CN106345232A - Method and device for removing siloxane in biomass gas through two-stage mode - Google Patents
Method and device for removing siloxane in biomass gas through two-stage mode Download PDFInfo
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- CN106345232A CN106345232A CN201610852267.2A CN201610852267A CN106345232A CN 106345232 A CN106345232 A CN 106345232A CN 201610852267 A CN201610852267 A CN 201610852267A CN 106345232 A CN106345232 A CN 106345232A
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- 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
- B01D53/007—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 by irradiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/10—Particle separators, e.g. dust precipitators, using filter plates, sheets or pads having plane surfaces
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- 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
- B01D53/14—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 by absorption
- B01D53/1487—Removing organic compounds
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- 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
- B01D53/14—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 by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/40—Absorbents explicitly excluding the presence of water
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/50—Combinations of absorbents
- B01D2252/504—Mixtures of two or more absorbents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/20—Capture or disposal of greenhouse gases of methane
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The invention relates to the field of utilization of renewable energy sources, and in particular to a method and a device for removing siloxan in biomass gas through a two-stage mode. The device comprises a pretreatment system, a first-stage biomass gas purifying system and a second-stage biomass gas purifying system. The method comprises the following steps: sequentially pumping biomass gas containing solid-phase and liquid-phase impurities into a net type filter and a gas-liquid two-phase vertical separator, and removing water, foams and solid granules in the biomass gas; pumping obtained biomass gas into an absorption tank filled with a methyldiethanolamine solution, and removing hydrogen sulfide in the biomass gas; then pressurizing, pumping the biomass gas into an absorption tower, entering first-stage and second-stage biomass gas purifying technologies, and storing methane gas. According to the device and the method, disclosed by the invention, the siloxane in the biomass is removed by adopting the two-stage method, purified methane gas is obtained, and the removal rate of the siloxane can be up to not less than 99 percent; the device and the method have important significance in reducing atmospheric pollution and optimizing an energy structure.
Description
Technical field
The present invention relates to field of renewable energy resource utilization, the side of siloxanes in especially a kind of two-part removing biogas
Method and device.
Background technology
Biogas, as a kind of new and effective renewable green energy resource, have developed marsh gas power generation, the resource such as biogas heats
Change and utilize technology, biogas, as fuel, can reduce the discharge of greenhouse gases, molecule and oxynitride, has wider
Wealthy development space and multiple economic and environmental benefit.Landfill yard and the biogas of sludge of sewage treatment plant anaerobic digestion generation
In addition to the key components such as methane, carbon dioxide, also contain other components, such as hydrogen sulfide and siloxanes etc., the presence of siloxanes is tight
Ghost image rings biogas and uses, and hinders the use value of biogas.The adverse effect that wherein siloxanes is applied to biogas is very big.
In recent years, many research institutions assessed the risk to the mankind and environment for the siloxanes.Bureau for Environmental Protection of Denmark is sent out
Existing hexamethyl disiloxane can stimulate skin, affect kidney, hexamethyl disiloxane is classified as dangerous substance.EPA
Report with Corning Incorporated and point out: decamethylcyclopentaandoxane is probably carcinogen.Canada it is reported that: in municipal water supply
Middle have siloxanes and be unfavorable for fish and the existence of aquatic tissue, octamethylcy-clotetrasiloxane, decamethylcyclopentaandoxane shadow simultaneously
Ring hormonal secretion, it is possible to impact mankind's breeding.China is siloxanes big producing country, the danger that surrounding is caused
Evil is immeasurable.
Purify siloxane treated and mainly adopt absorption method, absorption process, condensation at low temperature, biological method, Catalytic processes, membrance separation
Method, gas-permeable membrane separation etc..
Patent cn201210393660.1 " a kind of device and method of removal siloxane from combustible gas gas " describes
The method and apparatus that a kind of employing silica gel adsorption removes the siloxanes in fuel gas, this method utilizes silica gel adsorption, its
Efficiency can be affected by moisture in gas, in addition, the regeneration temperature of adsorbent is higher, needs substantial amounts of regenerated heat, increased
Cost.
