CN101884870A - Devices and methods for purifying sulphur-containing waste gas and recovering methane - Google Patents
Devices and methods for purifying sulphur-containing waste gas and recovering methane Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 246
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000005864 Sulphur Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000002912 waste gas Substances 0.000 title abstract description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 62
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 31
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 165
- 229910021536 Zeolite Inorganic materials 0.000 claims description 122
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 122
- 239000010457 zeolite Substances 0.000 claims description 122
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 76
- 239000000377 silicon dioxide Substances 0.000 claims description 76
- 238000001179 sorption measurement Methods 0.000 claims description 59
- 239000000463 material Substances 0.000 claims description 57
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 54
- 239000007789 gas Substances 0.000 claims description 52
- 238000011084 recovery Methods 0.000 claims description 50
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 229910052717 sulfur Inorganic materials 0.000 claims description 40
- 239000011593 sulfur Substances 0.000 claims description 40
- 238000003795 desorption Methods 0.000 claims description 33
- 238000000746 purification Methods 0.000 claims description 33
- 150000003568 thioethers Chemical class 0.000 claims description 33
- 239000002699 waste material Substances 0.000 claims description 29
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 25
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 21
- 238000007493 shaping process Methods 0.000 claims description 13
- 230000008929 regeneration Effects 0.000 claims description 12
- 238000011069 regeneration method Methods 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 10
- 230000008676 import Effects 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 239000002594 sorbent Substances 0.000 claims description 6
- 239000003463 adsorbent Substances 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 30
- 241000894006 Bacteria Species 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
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- 238000000855 fermentation Methods 0.000 description 5
- 230000004151 fermentation Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 241001672694 Citrus reticulata Species 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000004291 sulphur dioxide Substances 0.000 description 2
- 208000019901 Anxiety disease Diseases 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000009781 Myrtillocactus geometrizans Nutrition 0.000 description 1
- 240000009125 Myrtillocactus geometrizans Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000004130 lipolysis Effects 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- -1 sulphur compound Chemical class 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M21/00—Bioreactors or fermenters specially adapted for specific uses
- C12M21/04—Bioreactors or fermenters specially adapted for specific uses for producing gas, e.g. biogas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M47/00—Means for after-treatment of the produced biomass or of the fermentation or metabolic products, e.g. storage of biomass
- C12M47/18—Gas cleaning, e.g. scrubbers; Separation of different gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
- B01D2253/108—Zeolites
- B01D2253/1085—Zeolites characterized by a silicon-aluminium ratio
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/05—Biogas
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- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to devices for purifying sulphur-containing waste gas and recovering methane. The device for purifying sulphur-containing waste gas comprises an air blower, a vacuum pump, a valve combination and at least one sulphide purifying tower, is used for removing a sulphur-containing compound from the sulphur-containing waste gas, can be further combined with a methane recovering device to remove sulphide and carbon dioxide from the methane at the same time, and thus the methane is purified effectively. The invention also provides methods for purifying the sulphur-containing waste gas and recovering the methane.
Description
Technical field
The present invention is about the device and method of a kind of purifying sulphur-containing waste and fire damp recovery, particularly about a kind of device that can effectively remove sulfur-containing compound in the sulphur-containing exhaust gas, and this purifying sulphur-containing waste device is again in conjunction with a methane recovery device, can effectively remove the sulfur-containing compound in the biogas simultaneously and reclaim methane in this biogas.
Background technology
Biogas is that organic substance is in anaerobic environment, under the condition of certain temperature, humidity and acid-base value, Jing crosses the effect of Wei Sheng Wu Fermentation (sending out) ferment, a kind of fuel gas of generation, and owing to this kind gas is found in marsh, lake or pond at first, so be referred to as biogas by people.And containing the multiple gases composition in the biogas, wherein topmost combustible component is methane (CH
4).
In addition, biogas bacterium decomposing organic matter matter, and then the process of generation biogas then are referred to as Zhao Qi Fermentation ferment.According to the effect of each bacterioid in the gas fermentation process of natural pond, wherein the biogas bacterium can be divided into two big classes: bacterium is referred to as the first kind: decomposer, the effect of these decomposers are that the organic substance with complexity resolves into simple organic substance and carbon dioxide (CO
2) etc.Special decomposition of cellulose person is arranged in the middle of these decomposers, be referred to as cellulose-decomposing bacteria; Special decomposing protein person is also arranged, then be referred to as protein decomposing dacteria; Other person that do not reduce fat specially, other is referred to as the lipolysis bacterium; And second bacterioid is referred to as: contain methane bacteria, generally also be referred to as methane backeria, the effect of these methane bacterias then is that simple organic substance and carbon dioxide redox are become methane.Therefore, You machine Wu Zhi Fermentation ferment changes the process of biogas into, just as the twice program of a kind of product of plant produced: at first be via decomposing bacteria the organic substance of complexity such as ight soil, stalk, weeds to be processed into semi-finished product one compound simple in structure; Secondly then be to utilize the effect of methane bacteria De Fermentation ferment, simple compound be processed into product one promptly generate methane.
