CN107326048A - A kind of method that utilization NaOH pretreatment coal improves biological methane yield - Google Patents

A kind of method that utilization NaOH pretreatment coal improves biological methane yield Download PDF

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CN107326048A
CN107326048A CN201710740197.6A CN201710740197A CN107326048A CN 107326048 A CN107326048 A CN 107326048A CN 201710740197 A CN201710740197 A CN 201710740197A CN 107326048 A CN107326048 A CN 107326048A
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coal
utilization
sodium hydroxide
naoh pretreatment
methane yield
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郭红光
张金龙
梁卫国
李亚平
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Taiyuan University of Technology
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Taiyuan University of Technology
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    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P5/00Preparation of hydrocarbons or halogenated hydrocarbons
    • C12P5/02Preparation of hydrocarbons or halogenated hydrocarbons acyclic
    • C12P5/023Methane
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/30Fuel from waste, e.g. synthetic alcohol or diesel

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Abstract

The invention discloses the new method that a kind of utilization NaOH pretreatment coal improves biological methane yield, by during biodegradable coal methane phase, in advance using the means of NaOH pretreatment coal, strengthening the biological effectiveness of coal, improving the yield of biological methane.In preprocessing process, the concentration of sodium hydroxide is 0.1mol/L ~ 1.5mol/L, and processing time is the h of 4 h ~ 16.Using the inventive method, after being pre-processed to coal, acted on by the alkali of sodium hydroxide, the biological effectiveness of coal is improved, so as to effectively increase the methane content produced by biodegradable coal.Preprocess method of the present invention is simple and easy to apply, and used sodium hydroxide price is low, convenient material drawing, and the solution after processing is easily handled, and will not produce poisonous and harmful substance, environmental protection.

