, and described Claus tail gases comprises the O that is higher than the above nitrogen of 85 weight %, is lower than 1 weight % 2Content and SO 2, H 2The total amount of S is not higher than 6 weight %, and described preliminary treatment comprises dedusting, dehydration and drying, pretreated flue gas solid content≤0.01mg/Nm 3, H 2O≤1ppm.
Method provided by the present invention is applicable to that any nitrogen content is higher than the above and O of 85 weight % 2Content is lower than the Claus tail gases of 1 weight %, is particularly useful for nitrogen content and is higher than the above and O of 90 weight % 2Content is lower than the Claus tail gases of 0.5 weight %.Other composition comprises SO in the Claus tail gases 2, H 2S, COS, S, CO 2, H 2O etc., wherein SO 2, H 2The total amount of S preferably is not higher than 6 weight %, and the content of COS and S preferably is not higher than 1 weight %.All gas consist of 100%.
The preliminary treatment of Claus tail gases comprises dehydration dedusting, pressurization and heat exchange.Pretreated Claus tail gases also is weighed into film gas, its micronic dust content≤0.01mg/Nm 3, H 2O≤1ppm.
The dehydration dedusting comprises removes all diameters of carrying secretly in gas solid particle and mist of oil, water smoke and aerocolloidal all dust collection methods greater than 0.01 μ m, as inertial dust collection method, wet dedusting method, Cottrell process, filtering type process of cleaning, monotubular cyclone dust removal method and multi-cyclone process of cleaning and centrifugal force separation, gravitational settling, baffling separation, silk screen separation, ultra-filtration and separation, filler separation etc., preferred centrifugal force separates, the filtering type process of cleaning.Micronic dust content≤0.01mg/Nm 3, require remaining oil content less than 0.01 milligram/meter 3, and make into film gas and contain trace steam or do not contain steam, require H in the film gas 2O≤1ppm.
Can comprise that the pneumatic booster pump of any suitable sulfur-bearing, nitrogen or gas-booster make into film gas by supercharging mode and be pressurized to the preferred 1.5~2.0MPa of 1.0~2.5MPa.
Can make into film temperature degree by heat exchange mode and be reduced to 40~80 ℃ preferred 50~60 ℃, described flue gas heat exchange mode comprises various hybrid, heat accumulating types or dividing wall type heat exchanger, preferred dividing wall type heat exchanger, wherein dividing wall type heat exchanger can be the custom design heat exchanger of jacket type, tubular type, board-like or various special-shaped heat-transfer area composition.The type of flow of cold fluid and hot fluid in heat exchanger comprises following current, adverse current, cross-current, mixed flow, preferred adverse current.
Described membrane separator comprises the gas film separator of any flat, rolling that is applicable to that gas separates or the one or more formations of doughnut formula membrane module.Wherein membrane material comprises the compound of one or more materials in macromolecular material, inorganic material, the metal material, preferred polymeric membrane, more preferably composite high-molecular film.Polymeric membrane is selected from one or more in dimethyl silicone polymer (PDMS), polysulfones (PSF), Nomex, cellulose acetate (CA), ethyl cellulose (EA), Merlon (PC), polyimides, polyphenylene oxide, the silicone rubber membrane, the composite membrane that preferred polysulfones (PSF), polyimide film, methyl silicone rubber film or its Modified Membrane and several macromolecular material make.Membrane separator can adopt one-level flow process, two-stage process or multistage flow process.
The described residual air of oozing requires nitrogen gas concn to be higher than 99.5 weight %, SO 2And H 2S concentration is lower than 0.5 weight %.The conventional Claus tail gas of its non-embrane method sulfur method comprises that any alkali lye absorbs, amine liquid absorbs and molecular sieve, and the solid absorption desulfurization of active carbon and metal oxide etc. removes micro-H 2S and SO 2Method, the method for preferred metal oxide-loaded adsorption desulfurize.
Described infiltration gas is divided into two parts, and wherein a part is directly sent into the SO in the Claus technology after heat exchange 2With H 2The S reactor reclaims sulphur, and the Sulfur Recovery Unit reaction temperature is 200~370 ℃; Another part supercharging after desulfurization (sulfur method is identical with top nitrogen sulfur method) or not desulfurization enters membrane separator once more or the secondary membrane separator further reclaims wherein nitrogen, and its boosting method is identical with the unstripped gas boosting method.The weight ratio of sending into the infiltration gas of Cross unit and returning between the infiltration gas of membrane separator is 0.5~8.5 preferred 2.5~5.5.
The present invention compared with prior art has following characteristics:
1, as tail gas sulfur recovery technology, compare with the sulfur recovery of low-temperature Claus method, the present invention has that the equipment investment expense is low, simple to operate, advantage of low energy consumption.
2, the present invention handles good, the advantages such as separative efficiency is high, non-secondary pollution of Claus tail gases selectivity.
3, as nitrogen producing craft, to compare with the air making nitrogen by pressure swing adsorption, film system floor space is little, long service life; The equipment investment expense is low, and is simple to operate, and operating cost is low.
