CN107088348A - A kind of absorbent for reducing methane concentration and preparation method thereof - Google Patents
A kind of absorbent for reducing methane concentration and preparation method thereof Download PDFInfo
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- 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
- B01D53/1493—Selection of liquid materials for use as absorbents
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
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Abstract
The present invention relates to a kind of absorbent for reducing methane concentration and preparation method thereof, belong to natural gas line maintenance safety and coal mining shaft production security technology area, the absorbent is made up of following component：Bacterial concentration is 2 × 105‑6×105The cfu/ml 35mL of methane-oxidizing bacteria bacterium solution 20, the 16g of graphene particles 4, the 8mL of ten diformazan basic rings, six siloxanes 2, the 210mL of solution 120 of inorganic salts.The adsorbent is not only environmentally friendly, and can realize the dissolving to methane in a short time, so as to quickly reduce the concentration of methane, is overhauled for coal mining and natural gas line, security can be greatly improved.Meanwhile, the preparation method of the adsorbent is simple to operation, environmental protection.
Description
Technical field
The invention belongs to natural gas line maintenance safety and coal mining shaft production security technology area, and in particular to Yi Zhongneng
Absorbent of methane concentration and preparation method thereof in enough effectively reduction restricted clearances.
Background technology
Methane is to cause one of predominant gas of greenhouse effects, causes the effect of climate change to be every mole per mole of methane
26 times of carbon dioxide, therefore, reduce discharge of methane than reducing tribute of the CO2 emission of equivalent to reduction greenhouse effects
Offer and want big 20~60 times.Methane is the main component of natural gas and mine gas, and its explosion limit is usually 5%~16%, its
Explosion accident typically has contingency, paroxysmal feature, once occurring, death toll is often more, and easily causes secondary
Raw disaster.Conventional art often takes force ventilated method so that gas density is beyond blast limit, or reaches blast limit
Stop work immediately, but nonetheless, China is annual because personnel death's accident that mine gas explosion is caused still happens occasionally.
Gas explosion accident together occurs on November 27th, 2014, Guizhou Province Pan county Song He townshiies pine forest colliery, causes 11 people dead；2014
Gas explosion accident occurs on August 19, Huainan, Anhui east colliery, causes 21 people dead；On March 29th, 2013, Ji Meiji
Especially great gas explosion accident occurs for eight treasures (choice ingredients of certain special dishes) coal industry company of group, causes 36 people dead；On December 13rd, 2013 Xinjiang white poplar ditch
Coal mine gas from explosion causes 21 people dead.In addition, in the last few years, natural gas line explosion accident also happens occasionally, and gives people the people's livelihood
Life brings certain loss with property.For example, on November 22nd, 2013, blast, which occurs, for Qingdao Huang Island oil pipeline causes 62 people dead
Die.At present, received significant attention using methane adsorbent to reduce methane content, but existing methane adsorption agent is more inclined
Pure chemistry material mixture ratio is overweighted, it is not notable to the adsorption effect of methane, therefore, it is badly in need of a kind of methane high to methane adsorption amount
Adsorbent.
The content of the invention
In view of this, it is an object of the invention to：(1) a kind of absorbent of reduction methane concentration is provided；(2) provide a kind of
Reduce the preparation method of the absorbent of methane concentration.
To reach above-mentioned purpose, the present invention provides following technical scheme：
1st, a kind of to reduce the absorbent of methane concentration, the absorbent is made up of following component：Methane-oxidizing bacteria bacterium solution 20-
35mL, graphene particles 4-16g, ten diformazan basic ring six siloxanes 2-8mL, inorganic salt solution 120-210mL, the methane oxidation
Bacterium bacterial concentration is 2 × 105-6×105cfu/mL。
Further, methane-oxidizing bacteria strain number is in the methane-oxidizing bacteria bacterium solution：ATCC51626.
Further, the particle diameter of the graphene particles is 0.1-750 μm.