Content of the invention
The technical problem to be solved in the present invention is: propose a kind of low cost deep removal biogas in siloxanes and time
Receive process and the device of methane.
The technical solution adopted in the present invention is: a kind of method that two-part removes siloxanes in biogas, including with
Lower step:
1) biogas carrying solid phase and liquid phase impurity are passed through well strainer and vertical point of gas-liquid two-phase according to this
Water in device, removal biogas, foam and solid particle；
2) by step 1) process the biogas that obtain and be passed through tourie equipped with methyldiethanolamine solution, remove biological
Hydrogen sulfide in matter gas；
3) by above-mentioned steps 2) it is passed through absorption tower after the pressurization of the biogas that obtain, enter first paragraph biogas and purify work
Biogas containing siloxanes are carried out absorption cleaning process using absorbent by skill, the silica in preliminary removing biogas
Alkane；
4) by above-mentioned steps 3) in the concentrated sulphuric acid being passed through additional ultrasonic irradiation being tentatively stripped of siloxanes that obtains, enter
Row second segment biogas purify technique, further the siloxanes in removing biogas；
5) by above-mentioned steps 4) biogas that obtain are passed through air accumulator, store methane gas.
Further, siloxanes of the present invention is hexamethyl disiloxane, octamethyltrisiloxane, decamethyl four
Siloxanes, hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, decamethylcyclopentaandoxane, ten diformazan basic ring six siloxanes
One of or at least two combination.
Further say, in biogas of the present invention, the concentration of siloxanes is more than 10mg/nm3.
Further say, the operation temperature that first paragraph biogas of the present invention purify is room temperature.
Further say, the concentration of concentrated sulphuric acid of the present invention is 92%-97%, and temperature is 50-65 DEG C.
Further say, absorbent of the present invention is by NHD, phenanthrene, para-terpheny and dodecyl
Benzene sulfonic acid sodium salt compounds according to certain ratio and forms.The mass fraction of wherein NHD is 45%～70%, luxuriant and rich with fragrance
Mass fraction is 25%～40%, and the mass fraction of para-terpheny is 5%～15%；Described 2- octyldodecyl sodium sulfate
The concentration accounting for absorbent total solution is 2 × 10-4～5 × 10-4mol/l.
Meanwhile, present invention also offers a kind of two-part removes the device of siloxanes in biogas, including pre-treatment system
System, first paragraph biogas cleaning system, second segment biogas cleaning system；
Described preprocessing system includes well strainer, gas-liquid two-phase vertical separator, methyl diethanolamine fluid reservoir
And compressor；Described well strainer connects unstripped gas by suction line, and it is vertical to connect gas-liquid two-phase through outlet line
Separator；Described gas-liquid two-phase vertical separator discharging tube is provided with fluid level control valve, and gas outlet is provided with demister；Gas warp
Enter demister outlet line after demister, demister outlet line is provided with pressure-control valve；Described gas-liquid separator
Outlet gas line connect methyl diethanolamine fluid reservoir；The outlet of described methyl diethanolamine fluid reservoir connects compressor
Entrance, the outlet line of compressor connects the entrance of first paragraph biogas cleaning system, equipped with valve in connecting pipeline；
Described first paragraph biogas cleaning system includes absorbing flow container, centrifugal pump, absorption tower, connecting pipeline and control
Valve；The described absorbing liquid absorbing in flow container passes through centrifugal pumping absorption tower top entry, and absorption tower outlet at bottom connects to be inhaled
Receive flow container；Biogas enter from absorption tower bottom air inlet, and the gas outlet on absorption tower connects second segment biogas and purifies system
The entrance of system；
Described second segment biogas cleaning system include ultrasound wave slot type phonochemical reaction device, concentrated sulphuric acid fluid reservoir,
Methane recovery tank and connecting pipeline and control valve；The entrance of concentrated sulphuric acid fluid reservoir connects the gas outlet on absorption tower, biomass
Gas removes after siloxanes further through concentrated sulphuric acid, enters the storage of methane recovery tank.
