CN108277236A - A kind of method of acid processing coupling microorganism conversion lignite generation methane and lactic acid - Google Patents
A kind of method of acid processing coupling microorganism conversion lignite generation methane and lactic acid Download PDFInfo
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- CN108277236A CN108277236A CN201810112271.4A CN201810112271A CN108277236A CN 108277236 A CN108277236 A CN 108277236A CN 201810112271 A CN201810112271 A CN 201810112271A CN 108277236 A CN108277236 A CN 108277236A
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- 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
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Abstract
The invention discloses a kind of methods of acid processing coupling microorganism conversion lignite generation methane and lactic acid, belong to the low-order coals recycling applied technical field such as lignite, including:Crushing, acid processing, filter centrifugation and anaerobic fermentation step.The present invention is organic matter and humic acid this feature using the main component of lignite, by saccharide residue dissociation, the utilization in lignite humic acid, it is the compounds such as biological methane and lactic acid to convert lignite, under conditions of not adding exogenous nutrition substance, realize self supply of lignite microorganism conversion needed nutrient matter, reduce lignite conversion cost, it may additionally facilitate the industrialized production of biological methane and lactic acid, it is of great significance to the higher value application of lignite resource, opens the new way of the lignite clean energy resource and high level chemicals of rich reserves.
Description
Technical field
The invention belongs to low-order coal recycling applied technical fields, and in particular to a kind of acid processing coupling microorganism conversion is brown
The method of coal generation methane and lactic acid.
Background technology
Coal, as a kind of non-renewable energy, its finiteness and it exploit pollution during utilization by
Step highlights.How coal resources are rationally effectively utilized, has become a urgent problem to be solved.
Existing natural gas from coal, in particular by the project of the pressurization static bed gasification technology of broken coal, waste component is complicated,
Disposition difficulty is very big, and individual term height of eye organic matter, high slat-containing wastewater processing cost per ton are up to hundred yuan, are international coalification industrial and commercial banks
The problem that industry generally faces.Waste water dis posal is that natural gas from coal develops the main environment restraining factors faced.Western China
It is limited by natural environment, even if solving the technical issues of wastewater treatment by increasing investment and energy consumption, due to lacking blowdown
To being unable to the final disposal whereabouts of reuse waste water becomes one of most important restriction problem of natural gas from coal.
In addition, there are the features of contrary distribution for coal resources and water resource, especially with Xinjiang, Inner Mongol etc. for representative
Rich coal resources area, a large amount of natural gas from coal and coal-fired power project such as Inner Mongol Datang world Ke Shike rise natural gas from coal and have
Responsible company is limited, is in the layout of the area of these ecological environment frailties, the contradiction of shortage of water resources is more prominent, and is possible to cause
A series of regionality ecological environment problems and social concern.
Lignite is a kind of low-order coal, and compared with peat, lignite does not contain undecomposed plant residue, cellulose-less, half fiber
Dimension element, lignin and pectic substance ingredient;Compared with bituminous coal, anthracite, lignite contains humic acid (Humic acid).Lignite at present
It is mainly used as fuel, is used near coal-mine power benefit unobvious, and produce a large amount of dust, nitrogen oxygen during combustion power generation
The poisonous and harmful substances such as compound, oxysulfide and carbon monoxide cause serious environmental pollution.Due to lignite water content height (30-
50%) natural gas from coal, is carried out by raw material of lignite, it is less economical.Since the degree of coalification of lignite is minimum, chemical reaction is lived
The good, H/C of property determines that lignite can be as the raw material of microorganism conversion than high peculiar property.Lignite is micro- in laboratory at this stage
Bioconversion there is problems:First, coal sample must carry out nitric acid oxidation pretreatment, otherwise microorganism coal is not acted on or
Act on unobvious.This processing not only considerably increases cost, but also nitro is introduced in coal, will release when coal combustion additional
NOx.Secondly microorganism is to the transformation efficiency of lignite or relatively low.Although the also not up to industrial metaplasia of research at this stage
The requirement of production, but with brown coal liquefaction, the required high temperature of gasification, high pressure, energy consumption be big, compared with pollution, lignite microorganism turns
The advantages of change, it is also obvious that can such as carry out at normal temperatures, need not have equipment very high requirement, pollution relatively fewer
Deng.From the point of view of using energy source, environmental protection angularly, lignite microorganism conversion foreground is all good.