Further, the collocation method of the inorganic salt solution is：Xiang Shuizhong is separately added into potassium hydrogen phosphate, 12 hypophosphite monohydrates
Sodium dihydrogen, sodium nitrate, potassium sulfate, epsom salt, ferrous sulfate heptahydrate and Salzburg vitriol are final concentration of to potassium hydrogen phosphate
0.4-0.6g/L, the 12 final concentration of 1.8-2.5g/L of hypophosphite monohydrate sodium dihydrogen, the final concentration of 0.5-1.2g/L of sodium nitrate, sulfuric acid
The final concentration of 0.1-0.5g/L of potassium, the final concentration of 0.01-0.05g/L of epsom salt, ferrous sulfate heptahydrate is final concentration of
0.008-0.016g/L, the final concentration of 1-1.8mg/L of Salzburg vitriol.
Further, the collocation method of the solution of the inorganic salts is：Xiang Shuizhong is separately added into potassium hydrogen phosphate, 12 hydration phosphorus
Acid dihydride sodium, sodium nitrate, potassium sulfate, epsom salt, ferrous sulfate heptahydrate and Salzburg vitriol are to potassium hydrogen phosphate final concentration
For 0.53g/L, the 12 final concentration of 2.148g/L of hypophosphite monohydrate sodium dihydrogen, the final concentration of 0.85g/L of sodium nitrate, potassium sulfate is dense eventually
Spend for 0.174g/L, the final concentration of 0.037g/L of epsom salt, the final concentration of 0.012g/L of ferrous sulfate heptahydrate, five hydration sulphur
The sour final concentration of 1.43mg/L of copper.
2nd, a kind of preparation method of the absorbent of described reduction methane concentration, comprises the following steps：
(1) potassium hydrogen phosphate, 12 hypophosphite monohydrate sodium dihydrogens, sodium nitrate, potassium sulfate, seven water sulfuric acid are separately added into water
Magnesium, ferrous sulfate heptahydrate and Salzburg vitriol, inorganic salt solution is made after uniform mixing；
(2) methane-oxidizing bacteria bacterium solution is added in obtained inorganic salt solution into step (1), stirring is transparent outstanding to solution
Turbid liquid, solution surface has minute bubbles, then stands to solution clarification, the inorganic salt solution containing methane-oxidizing bacteria is made；
(3) siloxanes of ten diformazan basic ring six is added to the water to the siloxanes of ten diformazans basic ring six and be completely dissolved, is made
The siloxane solution of ten diformazan basic ring six, described ten are added by the obtained inorganic salt solution containing methane-oxidizing bacteria in step (2)
In the siloxane solution of diformazan basic ring six, after uniform mixing, graphene particles are added into mixed liquor equal to the graphene particles
It is even to be scattered in the mixed liquor, the absorbent of reduction methane concentration is made.
The beneficial effects of the present invention are：The invention provides a kind of absorbent for reducing methane concentration and its preparation side
Method, the absorbent contains ten diformazan basic rings six using the bigger graphene particles of specific surface area as solid-phase adsorbent and liquid phase
The methane-oxidizing bacteria bacterium solution mixing of siloxanes, not only increases adsorbance of the graphene to methane, and improve whole system
Methane adsorption amount.Wherein, the siloxanes of ten diformazan basic ring six has similar compatibility with methane, and it is empty that its own can adsorb periphery
Methane gas molecule in gas, reduces methane concentration, meanwhile, the specific surface area of graphene particles can reach 2630m2/ g, and
Common activated carbon specific surface area is 1500m2/ g, graphene particles have bigger specific surface area relative to activated carbon, to first
The adsorption capacity of alkane is stronger, its by methane adsorption in the liquid phase.Now, the methane-oxidizing bacteria in liquid phase is caught by ten diformazan basic rings
The formaldehyde that six siloxanes and graphene particles are adsorbed jointly, ultimately generates carbon dioxide and water.