Biogas is a kind of mist, and its main component is a methane, secondly then contains carbon dioxide, hydrogen sulfide (H
2S), nitrogen and some other compositions.In the composition of biogas, combustible component comprises gases such as methane, hydrogen sulfide, methyl mercaptan, carbon monoxide and heavy hydrocarbon; Not flammable composition comprises gases such as carbon dioxide, nitrogen and ammonia.Methane content is 55%～70% in the biogas composition, carbon dioxide content is 28%～44%, the hydrogen sulfide average content is 0.034%, the methyl mercaptan of trace (wherein hydrogen sulfide and methyl mercaptan belong to tool corrosivity after [and its oxidation together).
Moreover, biogas be a kind of colourless, have flavor, poisonous, smelly gas, its main component methane are arranged is a kind of colourless, tasteless, odorless, nontoxic gas at normal temperatures.The methane molecule formula is CH
4, be the simple hydrocarbon that combines with four hydrogen atom institutes by a carbon atom.Methane is 0.54 with respect to the weight ratio of air, and compared to the weight of air, its weight is about half of air.Methane solubility is very low, in 20 ℃, during 0.1KPa, the water of 100 unit volumes can only dissolve the methane of 3 unit volumes.
Methane is a simple organic compound, is the gaseous fuel of a high-quality also, is blue flame during methyl hydride combustion, and maximum temperature can reach about 1400 ℃, and simultaneously, every cubic metre of caloric value of pure methane is 36.8 kilojoules.About 23.4 kilojoules of the caloric value that biogas is every cubic metre are equivalent to 0.55 kilogram of diesel oil or the 0.8 kilogram of coal back liberated heat that fully burns.From Thermal Efficiency Analysis, every cubic metre of heat that biogas can utilize, the heat that the 3.03 kilograms of coals that are equivalent to burn can utilize.
And biogas can be regarded as a kind of biochemical gas, as long as this biogas is through purifying, its characteristic and natural gas are as good as, the gas supplier need remove the impurity such as moisture content, hydrogen sulfide and particulate in the biochemical gas, and for making that purified gas more can completing combustion, the gas supplier can reduce the carbon dioxide content in the gas.If the gas of handling without above-mentioned decontamination procedure sometimes with natural gas mixed combustion, but reach to the quality of pipeline transportation when biochemical gas cleaning, these gases can be referred to as " renewable natural gas ".
These gases through purifying are as good as in using to go up with natural gas, can apply to generate electricity and stove and accessory etc., and compressed gas also can become the substitute of compressed natural gas, can be used on the internal combustion engine or fuel cell of automobile.
And biogas source in Taiwan is quite abundant, mostly do not filled part utilization in the past and let alone discharging, cause the waste of the energy and the anxiety of air pollution is arranged, reason is to contain a large amount of carbon dioxide and a spot of hydrogen sulfide in biogas, not only calorific value is low than natural gas and has stink and corrosivity, and is quite restricted on feasible the utilization.
Summary of the invention
In order to improve the problem that above-mentioned prior art faces, purpose of the present invention is providing a kind of purifying sulphur-containing waste device, it comprises: an air blast, a vacuum pumps, valve member combination and at least more than one sulfide purifying column, it is characterized in that this sulfide purifying column is in order to the desorption sulfur-containing compound, and this sulfide purifying column fills a high silica alumina ratio zeolite adsorption material, and the silica alumina ratio of this high silica alumina ratio zeolite adsorption material is more than 10.(in the said apparatus, if there is pressurized source then can omit air blast; If need not carry out the regeneration of adsorption material, this vacuum pumps also can omit)
In the purifying sulphur-containing waste device of the present invention, when this sulfide purifying column is two when above, this sulfides purifying column can be purification run simultaneously or batch purification run.
And in the above-mentioned purifying sulphur-containing waste device, the sulfur-containing compound of this sulfide purifying column institute desorption is hydrogen sulfide (H
2S) or methyl alcohol sulphur (CH
3SH); Moreover wherein this high silica alumina ratio zeolite adsorption material is MCM-41 zeolite, y-type zeolite or silica-rich zeolite (Silicalite), and the best is a silica-rich zeolite.