In platform chemicals, lactic acid is a kind of multiduty greening platform compound, the poly- breast synthesized as monomer using lactic acid
Sour plastics are considered as one of the best substitute of petrochemical industry plastics.The wilderness demand of polylactic acid causes reduction lactic fermentation cost to be compeled
In the eyebrows and eyelashes.It is that can uniquely store, can be used as combustion using biological methane as the biomass energy of Typical Representative compared with solar energy, wind energy
The regenerative resource of material and chemical raw material.Biological methane is flourishing in Germany and Sweden etc. as strategic resource and regenerative resource
Country is rapidly developed.By taking lignite converts production biological methane as an example:
Patent 201210456311.X discloses a kind of method converting brown coal into methane using microorganism, utilizes external source
The method that methane is converted coal into after microbial acclimation utilizes grain using the flora in sludge sewage and biogas slurry
Coal dust of the diameter less than 0.075mm carries out after gradually purifying and taming, and converts coal into methane.The nutrient solution being wherein added is commercially available
Microbial fermentation nutrient solution, microbial nutrition salt prepare.
Patent 201310237902.2 discloses a kind of earth's surface biological coal bed gas conversion process and equipment, feature are:
Coal is put into container, methanogen and/or methanogen nutrient solution is added, the volatile matter of coal is converted to methane
Gas, then collect and utilize methane gas.
Patent 201010268938.3 discloses a kind of method producing natural gas in organism coal bed, using filling well by nutrition
Liquid or nutrient solution and microorganism are filled into coal seam, while extracting liquid from coal seam using a bite or more mouthfuls of circulation wells and sending
Filling well is returned, filling the filling pressure of well and the extraction pressure of circulation well by adjusting keeps body of groundwater height relative constant, real
Existing nutrient solution stablizes cycle;When the content of each nutritional ingredient in the water sample extracted from circulation well reaches filling well water sample
When 10% or more, stop filling and cycle, 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 makes the nutriment being filled into coal seam be sufficiently mixed by more wells, pump circulation technology, subtracts significantly
Lack adding amount, while efficient activation and promotion microorganism gas generation process, realizes the gas producing efficiency of maximum-norm, and will not cause
Environmental pollution.
The above patent is required for additional ingredients in the reaction system complicated when lignite microorganism conversion is biological methane
Nutriment, improves cost, seriously limits lignite using the mild industry for being changed into biological methane of microbe transformation method
Change, it was noticed that lignite is rich in outside organic matter, lignite humic acid (Humic acid) content is higher, is to contain generally 40%
The macromolecular aromatic compound of a variety of functional groups such as phenolic hydroxyl group ,-COOH ,-OH, basic structure are aromatic ring, alicyclic ring, mainly by carbon,
Three kinds of hydrogen, oxygen element compositions, chemical property is active, and structure is sufficiently complex, determines that its accurate structural is more difficult.How not add
Under conditions of exogenous nutrition substance, realizes self supply of lignite microorganism conversion needed nutrient matter, reduce lignite and be converted to
Originally the industrialized production for, promoting biological methane and lactic acid becomes the hot spot of those skilled in the art's research.
Invention content
In order to overcome the shortcomings of described in background technology, the present invention provides a kind of acid processing coupling microorganism conversion lignite generation
The method of object methane and lactic acid, this method contain a large amount of humic acids this features, the classical architecture model of humic acid using lignite
For Stevenson structural models (Stevenson FJ.Humus Chemistry:Genesis,Composition,
Reaction.John Wiley and Sons,1982:443-443), saccharide residue is contained in molecular structure, and microorganism is most
The carbon source of hobby is sugar, especially glucose, is based on this humic acid structural model, and applicant thinks by means of chemical reagent such as acid
Solution can disintegrate down the saccharide residue in humic acid, as the carbon source needed for microorganism conversion, for producing biological methane
The high valuable chemicals such as equal clean energy resourcies, lactic acid realize lignite to realize under conditions of not adding exogenous nutrition substance
Self supply of microorganism conversion needed nutrient matter, reduces lignite conversion cost, may additionally facilitate the work of biological methane and lactic acid
Industry metaplasia is produced, and is of great significance to the higher value application of lignite resource.