Further, in order to improve the removal effect to siloxanes for the concentrated sulphuric acid, concentrated sulphuric acid fluid reservoir of the present invention
It is arranged in ultrasound wave slot type phonochemical reaction device.
The invention has the beneficial effects as follows:
1. the present invention passes through to remove the siloxanes in biogas, the methane gas being purified, silicon using two-phase method
The removal efficiency of oxygen alkane is up to more than 99%；
2. the present invention is significant to minimizing atmospheric pollution, Optimization of Energy Structure.
Brief description
The present invention is further described with reference to the accompanying drawings and examples.
Fig. 1 is the process structure schematic diagram of the present invention；
In figure: 1- well strainer；3- gas-liquid two-phase vertical separator；4- demister；5- froth breaking plate；6- Liquid level
Valve；7- pressure-control valve；8- methyl diethanolamine fluid reservoir；9- gas compressor；11- absorption tower；12- absorption tower air inlet；
13- absorption tower gas outlet；15- concentrated sulphuric acid fluid reservoir；17- ultrasound wave slot type phonochemical reaction device；18- transducer；19- wire；
20- supersonic generator；22- methane recovery tank；25- centrifugal pump；27- absorbs flow container；2,10,14,16,19,21,23,24,
26- control valve.
Specific embodiment
Presently in connection with accompanying drawing and preferred embodiment, the present invention is further detailed explanation.These accompanying drawings are simplification
Schematic diagram, only illustrates the basic structure of the present invention, therefore it only shows the composition relevant with the present invention in a schematic way.
As shown in figure 1, device to include pretreatment system, first paragraph biogas cleaning system, second segment biogas net
Change system.
Preprocessing system comprises a well strainer 3, methyl diethanol of 1, gas-liquid two-phase vertical separator
Amine fluid reservoir 8 and a gas compressor 9.Unstripped gas enters well strainer 1 by pipeline, after removing solid particle, through going out
Mouth pipeline enters gas-liquid two-phase vertical separator 3.Gas-liquid two-phase vertical separator discharging tube is provided with fluid level control valve 6, and gas goes out
Mouth is provided with demister 4.Gas, through the laggard inlet/outlet pipeline of demister 4, outlet line is provided with pressure-control valve 7.Gas-liquid is divided
Outlet gas line from device connects methyl diethanolamine fluid reservoir, and the hydrogen sulfide in biogas is by methyldiethanolamine solution
Absorb.The outlet of methyl diethanolamine fluid reservoir connects suction port of compressor, and it is net that compressor outlet pipeline connects first paragraph biogas
The entrance of change system, equipped with valve in connecting pipeline.
First paragraph biogas cleaning system includes one and absorbs 25, absorption tower 11 of 27, centrifugal pump of flow container, connects
Adapter line and control valve.The absorbing liquid absorbing in flow container 27 send absorption tower 11 top entry by centrifugal pump 25, and absorbing liquid is inhaled
After having received the siloxanes in biogas, return to absorption flow container 27 from outlet at bottom.Biogas are from absorption tower 11 bottom air inlet
Mouth enters, and after absorbed liquid removes siloxanes, flows out from gas outlet, enters the entrance of second segment biogas cleaning system.
Second segment biogas cleaning system includes: 17, the concentrated sulphuric acid storage of a ultrasound wave slot type phonochemical reaction device
15, methane recovery tank 22 of flow container and connecting pipeline and control valve.From first paragraph biogas cleaning system out
Biogas enter the entrance of concentrated sulphuric acid fluid reservoir 15 by pipeline, and biogas remove after siloxanes further through concentrated sulphuric acid,
Enter methane recovery tank storage 22.Concentrated sulphuric acid fluid reservoir by ultrasound wave slot type phonochemical reaction device 17 irradiation, to improve concentrated sulphuric acid
Removal effect to siloxanes.
Technological process is as follows: by silicone-containing concentration be 250mg/nm3Biogas be passed through well strainer 1, remove
Solid particle therein.Then gas is passed through gas-liquid two-phase vertical separator 3, the water in removing biogas and foam.?