Description

A kind of method that utilization NaOH pretreatment coal improves biological methane yield
Technical field
The present invention relates to a kind of method that utilization NaOH pretreatment coal improves biological methane yield, belong to methane production Technical field.
Background technology
Microorganism produces methane by anaerobic degradation coal, the ground gasification of coal can not only be realized, while also can be real The gasification in situ of existing coal, the biological coal bed gas of volume increase.However, coal is a kind of macromolecular compound, molecular structure is complicated, comprising a large amount of Aromatic rings, heterocycle, limit the biological effectiveness of coal, cause microbial degradation coal institute methane production relatively low.Thus, chemistry is passed through Or physical method changes texture of coal, improves coal property, improves the biological effectiveness of coal, promote microbial degradation coal, increase is biological Development, popularization of the methane production to coal biogasification technology are particularly important.Physical method observable index is larger, practical application In do not have economic advantages;Chemical method is then handled using cheap chemical reagent, but after processing remaining reagent disposal It is the problem of should be noted.
The content of the invention
The present invention is intended to provide a kind of method that utilization NaOH pretreatment coal improves biological methane yield, utilizes hydrogen-oxygen Change sodium pretreatment coal to strengthen the biological effectiveness of coal, improve biological methane yield.
Coal is pre-processed present invention employs sodium hydroxide solution, the strong basicity of sodium hydroxide can interrupt coal molecule Between part chemical bond, reduce the chelation between the intermolecular active force of coal, reduction coal molecule, so that the complexity of coal is big Molecular structure depolymerization is small molecule;Hydrogen bond can also be destroyed simultaneously, so that the macromolecular structure of fine and close coal becomes sparse.Cause This, the matrix of coal after sodium hydroxide effect is easier to be attacked by active material outside microbial cell, so as to promote the conversion of coal Process.
The invention provides a kind of method that utilization NaOH pretreatment coal improves biological methane yield, in biodegradation Before, the biological effectiveness of coal is strengthened by the preprocess method of sodium hydroxide solution oxidized coal, improves coal inverting biological methane Yield.
In the above method, NaOH pretreatment is carried out before addition microorganism fungus kind, in processing procedure:Hydroxide The concentration of sodium solution is 0.1mol/L ~ 1.5mol/L, and processing time is 4 ~ 16 h.
In the above method, the solid coal that feed coal is obtained after NaOH pretreatment, for producing biological methane.
The above method specifically includes following steps:
(1)By coal by the way that crushing mechanism is into powder and is sieved, the particle size range after coal sieving is 0.15 ~ 0.25 mm;
(2)Coal dust is mixed with sodium hydroxide solution, 4 ~ 16 h are stirred at room temperature by magnetic stirring apparatus;
The ratio of coal dust and sodium hydroxide solution is:4 ~ 5ml sodium hydroxide solution is used per g coal dusts;Magnetic stirring apparatus is stirred Speed is mixed for 600 ~ 800 rpm;
(3)By step(2)Gained mixed solution carries out separation of solid and liquid, obtains solid coal, obtains after being used for after solid coal drying Continuous biodegradable methane phase process;
In the step, separation of solid and liquid is realized by the method for acid-base neutralization or pure water;
(4)With step(1)Gained coal is substrate, under conditions of nutritional ingredient is provided, screened from coal bed gas product water or coal, The functional flora of enrichment degraded coal methane phase, including cellulose-degrading bacteria, aromatic compound degradation bacteria, methanogen etc.;Institute Nutritional ingredient is stated including microorganism, especially the nutriment needed for methanogen growth in addition to carbon source, including basal nutrient, Trace element, vitamin etc..
(5)With step(3)Drying gained solid coal is substrate, and the functional flora obtained using enrichment realizes biodegradable coal Methane phase process, while in incubation, every 3-7 days using gas-chromatography to detect methane production.
The coal used in the present invention is the larger coal of the biodegradable difficulty of anthracite, bituminous coal etc.
In the above method, step(3)The acid-base neutralization method is specially:In mixed solution and dripping 1.5mol/L salt Acid, the pH value of solution is measured by pH meter, until solution turns into neutrality;Then liquid phase, retention are removed by Vacuum filtration device Solid coal, and dry, matching used in Vacuum filtration device is 0.22 μm of filter membrane.
In the above method, step(3)The pure water method is specially:Use Vacuum filtration device and supporting 0.22 μm filter membrane is filtered to mixed solution, carries out repeatedly washing to coal sample to remove remaining hydrogen using distilled water in filter process Residual coal is taken to be dried after sodium oxide molybdena, washing.
The larger coal of the biodegradable difficulty of anthracite, bituminous coal etc is employed herein, because anthracite, bituminous coal belong to In the coal of high degree of metamorphism, it is more difficult to be degraded by microorganisms, so, after being pre-processed by the inventive method to coal, by pre- The strong basicity effect of inorganic agent, enhances the biological effectiveness of coal, improves biological methane yield.
Beneficial effects of the present invention:
(1)Using sodium hydroxide to Coal pretreatment after, improve the biological effectiveness of coal, effectively increase coal biological methane Yield;
(2)During by the use of sodium hydroxide as pretreating agent, sodium hydroxide is easily neutralized by acids such as hydrochloric acid, reaction generation sodium chloride Deng sodium salt, environmental pollution is small, it is easy to dispose, the characteristic with environmental protection;
(3)Sodium hydroxide is as a kind of conventional reagent, and price is low, reduces cost.
Brief description of the drawings