Methane-oxidizing bacteria is to carry out the microorganism that assimilation and alienation are metabolized using methane as sole carbon source and the energy, is distributed model
Enclose extensively, tolerance is strong, can be survived under the extreme conditions such as acid, alkali, salt, high temperature, low temperature, shortage nutrition.Its absorption mechanism
As shown in figure 1, under aerobic or oxygen free condition, the methane-oxidizing bacteria in methane-oxidizing bacteria solution traps the free of surrounding space
After state methane, methane is converted into by methanol by an enzyme system starting with methane monooxygenase, methanol is in methanol dehydrogenase
Formic acid is converted under effect, formic acid is finally metabolized to carbon dioxide and water in the presence of hydrogenlyase, and in the process
Grown, the energy needed for breeding.And the addition of graphene particles and the siloxanes of ten diformazan basic ring six enables to whole mix
Close absorbent and be in suspension, inorganic salt solution provides existence nutriment in whole process for methane-oxidizing bacteria.Finally,
It together form an organic microbial environmental system.Therefore, the adsorbent is not only environmentally friendly, and can be in the short time
Dissolving of the interior realization to methane, so as to quickly reduce the concentration of methane, is overhauled, Neng Gouji for coal mining and natural gas line
It is big to improve security.Meanwhile, the preparation method of the adsorbent is simple to operation, environmental protection.
Brief description of the drawings
In order that the purpose of the present invention, technical scheme and beneficial effect are clearer, the present invention provides drawings described below and carried out
Explanation：
Fig. 1 is the mechanism figure that methane-oxidizing bacteria absorbs methane.
Embodiment
The preferred embodiments of the present invention will be described in detail below.
Embodiment 1
Prepare a kind of absorbent of reduction methane concentration
(1) potassium hydrogen phosphate, 12 hypophosphite monohydrate sodium dihydrogens, sodium nitrate, potassium sulfate, seven water sulfuric acid are separately added into water
Magnesium, ferrous sulfate heptahydrate and Salzburg vitriol are to the final concentration of 0.53g/L of potassium hydrogen phosphate, and 12 hypophosphite monohydrate sodium dihydrogens are dense eventually
Spend for 2.148g/L, the final concentration of 0.85g/L of sodium nitrate, the final concentration of 0.174g/L of potassium sulfate, epsom salt is final concentration of
0.037g/L, the final concentration of 0.012g/L of ferrous sulfate heptahydrate, the final concentration of 1.43mg/L of Salzburg vitriol；
(2) it is 2 × 10 20mL cell concentrations to be added in obtained inorganic salt solution into step (1)5Cfu/mL methane
Oxidation bacteria bacterium solution, is stirred to the transparent suspended liquid of solution, solution surface has minute bubbles, is then stood to solution clarification, is made
Inorganic salt solution containing methane-oxidizing bacteria；
(3) siloxanes of ten diformazan basic rings of 2mL six is added completely molten to the siloxanes of ten diformazans basic ring six in 450mL water
Solution, is made the siloxane solution of ten diformazan basic ring six, takes the inorganic salt solution containing methane-oxidizing bacteria made from 120mL steps (2)
Add in the siloxane solution of ten diformazans basic ring six, after uniform mixing, 4g graphene particles are added into mixed liquor to described
Graphene particles are dispersed in the mixed liquor, and the absorbent of reduction methane concentration is made.