In separator, liquid sedimentation, in the bottom of separator, is discharged through fluid level control valve 6；Gas through except mist eliminator 4 remove little droplet it
It is passed through gas compressor 8 by pressure-control valve 7.After compressor 8 supercharging, biogas are passed through absorption tower air inlet 12；With
When, absorb the absorbing liquid in flow container 27 and pump the top entering absorption tower 11 by centrifugal pump 25；In absorption tower, biogas
In siloxanes be absorbed by liquid absorption.Absorbing liquid returns through control valve 16 after absorbing siloxanes and absorbs in flow container 27, and removes
The biogas of siloxanes enter concentrated sulphuric acid fluid reservoir 15 from absorption tower gas outlet 13, further the silicon in removing biogas
Oxygen alkane.The concentration of concentrated sulphuric acid is 97%, and temperature is 60 DEG C.It is stored in methane from concentrated sulphuric acid fluid reservoir 15 biogas out to deposit
In storage tank 22.
After in biogas, siloxanes completes first paragraph purification in absorption tower, the extrusion rate of siloxanes is 91.23%；Warp
After overrich sulfuric acid absorption completes second segment purification, the removal efficiency 99.54% of siloxanes.
The specific embodiment of the simply present invention described in description above, the various illustrations not reality to the present invention
Matter Composition of contents limits, and person of an ordinary skill in the technical field can be to described in the past concrete after having read description
Embodiment is made an amendment or is deformed, without departing from the spirit and scope of the invention.
Claims (8)
1. a kind of two-part removes the method for siloxanes in biogas it is characterised in that comprising the following steps:
1) biogas carrying solid phase and liquid phase impurity are passed through well strainer and gas-liquid two-phase vertical separator according to this,
Water in removal biogas, foam and solid particle；
2) by step 1) process the biogas that obtain and be passed through tourie equipped with methyldiethanolamine solution, remove biogas
In hydrogen sulfide；
3) by above-mentioned steps 2) it is passed through absorption tower after the pressurization of the biogas that obtain, enter first paragraph biogas and purify technique,
Using absorbent, absorption cleaning process is carried out to the biogas containing siloxanes, the siloxanes in preliminary removing biogas；
4) by above-mentioned steps 3) in the concentrated sulphuric acid being passed through additional ultrasonic irradiation being tentatively stripped of siloxanes that obtains, carry out
Two-stage nitration biogas purify technique, further the siloxanes in removing biogas；
5) by above-mentioned steps 4) biogas that obtain are passed through air accumulator, store methane gas.
2. two-part as claimed in claim 1 remove siloxanes in biogas method it is characterised in that: described silica
Alkane is hexamethyl disiloxane, octamethyltrisiloxane, decamethyl tetrasiloxane, hexamethyl cyclotrisiloxane, prestox ring four
One of siloxanes, decamethylcyclopentaandoxane, ten diformazan basic ring six siloxanes or at least two combination.
3. two-part as claimed in claim 1 remove siloxanes in biogas method it is characterised in that: described biology
In matter gas, the concentration of siloxanes is more than 10mg/nm3.
4. two-part as claimed in claim 1 remove siloxanes in biogas method it is characterised in that: described first
The operation temperature that section biogas purify is room temperature.
5. two-part as claimed in claim 1 remove siloxanes in biogas method it is characterised in that: described dense sulfur
The concentration of acid is 92%-97%, and temperature is 50-65 DEG C.
6. two-part as claimed in claim 1 remove siloxanes in biogas method it is characterised in that: described absorption
Agent is compounded according to certain ratio by NHD, phenanthrene, para-terpheny and 2- octyldodecyl benzene sulfonic acid sodium salt and forms；
The mass fraction of wherein NHD is 45%～70%, and luxuriant and rich with fragrance mass fraction is 25%～40%, para-terpheny
Mass fraction is 5%～15%；Described 2- octyldodecyl sodium sulfate account for absorbent total solution concentration be 2 × 10-4～
5×10-4mol/l.
