CN108018319A - A kind of method of alkali process coupling microorganism conversion lignite production bio-fuel - Google Patents
A kind of method of alkali process coupling microorganism conversion lignite production bio-fuel Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P5/00—Preparation of hydrocarbons or halogenated hydrocarbons
- C12P5/02—Preparation of hydrocarbons or halogenated hydrocarbons acyclic
- C12P5/023—Methane
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- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
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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
- 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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Abstract
The invention discloses a kind of method of alkali process coupling microorganism conversion lignite production bio-fuel, belong to lignite resource applied technical field, including step：Lignite, alkali process, filter centrifugation, the several steps of anaerobic fermentation are crushed, last fermenting and producing goes out methane, the biological bio-fuel such as hydrogen or bio-ethanol.The present invention is realized under conditions of exogenous nutrition material is not added, self supply of lignite microorganism conversion needed nutrient matter, promote industrialized production, realize that chemistry of micro-organisms couples high level conversion lignite, by the high carbon resource low-carbon conversion of lignite, process green non-pollution, the lignite for opening rich reserves prepare the new way of clean energy resource, are of great significance to the higher value application of lignite resource.
Description
Technical field
The invention belongs to lignite resource applied technical field, and in particular to a kind of alkali process couples microorganism conversion lignite
The method for producing bio-fuel, prepares bio-fuel and high valuable chemicals using lignite, realizes lignite resource application.
Background technology
Bio-fuel is methane (bio-natural gas, the CH using the production of microbial fermentation organic matter4) and hydrogen, ethanol.
With the continuous improvement of living standard, people's environmental pollution pay attention to day by day gets up.Solve pollution problem, production and
The use of green novel energy source is an effective important means in life.Intergovernmental Panel on Climate Change is more
Secondary expression, various countries should more use green novel energy source, to prevent global climate disaster.As countries in the world need the energy
The continuous increasingly reinforcement increased with environmental protection asked, the popularization and application of green novel energy source are into inexorable trend.
Lignite is also known as bavin coal, is the low-order coal of brownish black of the degree of coalification between peat and bituminous coal, is that a kind of height is waved
Hair point (50% or so), high-moisture (30% or so), high ash content (30% or so), low heat value (14MJ/kg or so), low ash smelting point
Inferior fuel.The lignite of Eastern Inner Mongolia accounts for the 77.55% of the whole nation, is distributed mainly on the Xilinguole League in my area, exhales
Human relations Bell city, Tongliao City and Baotou and the northern area of Bayannur, are mainly used near coal-mine power generation, and lignite burning both wasted
Lignite resource, and produce a large amount of SO2、CO2, NOx etc. cause atmospheric haze, it has also become China's using energy source and Economic Sustainability
Develop the significant problem that must be faced.The reserves of Inner Mongolia Autonomous Region lignite almost account for the half of coal resources, how to close
Reason utilizes lignite resource, researchs and develops advanced, clean and effective lignite conversion natural gas technology, is of great significance.
Lignite is since total moisture is up to 20%-50%, and for lignite using upgrading is needed, the process of the upgrading of lignite is mainly brown
The dehydration of coal, after less than 250 DEG C temperature slough part, most of free water, becomes drying brown coal.Pass through lignite upgrading
Low-grade lignite is changed into high combustion value coal, improves efficiency of combustion.The technology path of lignite upgrading is complicated, there is shaping etc. and closes
Key technology problem is difficult to resolve certainly, and the lignite relapse rate after steam drying is big, the cost problem utilized on a large scale, do not obtain all the time compared with
Preferably solve.Extensive utilize of lignite upgrading is caused also to be not up to perfect condition.
By taking the biological methane in bio-fuel as an example, biomethanation is the method advantageously of lignite trans-utilization,
The lignite not upgrading dehydration of High water cut, is converted into biological methane (also known as biogas, biological day with the help of anaerobe
Right gas, CH4).Higher plant coalification all constantly has coal bed gas (gas, mainly contains for lignite, bituminous coal and anthracitic different times
Methane CH4) produce.Since the degree of coalification of lignite is low, its chemical reactivity is good, H/C determined than high peculiar property it is brown
Coal can be as the suitable raw material of microorganism conversion.
Patent 201310237902.2 discloses a kind of earth's surface biological coal bed gas conversion process and equipment, its feature is：
Coal is put into container, methanogen and/or methanogen nutrient solution is added, the volatile matter of coal is changed into methane
Gas, then collect and utilize methane gas.