In addition, in above-mentioned purifying sulphur-containing waste device, the shaping form of this high silica alumina ratio zeolite adsorption material is graininess or honeycomb.
Another purpose of the present invention provides a kind of fire damp retracting device, and it comprises: an air blast, a vacuum pumps, valve member combination and more than one fire damp recovery tower is characterized in that this fire damp recovery tower comprises:
The monosulfide adsorbent, it is in order to the desorption sulfur-containing compound, and this sulfide sorbent is a high silica alumina ratio zeolite adsorption material, and the silica alumina ratio of this high silica alumina ratio zeolite adsorption material is more than 10;
One fire damp recovery catalyst, this fire damp recovery catalyst are in order to carbon dioxide and methane in the separation biogas, and fire damp recovery catalyst system is made up of activated carbon and zeolite.(in the said apparatus, if there is pressurized source then can omit air blast; If need not carry out the regeneration of adsorption material, this vacuum pumps also can omit)
In the fire damp retracting device of the present invention, when this fire damp recovery tower is two when above, these fire damp recovery towers can be purification run simultaneously or batch purification run.
And in the above-mentioned fire damp retracting device, the sulfur-containing compound of this sulfide sorbent institute desorption is hydrogen sulfide (H
2S) or methyl alcohol sulphur (CH
3SH); Moreover wherein high silica alumina ratio zeolite adsorption material is MCM-41 zeolite, y-type zeolite or silica-rich zeolite; And this activated carbon is through Ca
2+, Mg
2+Or Cu
2+The activated carbon of upgrading; And this X type zeolite is Li-X, Ca-X, Sr-X, Mg-X or Na-X type zeolite.
And in the above-mentioned fire damp retracting device, this high silica alumina ratio zeolite adsorption material the best is a silica-rich zeolite; This activated carbon the best is through Cu
2+The activated carbon of upgrading; And this X type zeolite the best is a Li-X type zeolite.
In addition, in above-mentioned fire damp retracting device, the shaping form of this high silica alumina ratio zeolite adsorption material is graininess or honeycomb; And the shaping form of this activated carbon and zeolite is honeycomb (if graininess easily produces explosion when carrying out suction-operated).
Another object of the present invention provides a kind of two stage fire damp retracting devices, and it comprises: two air blasts, two vacuum pumps, the combination of two valve members, at least more than one sulfide purifying column and at least more than one methane purifying column is characterized in that:
This sulfide purifying column is in order to the desorption sulfur-containing compound, and this sulfide purifying column fills a high silica alumina ratio zeolite adsorption material, and the silica alumina ratio of this zeolite adsorption material is more than 10;
This methane purifying column is in order to carbon dioxide and methane in the separation biogas, and this fire damp purifying column is made up of activated carbon and zeolite.(in the said apparatus, if there is pressurized source then can omit air blast; If need not carry out the regeneration of adsorption material, this vacuum pumps also can omit)
In two stage fire damp retracting devices of the present invention, when this sulfide purifying column and methane purifying column are two when above, this sulfides purifying column and methane purifying column can be purification run simultaneously or batch purification run.
And above-mentioned two stage fire damp retracting devices, wherein the sulfur-containing compound of sulfide purifying column institute desorption is hydrogen sulfide (H
2S) or methyl alcohol sulphur (CH
3SH); Moreover wherein high silica alumina ratio zeolite adsorption material is MCM-41 zeolite, y-type zeolite or silica-rich zeolite; And this activated carbon is through Ca
2+, Mg
2+Or Cu
2+The activated carbon of upgrading; And this X type zeolite is Li-X, Ca-X, Sr-X, Mg-X or Na-X type zeolite.
And in the above-mentioned two stage fire damp retracting devices, this high silica alumina ratio zeolite adsorption material the best is a silica-rich zeolite; This activated carbon the best is through Cu
2+The activated carbon of upgrading; And this X type zeolite is a Li-X type zeolite.
In addition, in above-mentioned fire damp retracting device, wherein the shaping form of this high silica alumina ratio zeolite adsorption material is graininess or honeycomb; And the shaping form of this activated carbon and zeolite is honeycomb (if graininess easily produces explosion when carrying out suction-operated).
And above-mentioned two stage fire damp retracting devices, it further comprises a methane storage element, in order to store the fire damp through purifying.