7. a kind of be used for as claimed in claim 1 two-part remove siloxanes in biogas device it is characterised in that: bag
Include preprocessing system, first paragraph biogas cleaning system and second segment biogas cleaning system；
Described preprocessing system includes well strainer, gas-liquid two-phase vertical separator, methyl diethanolamine fluid reservoir and pressure
Contracting machine；Described well strainer connects unstripped gas by suction line, and connects the vertical separation of gas-liquid two-phase through outlet line
Device；Described gas-liquid two-phase vertical separator discharging tube is provided with fluid level control valve, and gas outlet is provided with demister；Gas is through demisting
Enter demister outlet line after device, demister outlet line is provided with pressure-control valve；The gas of described gas-liquid separator
Body outlet line connects methyl diethanolamine fluid reservoir；The outlet of described methyl diethanolamine fluid reservoir connects compressor and enters
Mouthful, the outlet line of compressor connects the entrance of first paragraph biogas cleaning system, equipped with valve in connecting pipeline；
Described first paragraph biogas cleaning system includes absorbing flow container, centrifugal pump, absorption tower, connecting pipeline and control valve
Door；The described absorbing liquid absorbing in flow container passes through centrifugal pumping absorption tower top entry, and absorption tower outlet at bottom connects absorption
Flow container；Biogas enter from absorption tower bottom air inlet, and the gas outlet on absorption tower connects second segment biogas cleaning system
Entrance；
Described second segment biogas cleaning system includes ultrasound wave slot type phonochemical reaction device, concentrated sulphuric acid fluid reservoir, methane
Recycling can and connecting pipeline and control valve；The entrance of concentrated sulphuric acid fluid reservoir connects the gas outlet on absorption tower, biogas warp
After concentrated sulphuric acid removes siloxanes further, enter the storage of methane recovery tank.
8. be used for as claimed in claim 7 two-part remove siloxanes in biogas device it is characterised in that: described
Concentrated sulphuric acid fluid reservoir is arranged in ultrasound wave slot type phonochemical reaction device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610852267.2A CN106345232A (en) | 2016-09-26 | 2016-09-26 | Method and device for removing siloxane in biomass gas through two-stage mode |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610852267.2A CN106345232A (en) | 2016-09-26 | 2016-09-26 | Method and device for removing siloxane in biomass gas through two-stage mode |
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| CN201610852267.2A Pending CN106345232A (en) | 2016-09-26 | 2016-09-26 | Method and device for removing siloxane in biomass gas through two-stage mode |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109233928A (en) * | 2018-10-22 | 2019-01-18 | 常州工程职业技术学院 | A kind of device and method for removing light-concentration siloxane in biogas |
| WO2019091521A1 (en) * | 2017-11-10 | 2019-05-16 | Peter Carl Sehestedt Schoubye | Process for purification of biogas without removing co2 or ch4 from the gas |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2676716A1 (en) * | 2012-06-22 | 2013-12-25 | Subramanian Iyer | System for removal of organic contaminants from bio-gas for renewable energy production |
| CN104711058A (en) * | 2015-02-06 | 2015-06-17 | 常州大学 | Method and device for deeply removing siloxane from garbage landfill gas/methane |
| CN206535385U (en) * | 2016-09-26 | 2017-10-03 | 常州工程职业技术学院 | The device of siloxanes in two-part removing biogas |
-
2016
- 2016-09-26 CN CN201610852267.2A patent/CN106345232A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2676716A1 (en) * | 2012-06-22 | 2013-12-25 | Subramanian Iyer | System for removal of organic contaminants from bio-gas for renewable energy production |
| CN104711058A (en) * | 2015-02-06 | 2015-06-17 | 常州大学 | Method and device for deeply removing siloxane from garbage landfill gas/methane |
| CN206535385U (en) * | 2016-09-26 | 2017-10-03 | 常州工程职业技术学院 | The device of siloxanes in two-part removing biogas |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019091521A1 (en) * | 2017-11-10 | 2019-05-16 | Peter Carl Sehestedt Schoubye | Process for purification of biogas without removing co2 or ch4 from the gas |
| CN109233928A (en) * | 2018-10-22 | 2019-01-18 | 常州工程职业技术学院 | A kind of device and method for removing light-concentration siloxane in biogas |
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