Patent 201210456311.X discloses a kind of method that methane is converted brown coal into using microorganism, utilizes external source
The method that methane is converted coal into after microbial acclimation, using the flora in sludge sewage and biogas slurry, utilizes grain
Coal dust of the footpath less than 0.075mm is carried out after progressively purifying and taming, and converts coal into methane.The nutrient solution wherein added is commercially available
Microbial fermentation nutrient solution, microbial nutrition salt prepare.
Patent 201010268938.3 discloses a kind of method for producing natural gas in organism coal bed, using filling well by nutrition
Liquid or nutrient solution and microorganism are filled into coal seam, while liquid is extracted from coal seam using a bite or more mouthfuls of circulation wells and is sent
Filling well is returned, makes body of groundwater height relative constancy by adjusting the filling pressure of filling well and the extraction pressure of circulation well, it is real
The stable circulation of existing nutrient solution；When the content of each nutritional ingredient in the water sample extracted from circulation well reaches filling well water sample
When more than 10%, stop filling and circulation, shut-in well a period of time, and monitor well head gas pressure；When well head air pressure reaches 10-20psi
When, start aerogenesis.This method is sufficiently mixed by the nutriment that more wells, pump circulation technology make to be filled into coal seam, is subtracted significantly
Lack adding amount, while efficient activation and promotion microorganism gas generation process, realize the gas producing efficiency of maximum-norm, and will not cause
Environmental pollution.
Above patent is required for the nutrients of additional ingredients complexity in the reaction system when lignite is converted into biological methane
Matter, improves cost, seriously limit lignite using microbe transformation method it is gentle be changed into the bio-fuels such as biological methane
Industrialization, it was noticed that lignite is rich in outside organic matter, also containing a large amount of humic acids (Humic acid), be phenolic hydroxy group ,-
The macromolecular aromatic compound of a variety of functional groups such as COOH ,-OH, basic structure is aromatic ring, alicyclic ring, mainly by carbon, hydrogen, three kinds of oxygen
Element forms, and chemical property is active, and structure is sufficiently complex, determines that its accurate structural is more difficult.How in lignite biology is converted into
Cost is reduced during the bio-fuels such as methane, the large-scale production of inexpensive high yield pulp1 is realized, reduces caused by environment
Pollution, becomes the hot spot of those skilled in the art's research.
The content of the invention
In order to overcome the shortcomings of described in background technology, the present invention provides a kind of alkali process coupling microorganism conversion lignite production
The method of bio-fuel, this method contain a large amount of humic acids this features using lignite, and the typical structure of humic acid is
The humic acid model of Stevenson, contains degradable saccharide residue in its molecular structure, and the carbon source that microorganism is most liked is
Sugar, especially glucose, based on this humic acid structural model, applicant is thought by means of chemical reagent, can be by humic acid
Fermentable saccharide residue disintegrate down, become the high valuable chemicals microbe conversion such as biological methane, hydrogen or ethanol, lactic acid
The carbon source of required microorganism, so as to fulfill under conditions of exogenous nutrition material is not added, is realized needed for lignite microorganism conversion
Self supply of nutriment, reduces conversion cost, promotes industrialized production, has to the higher value application of lignite resource great
Meaning.
The technical solution adopted by the present invention to solve the technical problems is：
A kind of method of alkali process coupling microorganism conversion lignite production bio-fuel, described method includes following steps：
(1) crush：Lignite is screened, and is added after being crushed in reaction bulb；
(2) alkali process：Lye is added in reaction bulb in step (1) and carries out alkali process, afterwards heating water bath；
(3) filter centrifugation：Product cooling, collected after centrifugation supernatant, the filtering that step (2) is obtained, after collecting filtering
Clear liquid, adjust pH；
(4) anaerobic fermentation：Microorganism is added in the product that step (3) obtains and carries out anaerobic fermentation, collects tunning,
Bio-fuel can be prepared.