The technical solution adopted by the present invention to solve the technical problems is:
A kind of method of acid processing coupling microorganism conversion lignite generation methane and lactic acid, the method includes following
Step:
(1) it crushes:Lignite is air-dried, is added in reaction bulb after being crushed;
(2) acid processing:Acid solution is added in reaction bulb in step (1) and carries out sour processing, later heating water bath;
(3) filter centrifugation:Product that step (2) obtains is cooling, supernatant, filtering is collected after centrifugation, after collecting filtering
Clear liquid;
(4) anaerobic fermentation:The product that step (3) obtains is divided into two parts, pH is adjusted respectively, is then respectively adding lactic acid
Microbial inoculum carries out anaerobic fermentation with methane fermentating microorganism, collects tunning, you can biological methane and lactic acid is prepared.
Preferably, in step (1), due to the hard difficult decomposition of lignite quality, the lignite is crushed to screen size and is
0.075-0.15mm, reaction rate that granularity is chemically reacted with acid solution, efficiency of pcr product are proportionate, pulverized particles degree
It is up to 0.75% to survey reduced sugar percentage composition less than 0.075mm DNS methods, effect unobvious, but lignite is ground into this and drastically rises
It is high.It is up to 0.22% that pulverized particles degree surveys reduced sugar percentage composition higher than 0.15mm DNS methods, does not reach peak value.
Preferably, in step (2), the acid solutions are 3-5%, and acid solution is sulfuric acid, sulfurous acid, hydrochloric acid, nitre
Any one in acid, carbonic acid, hydrofluoric acid, oxalic acid, phosphoric acid, boric acid, perchloric acid solution or two kinds of solution arbitrary proportion mixing.Acid
The purpose that solution is reacted with lignite is that the saccharide residue for making lignite humic acid molecule disintegrates down, and acid solutions and addition are straight
It connects and is related to Reducing sugar.Reduced sugar percentage composition first increases the trend reduced afterwards with acid solutions presentation, in acid solution
A concentration of 3-5% be exactly in the optimum concentration range for reaching peak, a concentration of the 8% of acid solution, reduced sugar percentage composition
Drastically fall to 0.44%.The acid solution of high concentration can destroy humic acid molecular structure, cause hydroxyl, carbonyl, carboxyl, quinonyl,
Methoxyl group and the parsing of aromatic rings isoreactivity group, influence Reducing sugar.
Preferably, in step (2), the solid-to-liquid ratio of the lignite and acid solution is (1:7)-(1:9) g/mL, solid-to-liquid ratio meaning
Taste acid solution addition, and reduced sugar percentage composition is first slowly increased the trend gradually reduced afterwards with the presentation of acid solution addition,
(1:7)-(1:9) g/mL is in the optimum concentration range for reaching peak.Solid-to-liquid ratio is more than (1:9) g/mL, water in reaction system
Mass fraction increases, and affects the progress of the reaction of acid processing, reduced sugar percentage composition is caused to fall to 0.50%.
Preferably, in step (2), the temperature of heating water bath is 70-95 DEG C, and heating water bath is until DNS methods survey reduced sugar hundred
It is that 0.5-1.0% is terminated to divide content.Bath temperature temperature condition at 70-95 DEG C is mild, suitable for humic acid molecule saccharide residue solution
From, while the fracture of humic acid molecule ethylene linkage, the depolymerization of aromatic ring structure will not be caused.The sugar that lignite humic acid can dissociate simultaneously
Residue is limited, and it is 1.0% to realize that data show that DNS methods survey the reduced sugar percentage composition upper limit.
Preferably, in step (3), 4000rpm centrifuges 5min after cooling;Supernatant is filtered with 0.22-0.45 μm of water system micropore
Membrane filtration.Acid solution is reacted with lignite, and the humic acid saccharide residue of dissociation enters liquid, is collected, is filtered to remove by centrifugation
The impurity such as lignite particle after reaction, while being filtered in 0.22-0.45 μm of water system miillpore filter, supernatant liquid filtering can be made to remove
Miscellaneous bacteria is prepared for specified microorganisms are added in next step.