Another purpose of the present invention provides a kind of method of purifying sulphur-containing waste, and it comprises the following step:
(1) provides aforesaid purifying sulphur-containing waste device, in order to the desorption sulfur-containing compound;
(2) sulphur-containing exhaust gas of the institute desire being handled via air blast imports this device, opens or/and close the related valves group, carrying out the desorption of sulfur-containing compound, and discharges simultaneously through absorption sulfur-containing compound after-purification gas;
(3) open or/and close the related valves group, utilize vacuum pumps to aspirate the interior sulfur-containing compound of this device, to carry out the regeneration of adsorption material.
The method that a further object of the present invention provides a kind of fire damp to reclaim, it comprises the following step:
(1) provides aforesaid fire damp retracting device, in order to reclaim fire damp;
(2) biogas of the institute desire being handled via air blast imports this device, opens or/and close the related valves group, with separating of the desorption that carries out sulfur-containing compound and carbon dioxide and methane, and reclaims methane through purified treatment simultaneously;
(3) open or/and close the related valves group, utilize vacuum pumps to aspirate this device interior sulfur-containing compound and carbon dioxide, to carry out the regeneration of adsorption material.
Purpose of the present invention promptly is to provide a kind of device and method of effective purification of sulphur-containing exhaust gas, with sulphur compound contained in effective purification of sulphur-containing exhaust gas, it also can apply to the sulfur-containing compound in the purifying marsh gas, and further combined with the device of a methane recovery, to obtain the higher renewable natural gas of purity.
Whereby, method and device that purifying sulphur-containing waste of the present invention and fire damp reclaim, effective purification of sulphur-containing exhaust gas, and reclaim fire damp simultaneously, and can fully effectively utilize the biogas resource, reach effective utilization of natural resources.
Description of drawings
Fig. 1 is the purifying sulphur-containing waste schematic representation of apparatus of the present invention's first specific embodiment.
Fig. 2 is the schematic diagram of the fire damp retracting device of the present invention's second specific embodiment.
Fig. 3 is the schematic diagram of two stage fire damp retracting devices of the present invention's the 3rd specific embodiment.
[primary clustering symbol description]
1 purifying sulphur-containing waste device
2 fire damp retracting devices
3 liang of stage fire damp retracting devices
10 air blasts
The 10-1 air blast
20 vacuum pumps
The 20-1 vacuum pumps
11,12 sulfide purifying columns
21～30 valves
31,32 fire damp recovery towers
41～59 valves
61,62 methane purifying columns
63 methane storage devices
The A gas access
B, B1, B2 waste gas outlet
The C gas vent
The D gas access
The specific embodiment
For making abundant understanding purpose of the present invention, feature and effect, existing by following specific embodiment, and cooperate appended graphicly, the present invention is described in detail, illustrate as afterwards:
A kind of purifying sulphur-containing waste device 1 of the present invention's first specific embodiment as shown in Figure 1, wherein this device comprises: an air blast 10, a vacuum pumps 20, valve member combination (21～30) and disulphide purifying column 11,12.And following each valve group unless otherwise indicated, is all closed condition.
The purification of sulphur-containing exhaust gas
At first, open air blast 10, and enter:
First step:
Second step:
And in the above-mentioned gas purification process, also can use single sulfide purifying column 11 to carry out purified treatment, when only using single sulfide purifying column 11 to carry out purifying sulphur-containing waste, only open valve 21,25 and 29; And, only also can utilize the switch of these valve groups, and reach a batch purification run in above-mentioned two sulfide purifying columns purification run simultaneously use.
The high silica alumina ratio zeolite adsorption material of in above-mentioned sulfide purifying column, being filled, wherein the silica alumina ratio of this high silica alumina ratio zeolite adsorption material is more than 10, and the sulfur-containing compound of institute's desorption is that hydrogen sulfide is or/and methyl alcohol sulphur; And these high silica alumina ratio adsorption material are MCM-41 zeolite, y-type zeolite or silica-rich zeolite, and the shaping form of these high silica alumina ratio zeolite adsorption materials is graininess or honeycomb.
Carry out the testing evaluation of this device usefulness with sulfur compound waste gas, wherein the composition of this sulfur compound waste gas is: hydrogen sulfide 600ppm, methyl mercaptan 150ppm, aqueous vapor 25000ppm, methane 65% and carbon dioxide 32.5%, and the temperature that becomes a mandarin is 25 ℃; And in this sulfides purifying column, fill respectively: MCM-41 zeolite (honeycomb), y-type zeolite (honeycomb), silica-rich zeolite (honeycomb and graininess) and activated carbon (honeycomb), carry out the test of sulfur compound waste gas purification, its result such as following table one:
Table one: different adsorbents are at the purification efficiency assessment of hydrogen sulfide and methyl alcohol sulphur
By the result of last table as can be known, when using MCM-41 zeolite, y-type zeolite and silica-rich zeolite, all can effectively remove hydrogen sulfide, also can remove methyl mercaptan simultaneously, only the MCM-41 zeolite only reaches more than 50% in the removal efficient of methyl mercaptan; But as if being the adsorption material of sulfide with the activated carbon, its effect is clear, only can remove hydrogen sulfide 50%, and methyl mercaptan more is lower than below 10%, so this activated carbon is not suitable for using as the sulfide adsorption material.