Preferably, in step (1), the lignite is crushed to 60-150 mesh, the screening conditions of lignite：Dry ash free basis is waved
Hair point >=37%, light transmittance ＜ 50%, constant temperature ash free basis high calorific power ＜ 24MJ/Kg.Decomposed since lignite is difficult, lignite crushes
Granularity is between 60-150 mesh, and reaction rate that granularity is chemically reacted with aqueous slkali, efficiency of pcr product are proportionate, powder
It is up to 1.9% that broken particle degree surveys reduced sugar percentage composition less than 60 mesh DNS methods, and lignite pulverized particles degree is higher than 150 mesh DNS methods
It is up to 3.9% to survey reduced sugar percentage composition, effect unobvious, but lignite is ground into this and drastically raises.According to Chinese coal point
Class standard, meets dry ash free basis volatile matter >=37%, light transmittance ＜ 50%, constant temperature ash free basis high calorific power ＜ 24MJ/Kg
Coal be divided into lignite.
Preferably, in step (2), the concentration of the lye is 3-8%, and the solid-to-liquid ratio of lye and lignite is (1:6)-(1:
14) g/mL, lye include ammonium hydroxide, calcium hydroxide, barium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate solution
In any one or more solution arbitrary proportion mixing.Lye and the purpose of lignite reaction are to make lignite humic acid molecule
Saccharide residue disintegrates down, and concentration of lye and addition are directly related to Reducing sugar.Reduced sugar percentage composition is with concentration of lye
The trend for first increasing and reducing afterwards is presented, is exactly in the optimum concentration range for reaching peak, lye for 3-8% in the concentration of lye
Concentration be 10%, reduced sugar percentage composition drastically falls to 1.7%, and the aqueous slkali of high concentration can cause humic acid molecular structure
Middle hydroxyl, carbonyl, carboxyl, the dissociation of quinonyl isoreactivity group, influence Reducing sugar.Solid-to-liquid ratio means lye addition, also
The trend that raw sugar percentage composition progressively reduces after being first slowly increased with the presentation of lye addition, (1:6)-(1:14) g/mL is in and reaches
To the optimum concentration range at peak.Solid-to-liquid ratio exceedes (1:14) g/mL, the mass fraction increase of water, have impact on alkali in reaction system
The progress of the reaction of processing, causes reduced sugar percentage composition to fall to 2.9%.
Preferably, in step (2), the temperature of heating water bath is 60-80 DEG C, and heating water bath is until DNS methods survey reduced sugar hundred
It is that 3.0-4.0% is terminated to divide content.For temperature at 60-80 DEG C, this temperature is gentle, suitable humic acid molecule saccharide residue dissociation, together
Shi Buhui causes humic acid molecule aromatic ring, the isostructural depolymerization of alicyclic ring.The saccharide residue that lignite humic acid can dissociate at the same time is limited,
It is 4.0% that experimental data, which shows that DNS methods survey the reduced sugar percentage composition upper limit,.
Preferably, in step (3), 5min is centrifuged in 4000rpm after product cooling；0.22-0.45 μm of water of supernatant
It is filtering with microporous membrane；The pH of adjusting is 4.0-7.0.Lye is reacted with lignite, and the humic acid saccharide residue of dissociation enters liquid, is led to
Centrifugation is crossed to be collected, be filtered to remove the impurity such as lignite particle after reaction, while with 0.22-0.45 μm of water system miillpore filter mistake
Filter, can make supernatant liquid filtering remove miscellaneous bacteria, prepare to add specified microorganisms in next step.
Preferably, in step (4), the microorganism is the amphimicrobe or volume integral of volume fraction 1-5%
One kind in the anaerobe of number 30-40%.Obtain that after microorganism likes the sugar that utilizes, it is micro- to add specific amphimicrobian
Biology or anaerobe, since the proliferative speed of microorganism, metabolic way, physicochemical property are different, add the micro- life of amphimicrobian
Object amount is volume fraction 1-5% or anaerobe amount is volume fraction 30-40%, particularly anaerobe, because micro- life
Thing is slow-growing, it is necessary to use heavy dose of inoculation.
Preferably, in step (4), the amphimicrobe is saccharomycete, and saccharomycete is saccharomyces cerevisiae or mark
Think one kind in kluyveromyces.Bio-ethanol is produced, it is necessary to be ethanol, saccharomyces cerevisiae or Marx using conversion of saccharomycetes sugar
Kluyveromyces have the features such as Seedling height speed, high temperature resistant, and the saccharide residue of humic acid dissociation can be utilized to be converted into ethanol.
Preferably, in step (4), the anaerobe is one kind in methanogen or production hydrogen microorganism,
Product according to biological methane or biological hydrogen is obtained need, it is necessary to add methanogen or produce in hydrogen microorganism one
Kind.