4, the present invention compares with pressure swing adsorption method, has no movable part, and preprocessing part is less, starts soon, does not need cooling water, advantage of low energy consumption.
Description of drawings
Fig. 1 is that the composite hollow fiber membrane separator divides separable flue gas to reclaim the nitrogen schematic diagram.
Fig. 2 is a composite hollow fiber membrane cyclone separator arrangement schematic diagram.
The specific embodiment
Further specify method provided by the present invention below in conjunction with accompanying drawing, but therefore the present invention is not subjected to any restriction.
Fig. 1 is that the composite hollow fiber membrane separator separates Claus tail gases recovery nitrogen schematic diagram.After gas centrifuge 1 is tentatively removed the solid particle and water that carries in the tail gas, enter high pressure storage tank 3 after being pressurized to 1.0~2.5MPa by gas-booster 2 from the normal temperature tail gas of claus process; Through further dehydration dedusting of active carbon filter 4, after counter-current pipe exchanger 5 heat exchange, make the Claus tail gases temperature reach 40~80 ℃ again, what obtain not moisture and micronic dust once more after accurate filter 6 is removed the solid particle of all diameters greater than 0.01 μ m goes into film gas, under the condition of 40~80 ℃ of pressure 1.5~2.5MPa, temperature, enter and be suitable for the composite hollow fiber membrane separator 7 that sour gas separates, isolate and contain oozing residual air and having concentrated SO of nitrogen-rich gas 2, H 2The infiltration gas of S.Wherein permeating gas draws through pipeline 14 from infiltration gas outlet and is divided into two parts, a part is returned Cross unit through pipeline 15 and is reclaimed sulphur, another part through pipeline 16, gas-booster 17, pipeline 18 active carbon filters 4, enters membrane separator once more and further reclaims nitrogen successively after heat exchanger 5 heat exchange, accurate filter 6 depth-type filtrations; Ooze that nitrogen content is higher than 99.5 weight % in the residual air, ℃ further absorb or the wherein micro-SO of adsorbing and removing through desulfurizer 8 in normal temperature~200 2, produce more high-purity nitrogen.
Fig. 2 is a composite hollow fiber membrane cyclone separator arrangement schematic diagram.The composite hollow fiber membrane separator has housing 10, be provided with membrane module 11 in the housing, at an end and the membrane module 11 parallel Claus tail gases inlets 9 that are provided with of housing 10, ooze residual air outlet 12 an end and membrane module 11 parallel being provided with of housing 10, the housing upper side is provided with infiltration gas outlet 13.Claus tail gases flows in the composite hollow fiber membrane component internal, walks the membrane module tube side as the nitrogen of gas slowly and discharges through nitrogen outlet, as the SO of fast gas 2, H 2S etc. appear membrane module and discharge through the outlet of infiltration gas.
The following examples will give further instruction to method provided by the invention, but therefore not make the present invention be subjected to any restriction.
The composition of employed unstripped gas is listed in table 1 among the embodiment.The ModeI#PA3030-P1-3A-00 separator that employed hollow-fibre membrane and membrane module are produced for Bai Meiya Co., Ltd.The embodiment of the invention adopts the hollow fiber film assembly parameter to see Table 1 respectively.
Embodiment 1~4
Embodiment 1~4 explanation: adopt method provided by the invention, investigate the result who handles different material under the different technology conditions with different membrane separators.
Be raw material, wherein SO with the listed Claus tail gases A~C of table 2 respectively 3Content all is lower than 10ppm, and through preliminary treatment, film separates and absorption.Concrete test procedure is as follows: Claus tail gases enters high pressure storage tank after preliminary centrifugation, supercharging, again through the dedusting of active carbon filter filtering means dehydration, and after heat exchange, the smart filtration, its micronic dust content≤0.01mg/Nm 3, H 2O≤1ppm enters different membrane separators such as PS membrane, polyimide film and methyl silicone rubber, isolate be rich in nitrogen ooze residual air and sulfur-bearing infiltration gas.Ooze residual air through 10 weight % sodium hydrate aqueous solutions, 40%N-methyldiethanolamine solution and the laggard one-step removals of different adsorbents adsorb such as commercially available zinc oxide, ferric oxide desulfurizer wherein Determination of Trace Sulfur make nitrogen-rich gas; Infiltration gas part is according to a certain percentage sent into the Sulfur Recovery Unit reactor as residual gas through heat exchange, the commercial claus reaction catalyst of the alumina base LS-981 that adopts Shandong Qilu Keli Chemical Research Institute Co., Ltd. to produce, sulphur is reclaimed in reaction under 200~370 ℃ of conditions; Return membrane separator after another part infiltration gas pressurizes as backflow gas and continue system nitrogen.Experimental condition, result of the test and nitrogen composition are listed in table 3.