Embodiment 2
Prepare a kind of absorbent of reduction methane concentration
(1) potassium hydrogen phosphate, 12 hypophosphite monohydrate sodium dihydrogens, sodium nitrate, potassium sulfate, seven water sulfuric acid are separately added into water
Magnesium, ferrous sulfate heptahydrate and Salzburg vitriol are to the final concentration of 0.48g/L of potassium hydrogen phosphate, and 12 hypophosphite monohydrate sodium dihydrogens are dense eventually
Spend for 1.8g/L, the final concentration of 1.0g/L of sodium nitrate, the final concentration of 0.5g/L of potassium sulfate, the final concentration of 0.01g/ of epsom salt
L, the final concentration of 0.006g/L of ferrous sulfate heptahydrate, the final concentration of 1.3mg/L of Salzburg vitriol；
(2) it is 4 × 10 25mL cell concentrations to be added in obtained inorganic salt solution into step (1)5Cfu/mL methane
Oxidation bacteria bacterium solution, is stirred to the transparent suspended liquid of solution, solution surface has minute bubbles, is then stood to solution clarification, is made
Inorganic salt solution containing methane-oxidizing bacteria；
(3) siloxanes of ten diformazan basic rings of 4mL six is added completely molten to the siloxanes of ten diformazans basic ring six in 450mL water
Solution, is made the siloxane solution of ten diformazan basic ring six, takes the inorganic salt solution containing methane-oxidizing bacteria made from 150mL steps (2)
Add in the siloxane solution of ten diformazans basic ring six, after uniform mixing, 8g graphene particles are added into mixed liquor to described
Graphene particles are dispersed in the mixed liquor, and the absorbent of reduction methane concentration is made.
Embodiment 3
Prepare a kind of absorbent of reduction methane concentration
(1) potassium hydrogen phosphate, 12 hypophosphite monohydrate sodium dihydrogens, sodium nitrate, potassium sulfate, seven water sulfuric acid are separately added into water
Magnesium, ferrous sulfate heptahydrate and Salzburg vitriol are to the final concentration of 0.6g/L of potassium hydrogen phosphate, and 12 hypophosphite monohydrate sodium dihydrogens are dense eventually
Spend for 2.0g/L, the final concentration of 0.5g/L of sodium nitrate, the final concentration of 0.3g/L of potassium sulfate, epsom salt is final concentration of
0.042g/L, the final concentration of 0.008g/L of ferrous sulfate heptahydrate, the final concentration of 1.0mg/L of Salzburg vitriol；
(2) it is 5 × 10 30mL cell concentrations to be added in obtained inorganic salt solution into step (1)5Cfu/mL methane
Oxidation bacteria bacterium solution, is stirred to the transparent suspended liquid of solution, solution surface has minute bubbles, is then stood to solution clarification, is made
Inorganic salt solution containing methane-oxidizing bacteria；
(3) siloxanes of ten diformazan basic rings of 6mL six is added completely molten to the siloxanes of ten diformazans basic ring six in 450mL water
Solution, is made the siloxane solution of ten diformazan basic ring six, takes the inorganic salt solution containing methane-oxidizing bacteria made from 180mL steps (2)
Add in the siloxane solution of ten diformazans basic ring six, after uniform mixing, 12g graphene particles are added into mixed liquor to described
Graphene particles are dispersed in the mixed liquor, and the absorbent of reduction methane concentration is made.
Embodiment 4
Prepare a kind of absorbent of reduction methane concentration
(1) potassium hydrogen phosphate, 12 hypophosphite monohydrate sodium dihydrogens, sodium nitrate, potassium sulfate, seven water sulfuric acid are separately added into water
Magnesium, ferrous sulfate heptahydrate and Salzburg vitriol are to the final concentration of 0.4g/L of potassium hydrogen phosphate, and 12 hypophosphite monohydrate sodium dihydrogens are dense eventually
Spend for 2.5g/L, the final concentration of 1.2g/L of sodium nitrate, the final concentration of 0.1g/L of potassium sulfate, the final concentration of 0.05g/ of epsom salt
L, the final concentration of 0.01g/L of ferrous sulfate heptahydrate, the final concentration of 1.8mg/L of Salzburg vitriol；
(2) it is 6 × 10 35mL cell concentrations to be added in obtained inorganic salt solution into step (1)5Cfu/mL methane
Oxidation bacteria bacterium solution, is stirred to the transparent suspended liquid of solution, solution surface has minute bubbles, is then stood to solution clarification, is made
Inorganic salt solution containing methane-oxidizing bacteria；
(3) siloxanes of ten diformazan basic rings of 8mL six is added completely molten to the siloxanes of ten diformazans basic ring six in 450mL water
Solution, is made the siloxane solution of ten diformazan basic ring six, takes the inorganic salt solution containing methane-oxidizing bacteria made from 210mL steps (2)
Add in the siloxane solution of ten diformazans basic ring six, after uniform mixing, 16g graphene particles are added into mixed liquor to described
Graphene particles are dispersed in the mixed liquor, and the absorbent of reduction methane concentration is made.