Preferably, in step (4), the methanogen is acid-producing bacteria and methanogen, from anaerobism activity dirt
Mud domestication is isolated.Anaerobic fermentation process includes hydrolysis of organic matter, production acid, methane phase or production 3 stages of hydrogen, and abovementioned steps are
Hydrolysis is completed through the chemical reaction by aqueous slkali and lignite and obtains fermentable sugars, and subsequent reactions need addition anaerobism to live
The property isolated acid-producing bacteria of sludge acclimatization such as clostridium (Clostridium) and methanogen are such as
Methanoculleus bourgensis, Methanoculleus horonobensis, Methanoregula boonei, it is complete
Into anaerobic fermentation process.
Preferably, in step (4), the production hydrogen microbial source self sealss are heated after 60 DEG C of waters bath with thermostatic control
The anaerobic activated sludge of 30min, sealing prevent oxygen from entering, and 30min is heated in 60 DEG C of waters bath with thermostatic control, can kill anaerobism activity
Asporulate hydrogen-consuming bacteria in sludge, such as methanogen, retains production hydrogen microorganism, promotes anaerobic fermentation to turn to hydrogen producing.
It is an advantage of the invention that：
(1) main component of lignite is organic matter and humic acid, and fermentable reduced sugar sugar in lignite humic acid is residual
Base dissociation, utilize, and is converted into the green low-carbon energy such as biological methane, it is residual that organic matter and undegraded complete humic acid stay in fermentation
In slag, it can further extract humic acid or high humic acid organic fertilizer is made, comprehensively utilize lignite component, be conducive to improve lignite
Macroeconomic is worth；
(2) lignite microbial-chemical coupling high level conversion, the high carbon resource low-carbon of lignite is converted, process green non-pollution,
Open the new way of the lignite clean energy resource of rich reserves.
Embodiment
Technical scheme is described further below by embodiment.
Embodiment 1
100g constant temperature ash free basis high calorific power is taken to be less than 24MJ/Kg, dry ash free basis volatile matter >=37%, light transmittance ＜
50%th, the lignite of constant temperature ash free basis high calorific power ＜ 24MJ/Kg is crushed to 100 mesh and adds in reaction bulb, is according to solid-to-liquid ratio
1:6g/mL adds 6% sodium hydroxide solution, and surveying reduced sugar percentage composition until DNS methods in 60 DEG C of heating water bath 60min reaches
3.4% terminates reaction, and 4000rpm centrifuges 5min after cooling, collects centrifuged supernatant, and 0.22 μm of water system miillpore filter filters,
Clear liquid after filtering is collected, it is 4.0 to adjust pH, adds the saccharomyces cerevisiae that volume fraction is 1%, and 38 DEG C carry out anaerobic fermentation 48h,
4000rpm centrifugations 30min collects tunning, and it is 4.25% to carry out chromatography and obtain ethanol content, meets applicant's expection
It is required that during preparation, realize self supply of lignite microorganism conversion needed nutrient matter, reduce conversion cost, promote
Into industrialized production.
Embodiment 2
500g constant temperature ash free basis high calorific power is taken to be less than 24MJ/Kg, dry ash free basis volatile matter >=37%, light transmittance ＜
50%th, the lignite of constant temperature ash free basis high calorific power ＜ 24MJ/Kg is crushed to 60 mesh and adds in reaction bulb, is 1 according to solid-to-liquid ratio:
10g/mL adds 5% potassium hydroxide solution, in 70 DEG C of heating water bath 80min until DNS methods measure reduced sugar percentage composition reaches
Reaction is terminated to 3.9%, 4000rpm centrifuges 5min after cooling, collects centrifuged supernatant, 0.45 μm of water system miillpore filter mistake
Filter, collects clear liquid after filtering, and it is 7.0 to adjust pH, and it is isolated to add the anaerobic activated sludge domestication that volume fraction is 35%
Acid-producing bacteria and methanogen, draining water gathering of gas law collect tunning biological methane, carry out high resolution gas chromatography analysis, methane content
For 62.5%, meet applicant and be expected to require, during preparation, realize lignite microorganism conversion needed nutrient matter from
I supplies, and reduces conversion cost, promotes industrialized production.