And the silica alumina ratio of these adsorption material MCM-41 zeolite, y-type zeolite and silica-rich zeolite is all greater than more than 10, and wherein this y-type zeolite is 35, and the silica alumina ratio of this silica-rich zeolite is 350, and at the purification of sulfide, is the best with this silica-rich zeolite again.
The regeneration of sulfide purifying column
After this purifying sulphur-containing waste is finished, the valve of being opened when closing former purification run, Open valve 23 is or/and 24 and vacuum pumps 20 again, in using the reduced vacuum mode, make and originally be adsorbed in this sulfides purifying column 11 or/and sulfide in 12 and methyl mercaptan by desorption, and discharge or reclaim through waste gas outlet B.
And in the above-mentioned desorption reaction, also Open valve 27 utilizes a gas access D or/and 28 and 30 synchronously, provides ozone, aqueous vapor or steam simultaneously, with the desorption of accelerated cure hydrogen and methyl mercaptan.
Embodiment 2
A kind of fire damp retracting device 2 of the present invention's second specific embodiment as shown in Figure 2, wherein this device comprises: an air blast 10, a vacuum pumps 20, valve member combination (41～57) and two fire damp recovery towers 31,32.And following each valve group unless otherwise indicated, is all closed condition.
The recovery of fire damp
At first, start or stop air blast 10, and carry out the open and close state according to the order that table two operating procedure program and valve member are opened explanation, when the absorption program, the biogas that gas access A handles institute's desire can be imported these fire damp recovery towers 31 or/and 32 via this air blast 10, in this fire damp recovery tower 31,32, fill a monosulfide adsorbent and a fire damp recovery catalyst, be used for purifying sulfur-containing compound and carbon dioxide, and then methane discharges via 44,54 and 57 to gas vent C1 after will purifying in biogas.
And in the above-mentioned fire damp removal process, also can use single fire damp recovery tower 31 to carry out purified treatment, when only using single fire damp recovery tower 31 to carry out purifying sulphur-containing waste, only open valve 41,44 and 57; And, only also can utilize the switch control of these valve groups, and reach a batch purification run in above-mentioned two fire damp recovery towers purification run simultaneously use.
Table two: operating procedure program and valve member are opened explanation
Wherein, when recovery tower 31 carried out a → b → c → d → e → f cyclic program, 32 of recovery towers carried out the corresponding cyclic program of d → e → f → a → b → c simultaneously;
Wherein, can further increase d1 low-pressure washing program after the reverse decompression desorption of the d step program, this moment, recovery tower 31,32 carried out valve member 43,45,51,54 and 57 unlatchings, and perhaps recovery tower 31,32 carries out valve member 41,44,53,55 and 57 unlatchings;
Perhaps, can further increase d2 high pressure product cleaning procedure after the reverse decompression desorption of the d step program, this moment, recovery tower 31,32 carried out valve member 42,46,51,54 and 57 unlatchings, and perhaps recovery tower 31,32 carries out valve member 41,44,52,56 and 57 unlatchings;
The sulfide sorbent of being filled in above-mentioned fire damp recovery tower is a high silica alumina ratio zeolite adsorption material, and wherein the silica alumina ratio of this high silica alumina ratio zeolite adsorption material is more than 10, and the sulfur-containing compound of institute's desorption is that hydrogen sulfide is or/and methyl alcohol sulphur; And these high silica alumina ratio adsorption material are MCM-41 zeolite, y-type zeolite or silica-rich zeolite, and the shaping form of these high silica alumina ratio zeolite adsorption materials is graininess or honeycomb; And fire damp recovery catalyst wherein is in order to separating carbon dioxide and the methane in the biogas, and the fire damp recovery catalyst is made up of activated carbon and zeolite, and this activated carbon is through Ca
2+, Mg
2+Or Cu
2+The activated carbon of upgrading; And this X type zeolite is Li-X, Ca-X, Sr-X, Mg-X or Na-X type zeolite.