Fig. 1 is the biological methane production curve of various concentrations NaOH pretreatment in embodiment 1;
Fig. 2 is the biological methane production curve that concentration is the pretreatment of 1.5mol/L sodium hydroxides different time in embodiment 2.
Embodiment
The present invention is further illustrated below by embodiment, but is not limited to following examples.
Embodiment 1:
Various concentrations sodium hydroxide solution pre-processes the h of anthracite 6, comprises the following steps:
The first step, after Qinshui basin target coal seam obtains anthracite coal sample, coal sample is crushed, sieved, and is chosen particle diameter and is 0.15 ~ 0.25 mm progress is tested;
Second step, compound concentration is respectively 0.1mol/L, 0.5mol/L, 1.5mol/L sodium hydroxide.
3rd step, is separately added into the sodium hydroxide solution 25ml prepared and 5 g coals in 100 ml beakers.In 25 DEG C of bars Mixed solution is obtained after continuously stirring 6 h, stirring by magnetic stirring apparatus with 700 r/min speed under part.
4th step, the separation of solid and liquid of mixed liquor is mainly carried out using the method for pure water, and filtering is using 0.22 μm of filter membrane Filtered, fully wash coal in filter process with lot of pure water, separated obtained coal and 6 h are dried under the conditions of 45 DEG C, The substrate tested as biomethanation.
5th step, coal bed gas product water is gathered from Qinshui basin, using anthracite as sole carbon source, in the bar of addition culture medium The mixed bacterial of degraded coal methane phase under part, is screened, is enriched with from output water.It is 35 DEG C, quiescent culture to be enriched with temperature.
Wherein, the enriched medium component of methanogen floras is:
1L enriched mediums:Include K2HPO40.4 g, MgCl22.0 g, KH2PO40.4g, yeast extract 1.0 g, NH4Cl 1.0 g, the g of resazurin 0.001, cysteine 0.5 g, Na2S 0.2 g, NaHCO30.2 g, sodium acetate 2.0 g, KCl 0.2 The g of g, NaCl 2.0, the ml of trace element solution 10.0, vitamin solution 10.0 ml, pH 7.0.
1L trace element solutions include:FeCl2·4H2O 1.5mg, AlK (SO4)210mg, ZnCl270mg, NiCl2· 6H2O 24mg, MnCl2·4H2O 100mg, NaMoO46mg, CuCl22mg, H3BO336mg, CoCl2·6H2The mg of O 190, 25% HCl 10 ml/L
1L vitamin solutions include:Biotin 2mg, folic acid 2mg, B6 10mg, B2 5mg, B1 5mg, nicotinic acid 5mg, B12 0.1mg, lipoic acid 5mg, p-aminobenzoic acid 5mg.
After 15 Secondary Cultures, the function Mixed Microbes based on Enterobacter and Methanosaeta are obtained Group.
6th step, in 140 ml serum bottles, the coal after being dried using 1 g through the 4th step utilizes the as reaction substrate The methane phase mixed bacterial that five steps are obtained, continuous culture 40 days at 35 DEG C, to realize the biodegradable methane phase of coal.Anti- Period methane production should once be monitored every 5 days.
Shown in coal biological methane yield as accompanying drawing 1.After 40 days, the average methane production after 0.1mol/L naoh treatments Measure as 216 μm of ol/g coals;Average methane production after 0.5mol/L NaOH pretreatments is 226 μm of ol/g coals;1.5mol/ Average methane production after L NaOH pretreatments is 233 μm of ol/g coals.
Comparative example 1:
Do not add naoh treatment coal in this example, other process conditions are same as Example 1.Biological methane yield is shown in the institute of accompanying drawing 1 Show.In comparative example 1, after cultivating 40 days, average methane production is 204 μm of ol/g coals.
By comparing embodiment 1 and comparative example 1, find:After 0.1mol/L naoh treatments 6, biological methane is produced Amount adds 5.9%;After 0.5mol/L naoh treatments 6h, biological methane yield adds 10.8%;Through 1.5mol/L hydrogen After sodium oxide molybdena processing 6h, biological methane yield adds 14.2%.
Understood by Fig. 1 contrasts, after the present invention is pre-processed using sodium hydroxide to coal, effectively increase coal system biological The yield of methane.
Embodiment 2:
Using 1.5mol/L NaOH pretreatment anthracite 4h, 8h, 12h, 16h, comprise the following steps:
The present embodiment is using anthracite similarly to Example 1.
The first step, coal sample is crushed, sieved, and is chosen particle diameter and is tested for 0.15 ~ 0.25 mm progress;
Second step, compound concentration is 1.5mol/L sodium hydroxide.
3rd step, is separately added into the ml of 1.5mol/L sodium hydroxides 25 and 5 g coals in 100 ml beakers.In 25 DEG C of conditions Continuously stirred respectively with 700 r/min speed by magnetic stirring apparatus down and obtain mixing molten after 4h, 8h, 12h, 16h, stirring Liquid.
4th step, the separation of solid and liquid of mixed liquor is mainly carried out using the method for pure water, and filtering is using 0.22 μm of filter membrane Filtered, fully wash coal in filter process with lot of pure water, separated obtained coal and 6 h are dried under the conditions of 45 DEG C, The substrate tested as biomethanation.
5th step, the present embodiment uses functional flora same as Example 1, is equally to gather coal bed gas from Qinshui basin It is enriched with and obtains in output water.
6th step, in 140 ml serum bottles, the coal after being dried using 1 g through the 4th step utilizes the as reaction substrate The methane phase mixed bacterial that five steps are obtained, continuous culture 40 days at 35 DEG C, to realize the biodegradable methane phase of coal.Anti- Should period periodic detection methane production.
Shown in coal biological methane yield as accompanying drawing 2.After being cultivated through 40 days, 1.5mol/L NaOH pretreatment anthracites 4h average methane production is 216 μm of ol/g coals;1.5mol/L NaOH pretreatment anthracites 8h average methane production is 230 μm of ol/g coals;1.5mol/L NaOH pretreatment anthracites 12h average methane production is 240 μm of ol/g coals; 1.5mol/L NaOH pretreatment anthracites 16h average methane production is 238 μm of ol/g coals.
By comparing embodiment 2 and comparative example 1, find:After 1.5mol/L naoh treatments 4h, biological methane is produced Amount adds 5.9 %;After 1.5mol/L naoh treatments 8h, biological methane yield adds 12.7 %;Through 1.5mol/ After L naoh treatments 12h, biological methane yield adds 17.6 %;It is raw after 1.5mol/L naoh treatments 16h Thing Methane production adds 16.7 %.
Understood by Fig. 2 contrasts, after the present invention is pre-processed using sodium hydroxide to coal, significantly increase coal system biological The yield of methane.