Preferably, in step (4), it is 5.5-6.0 that a copy of it clear liquid, which adjusts pH, and the breast that volume fraction is 1-3% is added
Sour microbial inoculum, regulation system temperature are 36-45 DEG C of progress anaerobic fermentation 10-24h, collect tunning, you can lactic acid is prepared;
In addition it is 6.5-8.0 that a clear liquid, which adjusts pH, and the methane fermentating microorganism that volume fraction is 15-30%, regulation system temperature is added
Degree is 50-55 DEG C of progress anaerobic fermentation 0.5-3d, collects tunning, you can methane is prepared.It obtains microorganism and likes profit
After the fermentable reduced sugar of carbon source, specific agent of lactic acid bacteria and methane fermentating microorganism is added, it is numerous due to microorganism
It is different to grow rate, metabolic way, physicochemical property, needs to provide corresponding lactic acid bacteria condition of culture to obtain purpose product lactic acid,
Need adjust pH be 5.5-6.0, be added volume fraction be 1-3% agent of lactic acid bacteria, adjust fermentation system temperature be 36-45 DEG C into
Row anaerobic fermentation 10-24h;It needs to provide corresponding methane fermentating microorganism condition of culture to obtain purpose product biological methane,
PH is 6.5-8.0, and the methane fermentating microorganism that volume fraction is 15-30% is added, and regulation system temperature is 50-55 DEG C and is detested
Aerobe fermentation 0.5-3d, especially anaerobe need because microorganism is slow-growing using large dosage inoculation 15-30%, this
Outside due to having obtained fermentable reduced sugar, anaerobic fermentation process can be omitted hydrolysis stage, be directly entered production acid, methane phase
Stage, so fermentation time reduction is 0.5-3d.
Preferably, in step (4), the agent of lactic acid bacteria is Bifidobacterium, lactobacillus bulgaricus, streptococcus thermophilus, thermophilic
Any one in Lactobacillus lactis or two kinds of bacterium powder arbitrary proportion mixing.Bifidobacterium is strictly anaerobic microorganism, Bulgaria
Lactobacillus, streptococcus thermophilus, lactobacillus acidophilus are amphimicrobes, can individually be generated under anaerobic using sugar
Lactic acid, two kinds of bacterium powder arbitrary proportions mixing in Bifidobacterium, lactobacillus bulgaricus, streptococcus thermophilus, lactobacillus acidophilus is such as
Produce common lactobacillus bulgaricus, streptococcus thermophilus mixing lactic acid producing is applied to the production of Yoghourt.
Preferably, in step (4), the methane fermentating microorganism is that life sludge sewage anaerobic acclimation obtains
It arrives.Activated sludge is the general name of micropopulation and organic substance and inorganic substances that they are depended on, and activated sludge can be divided into
Aerobic activated sludge and anaerobic activated sludge, anaerobic activated sludge can be by providing anaerobic condition from sewage treatment plants
Aerobic activated sludge domestication obtains, rich in hydrolytic bacteria, zymogenous bacteria, hydrogen bacteria and acetic acid bacteria, methane backeria, sulfate reduction
Bacterium, wherein methanogenic thrix are the center frameworks of anaerobic activated sludge, are the main sources of methane fermentating microorganism, disclosure satisfy that
The microorganism fungus kind of methane phase needs.
It is an advantage of the invention that:
(1) main component of lignite is that organic matter and humic acid turn saccharide residue dissociation, the utilization in lignite humic acid
It is that compounds, organic matter and the undegraded complete humic acids such as biological methane and lactic acid are stayed in fermentation residue, can be made to change lignite
At high humic acid organic fertilizer, lignite is made to be classified high level conversion, is conducive to improve lignite macroeconomic value;
(2) lignite microbial-chemical couples high level conversion, and the high carbon resource low-carbon of lignite is converted, process green non-pollution,
Open the new way of the lignite conversion of rich reserves.