As can be seen from Table 3, the different Claus tail gases of forming are at 500~1000Nm 3Under/h the different in flow rate, through the film processor processing, ooze residual air after desulfur technology is handled, all more than 60.9 weight %, its purity is all more than 99.5% for the nitrogen yield; Send into Cross unit infiltration gas, under different temperatures, react its SO through Sulfur Recovery Unit 2The rate of recovery is all more than 97.1%, H 2The S rate of recovery is all more than 95.3%.
Table 1, membrane module parameter
Figure GSB00000606836100061
Table 2, Claus tail gases raw material are formed
The unstripped gas numbering A B C
N 2, weight % 86.6 90.9 96.2
SO 2, weight % 2.7 1.5 0.38
H 2S, weight % 4.8 2.8 0.9
CO 2, weight % 4 2.5 0.47
H 2O, weight % 0.7 0.9 0.2
O 2, weight % 0.2 0.5 0.9
COS, weight % 0.8 0.4 0.1
S, weight % 0.2 0.5 0.85
Amount to weight % 100.00 100.00 100.00
Table 3, experimental condition and result
Figure GSB00000606836100081
Remarks (1): suitably mend H in the experimentation 2S makes H in the course of reaction 2S and SO 2The molar flow rate ratio near 2: 1.

Claims (10)

1. a method that adopts film separating treatment Claus tail gases is characterized in that Claus tail gases after preliminary treatment, enters membrane separator under the condition of 40~80 ℃ of pressure 1.0~2.5MPa, temperature, isolates to contain oozing residual air and having concentrated SO of nitrogen 2, H 2The infiltration gas of S wherein permeates gas and partly returns Cross unit recovery sulphur, and another part returns membrane separator and further reclaims wherein nitrogen, and described Claus tail gases comprises the O that is higher than the above nitrogen of 85 weight %, is lower than 1 weight % 2Content and SO 2, H 2The total amount of S is not higher than 6 weight %, and described preliminary treatment comprises dedusting, dehydration and drying, pretreated flue gas solid content≤0.01mg/Nm 3, H 2O≤1ppm.
2. according to the method for claim 1, it is characterized in that described Claus tail gases comprises the O that is higher than the above nitrogen of 90 weight %, is lower than 0.5 weight % 2The SO that content is following with being lower than 2 weight % 2, be lower than the following H of 4 weight % 2S.
3. according to the method for claim 1, it is characterized in that the condition that film separates is: 50~60 ℃ of pressure 1.5~2.0MPa, temperature.
4. according to the method for claim 1, it is characterized in that described membrane separator is made of one or more flat, rollings or doughnut formula membrane module, wherein membrane material comprises the compound of one or more materials in macromolecular material, inorganic material, the metal material.
5. according to the method for claim 4, it is characterized in that described macromolecular material is selected from one or more in dimethyl silicone polymer, polysulfones, Nomex, cellulose acetate, ethyl cellulose, Merlon, polyimides, polyphenylene oxide, the silicone rubber membrane.
6. according to the method for claim 1 or 5, it is characterized in that described membrane separator adopts one-level flow process, two-stage process or multistage flow process.
7. according to the method for claim 1, it is characterized in that describedly oozing that nitrogen gas concn is higher than 99.5 weight %, SO in the residual air 2With H 2The total amount of S concentration is lower than 0.5 weight %.
8. according to the method for claim 1, the weight ratio between the infiltration gas that it is characterized in that sending into the infiltration gas of Cross unit and returning membrane separator is 0.5~8.5.
9. according to the method for claim 8, the weight ratio between the infiltration gas that it is characterized in that sending into the infiltration gas of Cross unit and returning membrane separator is 2.5~5.5.
10. according to the method for claim 1, it is characterized in that described Cross unit reaction temperature is 200~370 ℃, H in the course of reaction 2S and SO 2The molar flow rate ratio near 2: 1.
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US7901646B2 (en) * 2009-08-05 2011-03-08 General Electric Company System and method for sulfur recovery
CN102198362B (en) * 2010-03-25 2014-03-12 中国石油化工股份有限公司 Method for recovering nitrogen in flue gas with membrane
CN102989268B (en) * 2011-09-15 2015-11-25 中国石油化工股份有限公司 A kind of method adopting membrane separation Claus tail gases
CN105457455A (en) * 2014-09-23 2016-04-06 中国石油化工股份有限公司 Method for removing acidic gases in shift gas
CN104524893A (en) * 2014-12-15 2015-04-22 成都昊特新能源技术股份有限公司 Process for carrying out combined dust removal on tar-containing flue gas by utilizing dust remover of particle layer of flowing bed and flat-plate membrane filter
US10106410B2 (en) * 2017-03-10 2018-10-23 Saudi Arabian Oil Company Enhancement of Claus tail gas treatment by sulfur dioxide-selective membrane technology
US10106411B2 (en) * 2017-03-13 2018-10-23 Saudi Arabian Oil Company Enhancement of claus tail gas treatment by sulfur dioxide-selective membrane technology and sulfur dioxide-selective absorption technology
US10239763B1 (en) * 2017-12-05 2019-03-26 Saudi Arabian Oil Company System for tail gas treatment of sulfur recovery units

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