Claims (10)

1. a kind of method that utilization NaOH pretreatment coal improves biological methane yield, it is characterised in that:Hydrogen-oxygen is used first Change sodium solution to pre-process coal, then add microorganism fungus kind, realize the process of biodegradable coal methane phase.
2. the method that utilization NaOH pretreatment coal according to claim 1 improves biological methane yield, its feature exists In:In preprocessing process, the concentration of sodium hydroxide solution is 0.1mol/L ~ 1.5mol/L, and processing time is 4 ~ 16h.
3. the method that utilization NaOH pretreatment coal according to claim 1 improves biological methane yield, its feature exists In:Comprise the following steps:
(1)By coal by the way that crushing mechanism is into powder and is sieved, the particle size range after coal sieving is 0.15 ~ 0.25 mm;
(2)Coal dust is mixed with the sodium hydroxide solution prepared, 4 ~ 16 h are stirred at room temperature by magnetic stirring apparatus;
The ratio of coal dust and sodium hydroxide solution is:4 ~ 5 ml sodium hydroxide solution is used per g coal dusts;Magnetic stirring apparatus Mixing speed is 600 ~ 800 rpm;
(3)By step(2)Gained mixed solution removes remaining reagent, carries out separation of solid and liquid, obtains solid coal, and dry;
(4)With step(1)Coal used is substrate, under conditions of nutritional ingredient is provided, screened from coal bed gas product water or coal, The functional flora of enrichment degraded coal methane phase;
(5)With step(3)Drying gained solid coal is substrate, and the functional flora obtained using enrichment realizes that biodegradable coal produces first Alkane process, while in incubation, every 3-7 days using gas-chromatography to detect methane production.
4. the method that utilization NaOH pretreatment coal according to claim 3 improves biological methane yield, its feature exists In:The coal is anthracite or bituminous coal.
5. the method that utilization NaOH pretreatment coal according to claim 3 improves biological methane yield, its feature exists In:Step(3)In, residual agent is removed by the method for acid-base neutralization or pure water, separation of solid and liquid is realized.
6. the method that utilization NaOH pretreatment coal according to claim 5 improves biological methane yield, its feature exists In:The acid-base neutralization method is specially:In mixed solution and dripping 1.5mol/L hydrochloric acid, the pH of solution is measured by pH meter Value, until solution turns into neutrality;Then liquid phase is removed by Vacuum filtration device and supporting 0.22 μm of filter membrane, retains solid coal, And dry.
7. the method that utilization NaOH pretreatment coal according to claim 5 improves biological methane yield, its feature exists In:The pure water method is specially:Mixed solution is filtered using Vacuum filtration device, made in Vacuum filtration device It is 0.22 μm of filter membrane, repeatedly washing is carried out to coal sample to remove residual sodium hydroxide using distilled water in filter process, Residual coal is taken to be dried after washing.
8. the method that utilization NaOH pretreatment coal according to claim 3 improves biological methane yield, its feature exists In:Step(3)In, drying temperature is 35 ~ 45 DEG C, and drying time is 6 ~ 12 h.
9. the method that utilization NaOH pretreatment coal according to claim 3 improves biological methane yield, its feature exists In:Step(4)In, it is described degraded coal methane phase functional flora include cellulose-degrading bacteria, aromatic compound degradation bacteria or Methanogen.
10. the method that utilization NaOH pretreatment coal according to claim 3 improves biological methane yield, its feature exists In:Step(4)In, the nutritional ingredient includes basal nutrient, trace element or vitamin.
CN201710740197.6A 2017-08-25 2017-08-25 A kind of method that utilization NaOH pretreatment coal improves biological methane yield Pending CN107326048A (en)

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Publication number Priority date Publication date Assignee Title
CN102517368A (en) * 2011-12-15 2012-06-27 河南理工大学 Method for preparing biogas by degrading coal with microorganisms
CN102822346A (en) * 2009-12-18 2012-12-12 西里斯能源公司 Biogasification of coal to methane and other useful products
WO2014152830A1 (en) * 2013-03-14 2014-09-25 The University Of Wyoming Research Corporation Methods and systems for biological coal-to-biofuels and bioproducts

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102822346A (en) * 2009-12-18 2012-12-12 西里斯能源公司 Biogasification of coal to methane and other useful products
CN102517368A (en) * 2011-12-15 2012-06-27 河南理工大学 Method for preparing biogas by degrading coal with microorganisms
WO2014152830A1 (en) * 2013-03-14 2014-09-25 The University Of Wyoming Research Corporation Methods and systems for biological coal-to-biofuels and bioproducts

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ZAIXING HUANG等: "Bioassay of chemically treated subbituminous coal derivatives using Pseudomonas putida F1", 《INTERNATIONAL JOURNAL OF COAL GEOLOGY》 *
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