Embodiment 5
Respectively by lauryl sodium sulfate (SDS) solution that mass fraction is 10%, mass fraction is 10% dodecane
Basic sodium sulfonate (SDBS) solution, mass fraction is 10% sodium oleate solution, and mass fraction is 10% fatty alcohol polyoxy second
It is 70% that the absorbent of the reduction methane concentration prepared in alkene ether carboxylate (AEC) solution, embodiment 1-4, which is placed in methane concentration,
24h in environment, each adsorbent is shown in Table 1 to the adsorption effect of methane.
The different methane adsorbents of table 1 are to methane adsorption Contrast on effect
As shown in Table 1, mass fraction is 10% lauryl sodium sulfate (SDS) solution, quality as can be seen from the table
Fraction is the 10% basic sodium sulfonate of dodecane (SDBS) solution, and mass fraction is 10% sodium oleate solution, and mass fraction is
10% aliphatic alcohol polyethenoxy ether carboxylate (AEC) solution is respectively 6.31%, 5.24% to the adsorption effect of methane,
7.82% and 5.38%, embodiment 1-4 are respectively 13.95%, 19.82%, 26.37% He to the adsorption effect of methane
32.61%.The adsorption effect to methane of single chemical absorbent is below embodiment 1-4 assimilation effect, from embodiment 1 to
Embodiment 4, due to methane-oxidizing bacteria bacterial concentration, the siloxanes volume of ten diformazan basic ring six, the increase of graphene particles quality is right
The adsorption effect of methane gradually strengthens.
Embodiment 6
Graphene particles in embodiment 1-4 are replaced with into activated carbon in equal amount particle, 4 kinds are prepared containing activated carbon granule
Absorbent, then puts the above-mentioned 4 kinds absorbents (control group 1-4) containing activated carbon granule with the absorbent in embodiment 1-4
The 12h in methane concentration is 70% environment, each adsorbent is shown in Table 2 to the adsorption effect of methane.
The adsorbent of the carbon containing equivalent amount of active of table 2 and graphene is to methane adsorption Contrast on effect
As shown in Table 2, the control group 1-4 containing activated carbon in equal amount particulate absorbent contains equivalent compared with embodiment 1-4
The adsorbent of graphene is substantially higher in the adsorbent containing equivalent amount of active carbon to the assimilation effect of methane.Wherein, embodiment 1 compared with
Control group 1,4.12% will be higher by the adsorption effect of methane；Embodiment 2 will be higher by compared with control group 2 to the adsorption effect of methane
4.6%；Embodiment 3 will be higher by 6.04% compared with control group 3 to the adsorption effect of methane；Embodiment 4 is compared with control group 4, to methane
Adsorption effect will be higher by 6.01%.As can be seen here, the bigger graphene of specific surface area has more advantage for the adsorption effect of methane.
Finally illustrate, preferred embodiment above is merely illustrative of the technical solution of the present invention and unrestricted, although logical
Cross above preferred embodiment the present invention is described in detail, it is to be understood by those skilled in the art that can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (6)
1. a kind of reduce the absorbent of methane concentration, it is characterised in that the absorbent is made up of following component：Methane-oxidizing bacteria
Bacterium solution 20-35mL, graphene particles 4-16g, the siloxanes 2-8mL of ten diformazan basic ring six, inorganic salt solution 120-210mL are described
Methane-oxidizing bacteria bacterial concentration is 2 × 105-6×105cfu/mL。
2. a kind of absorbent of reduction methane concentration as claimed in claim 1, it is characterised in that the methane-oxidizing bacteria bacterium solution
Middle methane-oxidizing bacteria strain number is：ATCC51626.