Specific implementation mode
Technical scheme of the present invention is described further below by embodiment.
Embodiment 1
It is 0.075mm to take 500g In Xilingol League In Inner Mongolia Shengli Coalfields to air-dry lignite to be crushed to screen size, is added anti-
It answers in bottle, is 1 according to solid-to-liquid ratio:7 are added 3% sulfuric acid solution, in 70 DEG C of heating water bath 80min until DNS methods survey reduced sugar
Percentage composition terminates reaction when reaching 0.5%, 4000rpm centrifuges 5min after cooling, collects centrifuged supernatant, 0.22 μm of water system
Filtering with microporous membrane collects clear liquid after filtering;Clear liquid after taking half to filter, it is 5.5 to adjust pH, and it is 1% that volume fraction, which is added,
44 DEG C of anaerobic fermentation 10h of streptococcus thermophilus collect tunning, carry out liquid-phase chromatographic analysis and obtain lactic acid content 1.4g/L.Separately
Clear liquid after taking half to filter, it is 6.5 to adjust pH, and the sewage treatment plants activated sludge anaerobism that volume fraction is 15% is added and tames and dociles
Change obtains, and is rich in the methane fermentating microorganism of acid-producing bacteria and methanogen, and 50 DEG C of anaerobic fermentation 3d collect tunning, carry out
Gas chromatographic analysis obtains biological methane content 57%, meets the expected of applicant and requires, exogenous nutrition object is not being added in realization
Under conditions of matter, self supply of lignite microorganism conversion needed nutrient matter reduces lignite conversion cost, promotes biological methane
With the industrialized production of lactic acid.
Embodiment 2
It is 0.15mm to take 1000g In Xilingol League In Inner Mongolia Shengli Coalfields to air-dry lignite to be crushed to screen size, is added anti-
It answers in bottle, is 1 according to solid-to-liquid ratio:8 are added 4% hydrochloric acid solution, are restored in 80 DEG C of heating water bath 60min until DNS methods measure
Sugared percentage composition terminates reaction when reaching 0.7%, 4000rpm centrifuges 5min after cooling, collects centrifuged supernatant, 0.22 μm of water
It is filtering with microporous membrane, collects clear liquid after filtering;Clear liquid after taking half to filter, it is 6.0 to adjust pH, and it is 2% that volume fraction, which is added,
37 DEG C of anaerobic fermentation 12h of lactobacillus acidophilus, collect tunning, carry out liquid-phase chromatographic analysis obtain lactic acid content 1.6g/L.
Another clear liquid after taking half filtering, it is 6.5 to adjust pH, and the sewage treatment plants activated sludge anaerobism that volume fraction is 20% is added
Domestication obtains, and the methane fermentating microorganism rich in hydrolytic bacteria, acidogenic bactria and methanogen, 50 DEG C of anaerobic fermentation 3d are collected
Tunning carries out gas chromatographic analysis and obtains biological methane content 59%, meets the expected of applicant and requires, realization is not adding
Under conditions of adding exogenous nutrition substance, self supply of lignite microorganism conversion needed nutrient matter reduces lignite conversion cost,
Promote the industrialized production of biological methane and lactic acid.
Embodiment 3
It is 0.075mm to take the Chifengs the 500g mining areas Ping Zhuan to air-dry lignite to be crushed to screen size, and reaction bulb is added
In, it is 1 according to solid-to-liquid ratio:9 are added 5% salpeter solution, in 70 DEG C of heating water bath 100min until DNS methods measure reduced sugar hundred
Point content terminates reaction when reaching 1.0%, it is cooling after 4000rpm centrifuge 5min, collect centrifuged supernatant, 0.45 μm of water system is micro-
Hole membrane filtration collects clear liquid after filtering;Clear liquid after taking half to filter, it is 5.5 to adjust pH, be added volume fraction be 1% it is double
44 DEG C of anaerobic fermentation 10h of discrimination bacillus collect tunning, carry out liquid-phase chromatographic analysis and obtain lactic acid content 1.8g/L.Separately take one
Clear liquid after half filtering, it is 7.0 to adjust pH, and the sewage treatment plants activated sludge anaerobic acclimation that volume fraction is 20% is added and obtains
It arrives, the methane fermentating microorganism rich in hydrolytic bacteria, acidogenic bactria and methanogen, 55 DEG C of anaerobic fermentation 2d collect fermentation production
Object carries out gas chromatographic analysis and obtains biological methane content 60%, meets the expected of applicant and requires, external source is not being added in realization
Under conditions of nutriment, self supply of lignite microorganism conversion needed nutrient matter reduces lignite conversion cost, promotes life
The industrialized production of object methane and lactic acid.