Carry out the testing evaluation of this device usefulness with biogas, wherein the composition of this biogas is: hydrogen sulfide 120ppm, methyl mercaptan 20ppm, aqueous vapor 3.5% percent by volume, methane 68% and carbon dioxide 28.5%, and the temperature that becomes a mandarin is 29 ℃; And the sulfide adsorption material silica-rich zeolite (silica alumina ratio is 450) of filling and this activated carbon are for through Cu
2+The activated carbon of upgrading; And this zeolite is a Li-X type zeolite, carries out fire damp and reclaims test.
Result after above-mentioned test, the efficient that this fire damp reclaims is: the clearance of this hydrogen sulfide is more than 99%, the clearance of methyl alcohol sulphur is more than 98%, the clearance of carbon dioxide is more than 98%, and the rate of recovery of this methane is more than 90%, can effectively remove hydrogen sulfide, methyl alcohol sulphur and carbon dioxide in the biogas, and purify the methane that reclaims more than 90%.
The regeneration of fire damp recovery tower
After this fire damp recovery is finished, the valve of being opened when closing former methane reclaimer operation, Open valve 42,52,48 and vacuum pumps 20 again, in using the reduced vacuum mode, make the sulfide, methyl mercaptan and the carbon dioxide that originally are adsorbed in these fire damp recovery towers 31,32 by desorption, and discharge or reclaim through waste gas outlet B1.
A kind of two stage fire damp retracting devices 3 of the present invention's the 3rd specific embodiment as shown in Figure 3, wherein this device comprises: two air blasts 10,10-1, two vacuum pumps 20,20-1, the combination of two valve members (21～30), (41～57), disulphide purifying column 11,12 and bismethane purifying column 61,62.And following each valve group unless otherwise indicated, is all closed condition.
The recovery of fire damp
At first, start or stop air blast 10,10-1, valve 21,22,25,26,29,41,51,44,54 and 57, the biogas that gas access A handles institute's desire can be imported this sulfide purifying column 11 and 12 via this air blast 10, in this sulfides purifying column 11, filling and vulcanization thing adsorbent in 12, be used for purifying sulfur-containing compound in biogas, and through the biogas valve 25 of flowing through again of absorption sulfide, 26 and 29, and through gas vent C flow through again air blast 10-1 and valve 41,51 import these methane recovery towers 61, among 62, and then contained carbon dioxide and methane in the divided gas flow, will purify back methane again via 44,54 and 57 to gas vent C2 discharge.
And in the two above-mentioned stage fire damp removal process, also can use single sulfide purifying column 11 and single methane recovery tower 61 to carry out purified treatment, when only using single fire damp recovery tower 61 to carry out purifying sulphur-containing waste, the valve group of only opening related needs gets final product; And in above-mentioned two stages during the fire damp reclaimer operation, the purification run simultaneously of these disulphide purifying columns and two fire damp recovery towers is used, and only also can utilize the switch control of these valve groups, and reach a batch purification run.
The sulfide sorbent of being filled in above-mentioned sulfide purifying column is a high silica alumina ratio zeolite adsorption material, and wherein the silica alumina ratio of this high silica alumina ratio zeolite adsorption material is more than 10, and the sulfur-containing compound of institute's desorption is that hydrogen sulfide is or/and methyl alcohol sulphur; And these high silica alumina ratio adsorption material are MCM-41 zeolite, y-type zeolite or silica-rich zeolite, and the shaping form of these high silica alumina ratio zeolite adsorption materials is graininess or honeycomb; And fire damp recovery tower wherein is in order to separating carbon dioxide and the methane in the biogas, and interior fire damp recovery catalyst is made up of activated carbon and zeolite, and this activated carbon is through Ca
2+, Mg
2+Or Cu
2+The activated carbon of upgrading; And this X type zeolite is Li-X, Ca-X, Sr-X, Mg-X or Na-X type zeolite.
Carry out the testing evaluation of this device usefulness with biogas, wherein the composition of this biogas is: hydrogen sulfide 120ppm, methyl mercaptan 20ppm, aqueous vapor 3.5% percent by volume, methane 68% and carbon dioxide 28.5%, and the temperature that becomes a mandarin is 29 ℃; And the sulfide adsorption material silica-rich zeolite (silica alumina ratio is 450) of filling and this activated carbon are for through Cu
2+The activated carbon of upgrading; And this zeolite is a Li-X type zeolite, carries out fire damp and reclaims test.
Result after above-mentioned test, the efficient that this fire damp reclaims is: the clearance of this hydrogen sulfide is more than 95%, the clearance of methyl alcohol sulphur is more than 70%, the clearance of carbon dioxide is more than 98%, and the rate of recovery of this methane is more than 85%, can effectively remove hydrogen sulfide, methyl alcohol sulphur and carbon dioxide in the biogas, and purify the methane that reclaims more than 85%.