Embodiment 3
1000g constant temperature ash free basis high calorific power is taken to be less than 24MJ/Kg, dry ash free basis volatile matter >=37%, light transmittance
＜ 50%, the lignite of constant temperature ash free basis high calorific power ＜ 24MJ/Kg are crushed to 150 mesh and add in reaction bulb, according to solid-to-liquid ratio
For 1:14g/mL adds 3% sodium carbonate liquor, in 80 DEG C of heating water bath 120min until DNS methods measure reduced sugar percentage composition
Reach 3.1% termination reaction, 4000rpm centrifuges 5min after cooling, collects centrifuged supernatant, 0.22 μm of water system miillpore filter mistake
Filter, collects clear liquid after filtering, and it is 5.0 to adjust pH, adds the production hydrogen microorganism that volume fraction is 30%, collects tunning generation
Hydrogen, carries out high resolution gas chromatography analysis, and hydrogen content 61.2%, meets applicant and be expected to require, during preparation,
Realize self supply of lignite microorganism conversion needed nutrient matter, reduce conversion cost, promote industrialized production.
Claims (10)
- A kind of 1. method of alkali process coupling microorganism conversion lignite production bio-fuel, it is characterised in that the described method includes Following steps：(1) crush：Lignite is screened, and is added after being crushed in reaction bulb；(2) alkali process：Lye is added in reaction bulb in step (1) and carries out alkali process, afterwards heating water bath；(3) filter centrifugation：Product cooling, collected after centrifugation supernatant, the filtering that step (2) is obtained, are collected clear after filtering Liquid, adjusts pH；(4) anaerobic fermentation：Microorganism is added in the product that step (3) obtains and carries out anaerobic fermentation, collects tunning, you can Bio-fuel is prepared.
- 2. a kind of method of alkali process coupling microorganism conversion lignite production bio-fuel as claimed in claim 1, its feature It is, in step (1), the lignite is crushed to 60-150 mesh, the screening conditions of lignite：Dry ash free basis volatile matter >= 37%th, light transmittance ＜ 50%, constant temperature ash free basis high calorific power ＜ 24MJ/Kg.
- 3. a kind of method of alkali process coupling microorganism conversion lignite production bio-fuel as claimed in claim 2, its feature It is, in step (2), the concentration of the lye is 3-8%, and the solid-to-liquid ratio of lye and lignite is (1:6)-(1:14) g/mL, alkali Liquid includes any one in ammonium hydroxide, calcium hydroxide, barium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate solution Kind or the mixing of a variety of solution arbitrary proportions.
- 4. a kind of method of alkali process coupling microorganism conversion lignite production bio-fuel as claimed in claim 3, its feature It is, in step (2), the temperature of heating water bath is 60-80 DEG C, and heating water bath is until DNS methods survey reduced sugar percentage composition is 3.0-4.0% is terminated.
- 5. a kind of method of alkali process coupling microorganism conversion lignite production bio-fuel as claimed in claim 4, its feature It is, in step (3), 5min is centrifuged in 4000rpm after product cooling；0.22-0.45 μm of water system miillpore filter of supernatant Filtering；The pH of adjusting is 4.0-7.0.
- 6. a kind of method of alkali process coupling microorganism conversion lignite production bio-fuel as claimed in claim 5, its feature It is, in step (4), amphimicrobe or volume fraction 30-40% that the microorganism is volume fraction 1-5% One kind in anaerobe.
- 7. a kind of method of alkali process coupling microorganism conversion lignite production bio-fuel as claimed in claim 6, its feature It is, in step (4), the amphimicrobe is saccharomycete, and saccharomycete ties up ferment for saccharomyces cerevisiae or Marx's Crewe One kind in mother.
- 8. a kind of method of alkali process coupling microorganism conversion lignite production bio-fuel as claimed in claim 7, its feature It is, in step (4), the anaerobe is one kind in methanogen or production hydrogen microorganism.
- 9. a kind of method of alkali process coupling microorganism conversion lignite production bio-fuel as claimed in claim 8, its feature It is, in step (4), the methanogen is acid-producing bacteria and methanogen, tames and separates from anaerobic activated sludge Obtain.
- 10. a kind of method of alkali process coupling microorganism conversion lignite production bio-fuel as claimed in claim 9, its feature It is, in step (4), the anaerobism that 30min is heated in the production hydrogen microbial source self sealss after 60 DEG C of waters bath with thermostatic control is lived Property sludge.
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