Claims (9)
1. a kind of method of acid processing coupling microorganism conversion lignite generation methane and lactic acid, which is characterized in that the side
Method includes the following steps:
(1) it crushes:Lignite is air-dried, is added in reaction bulb after being crushed;
(2) acid processing:Acid solution is added in reaction bulb in step (1) and carries out sour processing, later heating water bath;
(3) filter centrifugation:Product that step (2) obtains is cooling, supernatant, filtering is collected after centrifugation, collect filtered clear
Liquid;
(4) anaerobic fermentation:The product that step (3) obtains is divided into two parts, pH is adjusted respectively, is then respectively adding agent of lactic acid bacteria
Anaerobic fermentation is carried out with methane fermentating microorganism, collects tunning, you can biological methane and lactic acid is prepared.
2. the method for a kind of acid processing coupling microorganism conversion lignite generation methane and lactic acid as described in claim 1,
It is characterized in that, in step (1), it is 0.075-0.15mm that the lignite, which is crushed to screen size,.
3. the method for a kind of acid processing coupling microorganism conversion lignite generation methane and lactic acid as claimed in claim 2,
It is characterized in that, in step (2), the acid solutions are 3-5%, and acid solution is sulfuric acid, sulfurous acid, hydrochloric acid, nitric acid, carbon
Any one in acid, hydrofluoric acid, oxalic acid, phosphoric acid, boric acid, perchloric acid solution or two kinds of solution arbitrary proportion mixing.
4. the method for a kind of acid processing coupling microorganism conversion lignite generation methane and lactic acid as claimed in claim 3,
It is characterized in that, in step (2), the solid-to-liquid ratio of the lignite and acid solution is (1:7)-(1:9)g/mL.
5. the method for a kind of acid processing coupling microorganism conversion lignite generation methane and lactic acid as claimed in claim 4,
It is characterized in that, in step (2), the temperature of heating water bath is 70-95 DEG C, and heating water bath is until DNS methods survey reduced sugar percentage composition
It is terminated for 0.5-1.0%.
6. the method for a kind of acid processing coupling microorganism conversion lignite generation methane and lactic acid as claimed in claim 5,
It is characterized in that, in step (3), 4000rpm centrifuges 5min after cooling;Supernatant is filtered with 0.22-0.45 μm of water system miillpore filter.
7. the method for a kind of acid processing coupling microorganism conversion lignite generation methane and lactic acid as claimed in claim 6,
It being characterized in that, in step (4), it is 5.5-6.0 that a copy of it clear liquid, which adjusts pH, and the agent of lactic acid bacteria that volume fraction is 1-3% is added,
Regulation system temperature is 36-45 DEG C of progress anaerobic fermentation 10-24h, collects tunning, you can lactic acid is prepared;Other one
It is 6.5-8.0 that part clear liquid, which adjusts pH, and the methane fermentating microorganism that volume fraction is 15-30% is added, and regulation system temperature is 50-
55 DEG C of progress anaerobic fermentation 0.5-3d, collect tunning, you can methane is prepared.
8. the method for a kind of acid processing coupling microorganism conversion lignite generation methane and lactic acid as claimed in claim 7,
It is characterized in that, in step (4), the agent of lactic acid bacteria is Bifidobacterium, lactobacillus bulgaricus, streptococcus thermophilus, acidophilus breast bar
Any one in bacterium or two kinds of bacterium powder arbitrary proportion mixing.
9. the method for a kind of acid processing coupling microorganism conversion lignite generation methane and lactic acid as claimed in claim 8,
It is characterized in that, in step (4), the methane fermentating microorganism is that life sludge sewage anaerobic acclimation obtains.
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