3. a kind of absorbent of reduction methane concentration as claimed in claim 1, it is characterised in that the grain of the graphene particles
Footpath is 0.1-750 μm.
4. as claimed in claim 1 a kind of reduce the absorbent of methane concentration, it is characterised in that the inorganic salt solution is matched somebody with somebody
The method of putting is：Xiang Shuizhong is separately added into potassium hydrogen phosphate, 12 hypophosphite monohydrate sodium dihydrogens, sodium nitrate, potassium sulfate, epsom salt,
Ferrous sulfate heptahydrate and Salzburg vitriol are to the final concentration of 0.4-0.6g/L of potassium hydrogen phosphate, and 12 hypophosphite monohydrate sodium dihydrogens are dense eventually
Spend for 1.8-2.5g/L, the final concentration of 0.5-1.2g/L of sodium nitrate, the final concentration of 0.1-0.5g/L of potassium sulfate, epsom salt end
Concentration is 0.01-0.05g/L, the final concentration of 0.008-0.016g/L of ferrous sulfate heptahydrate, the final concentration of 1- of Salzburg vitriol
1.8mg/L。
5. the absorbent of a kind of reduction methane concentration as claimed in claim 1, it is characterised in that the solution of the inorganic salts
Collocation method is：Xiang Shuizhong is separately added into potassium hydrogen phosphate, 12 hypophosphite monohydrate sodium dihydrogens, sodium nitrate, potassium sulfate, seven water sulfuric acid
Magnesium, ferrous sulfate heptahydrate and Salzburg vitriol are to the final concentration of 0.53g/L of potassium hydrogen phosphate, and 12 hypophosphite monohydrate sodium dihydrogens are dense eventually
Spend for 2.148g/L, the final concentration of 0.85g/L of sodium nitrate, the final concentration of 0.174g/L of potassium sulfate, epsom salt is final concentration of
0.037g/L, the final concentration of 0.012g/L of ferrous sulfate heptahydrate, the final concentration of 1.43mg/L of Salzburg vitriol.
6. a kind of preparation method of the absorbent of reduction methane concentration described in claim any one of 1-5, it is characterised in that bag
Include following steps：
(1) potassium hydrogen phosphate, 12 hypophosphite monohydrate sodium dihydrogens, sodium nitrate, potassium sulfate, epsom salt, seven are separately added into water
Aqueous ferrous sulfate and Salzburg vitriol, inorganic salt solution is made after uniform mixing；
(2) methane-oxidizing bacteria bacterium solution, stirring to the transparent suspension of solution are added in obtained inorganic salt solution into step (1)
Shape, solution surface has minute bubbles, then stands to solution clarification, the inorganic salt solution containing methane-oxidizing bacteria is made；
(3) siloxanes of ten diformazan basic ring six is added to the water to the siloxanes of ten diformazans basic ring six and be completely dissolved, be made 12
The siloxane solution of methyl ring six, ten diformazan is added by the obtained inorganic salt solution containing methane-oxidizing bacteria in step (2)
In the siloxane solution of basic ring six, after uniform mixing, into mixed liquor, addition graphene particles to the graphene particles are uniformly divided
Dissipate in the mixed liquor, the absorbent of reduction methane concentration is made.
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| CN110368803A (en) * | 2019-07-22 | 2019-10-25 | 煤科集团沈阳研究院有限公司 | A kind of gas absorbent and its preparation method and application |
| CN110368803B (en) * | 2019-07-22 | 2021-10-22 | 煤科集团沈阳研究院有限公司 | Gas absorbent and preparation method and application thereof |
| CN114196664A (en) * | 2021-12-14 | 2022-03-18 | 重庆大学 | Methane-oxidizing bacteria-porous adsorbent compound and application thereof |
| CN114196664B (en) * | 2021-12-14 | 2023-12-01 | 重庆大学 | Methane-oxidizing bacteria-porous adsorbent compound and application thereof |
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