In addition, two stage fire damp retracting devices of the present invention can further comprise a methane storage element 63, it is used to store the methane that reclaims through purifying, its operation utilizes the operation of related valve 57,58 and 59, can reach and store the effect that purifies methane, and this methane storage element 63 can be made of the activated carbon through the phosphoric acid activation preparation.
The regeneration of sulfide purifying column and fire damp recovery tower
After this fire damp recovery is finished, the valve of being opened when closing former fire damp reclaimer operation, open suitable valve and vacuum pumps again, utilize the reduced vacuum mode, make the sulfide, methyl mercaptan and the carbon dioxide that originally are adsorbed in this sulfides purifying column and fire damp recovery tower by desorption, and discharge or reclaim via waste gas outlet B and B2 (not shown among Fig. 3) respectively.
Also provide a kind of method of purifying sulphur-containing waste by said apparatus the present invention, it comprises the following step:
(1) provides aforesaid purifying sulphur-containing waste device, in order to the desorption sulfur-containing compound;
(2) sulphur-containing exhaust gas of the institute desire being handled via air blast imports this device, opens or/and close the related valves group, carrying out the desorption of sulfur-containing compound, and discharges simultaneously through absorption sulfur-containing compound after-purification gas;
(3) open or/and close the related valves group, utilize vacuum pumps to aspirate the interior sulfur-containing compound of this device, to carry out the regeneration of adsorption material.
Simultaneously, the method that the present invention also provides a kind of fire damp to reclaim, it comprises the following step:
(1) provides aforesaid fire damp retracting device, in order to reclaim fire damp;
(2) biogas of the institute desire being handled via air blast imports this device, opens or/and close the related valves group, with separating of the desorption that carries out sulfur-containing compound and carbon dioxide and methane, and reclaims methane through purified treatment simultaneously;
(3) open or/and close the related valves group, utilize vacuum pumps to aspirate this device interior sulfur-containing compound and carbon dioxide, to carry out the regeneration of adsorption material.
Whereby, method and device that purifying sulphur-containing waste of the present invention and fire damp reclaim, effective purification of sulphur-containing exhaust gas, and reclaim fire damp simultaneously, and can fully effectively utilize the biogas resource, reach effective utilization of natural resources.
Claims (21)
1. purifying sulphur-containing waste device, it comprises: an air blast, a vacuum pumps, valve member combination and at least more than one sulfide purifying column, it is characterized in that this sulfide purifying column is in order to the desorption sulfur-containing compound, and this sulfide purifying column fills a high silica alumina ratio zeolite adsorption material, and the silica alumina ratio of this high silica alumina ratio zeolite adsorption material is more than 10.
2. purifying sulphur-containing waste device as claimed in claim 1, wherein when this sulfide purifying column be two when above, this sulfides purifying column is purification run simultaneously or batch purification run.
3. purifying sulphur-containing waste device as claimed in claim 1, wherein the sulfur-containing compound of this sulfide purifying column institute desorption is hydrogen sulfide and/or methyl alcohol sulphur.
4. purifying sulphur-containing waste device as claimed in claim 1, wherein this high silica alumina ratio zeolite adsorption material is MCM-41 zeolite, y-type zeolite or silica-rich zeolite.
5. purifying sulphur-containing waste device as claimed in claim 3, wherein this high silica alumina ratio zeolite adsorption material is a silica-rich zeolite.
6. purifying sulphur-containing waste device as claimed in claim 1, wherein the shaping form of this high silica alumina ratio zeolite adsorption material is graininess or honeycomb.
7. fire damp retracting device, it comprises: an air blast, a vacuum pumps, valve member combination and more than one fire damp recovery tower is characterized in that this fire damp recovery tower comprises:
The monosulfide adsorbent, it is in order to the desorption sulfur-containing compound, and this sulfide sorbent is a high silica alumina ratio zeolite adsorption material, and the silica alumina ratio of this high silica alumina ratio zeolite adsorption material is more than 10;
One fire damp recovery catalyst, this fire damp recovery catalyst is in order to carbon dioxide and methane in the separation biogas, and the fire damp recovery catalyst is made up of activated carbon and zeolite.
8. fire damp retracting device as claimed in claim 7, wherein when this fire damp recovery tower be two when above, these fire damp recovery towers are purification run simultaneously or batch purification run.
9. fire damp retracting device as claimed in claim 7, wherein the sulfur-containing compound of this sulfide sorbent institute desorption is hydrogen sulfide and/or methyl alcohol sulphur.
10. fire damp retracting device as claimed in claim 7, wherein high silica alumina ratio zeolite adsorption material is MCM-41 zeolite, y-type zeolite or silica-rich zeolite; And this activated carbon is the activated carbon through Ca2+, Mg2+ or Cu2+ upgrading; And this X type zeolite is Li-X, Ca-X, Sr-X, Mg-X or Na-X type zeolite.
11. fire damp retracting device as claimed in claim 10, wherein high silica alumina ratio zeolite adsorption material is a silica-rich zeolite; This activated carbon is through Cu
2+The activated carbon of upgrading; And this X type zeolite is a Li-X type zeolite.
12. fire damp retracting device as claimed in claim 7, wherein the shaping form of this high silica alumina ratio zeolite adsorption material is graininess or honeycomb; And the shaping form of this activated carbon and zeolite is a honeycomb.
13. a stage fire damp retracting device, it comprises: two air blasts, two vacuum pumps, the combination of two valve members, at least more than one sulfide purifying column and at least more than one methane purifying column is characterized in that:
This sulfide purifying column is in order to the desorption sulfur-containing compound, and this sulfide purifying column fills a high silica alumina ratio zeolite adsorption material, and the silica alumina ratio of this zeolite adsorption material is more than 10;
This methane purifying column is in order to carbon dioxide and methane in the separation biogas, and this fire damp purifying column is made up of activated carbon and zeolite.
14. two stage fire damp retracting devices as claimed in claim 13, wherein when this sulfide purifying column and methane purifying column be two when above, this sulfides purifying column and methane purifying column are purification run simultaneously or batch purification run.
15. two stage fire damp retracting devices as claimed in claim 13, wherein the sulfur-containing compound of sulfide purifying column institute desorption is hydrogen sulfide and/or methyl alcohol sulphur.
16. two stage fire damp retracting devices as claimed in claim 13, wherein high silica alumina ratio zeolite adsorption material is MCM-41 zeolite, y-type zeolite or silica-rich zeolite; And this activated carbon is through Ca
2+, Mg
2+Or Cu
2+The activated carbon of upgrading; And this X type zeolite is Li-X, Ca-X, Sr-X, Mg-X or Na-X type zeolite.
17. two stage fire damp retracting devices as claimed in claim 16, wherein high silica alumina ratio zeolite adsorption material is a silica-rich zeolite; This activated carbon is through Cu
2+The activated carbon of upgrading; And this X type zeolite is a Li-X type zeolite.
18. two stage fire damp retracting devices as claimed in claim 17, wherein the shaping form of this high silica alumina ratio zeolite adsorption material is graininess or honeycomb; And the shaping form of activated carbon and zeolite is a honeycomb.
19. two stage fire damp retracting devices as claimed in claim 13, it further comprises a methane storage element, in order to store the fire damp through purifying.
20. the method for a purifying sulphur-containing waste, it comprises the following step:
(1) provides as each described purifying sulphur-containing waste device of claim 1 to 6, in order to the desorption sulfur-containing compound;
(2) sulphur-containing exhaust gas of the institute desire being handled via air blast imports this device, opens and/or close the related valves group, carrying out the desorption of sulfur-containing compound, and discharges simultaneously through absorption sulfur-containing compound after-purification gas;
(3) open and/or close the related valves group, utilize vacuum pumps to aspirate the interior sulfur-containing compound of this device, to carry out the regeneration of adsorption material.
21. the method that fire damp reclaims, it comprises the following step:
(1) provides as each described fire damp retracting device of claim 7 to 19, in order to reclaim fire damp;
(2) biogas of the institute desire being handled via air blast imports this device, opens and/or close the related valves group, with separating of the desorption that carries out sulfur-containing compound and carbon dioxide and methane, and reclaims methane through purified treatment simultaneously;
(3) open and/or close the related valves group, utilize vacuum pumps to aspirate this device interior sulfur-containing compound and carbon dioxide, to carry out the regeneration of adsorption material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107466249A (en) * | 2015-02-19 | 2017-12-12 | 帕奎勒有限责任公司 | The method of gas of the processing comprising hydrogen sulfide and mercaptan |
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2009
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107466249A (en) * | 2015-02-19 | 2017-12-12 | 帕奎勒有限责任公司 | The method of gas of the processing comprising hydrogen sulfide and mercaptan |
| CN107466249B (en) * | 2015-02-19 | 2020-09-15 | 帕奎勒有限责任公司 | Method for treating a gas containing hydrogen sulphide and mercaptans |
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