CN105038836A - Cracking process for producing light oil and fuel gas from coal slime - Google Patents
Cracking process for producing light oil and fuel gas from coal slime Download PDFInfo
- Publication number
- CN105038836A CN105038836A CN201510520991.0A CN201510520991A CN105038836A CN 105038836 A CN105038836 A CN 105038836A CN 201510520991 A CN201510520991 A CN 201510520991A CN 105038836 A CN105038836 A CN 105038836A
- Authority
- CN
- China
- Prior art keywords
- coal slime
- carbon
- time
- reaction
- ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Processing Of Solid Wastes (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a cracking process for producing light oil and fuel gas from coal slime. The cracking process for producing the light oil and fuel gas from the coal slime comprises the following steps: blending coal slime into a liquid state to obtain a coal slime solution, thickening and acidifying the coal slime solution to obtain a thickened and acidified coal slime solution; culturing microflora, mixing the thickened and acidified coal slime solution with the microflora to obtain a mixture, and then fermenting the mixture to obtain carbon phagocytizing bacteria; decomposing water in the presence of catalytic ions, so that a hydrogen component is obtained; breaking a carbon bond in a carbon group in the presence of superstrong ammonium ion NH<4+>*4; then mixing the hydrogen component with the broken carbon bond, and carrying out primary carbon hydrogen combination reaction and primary carbon hydrogen ionization reaction while stirring, so that a mixed oil product is obtained; and then generating a secondary hydrogen component, and carrying out secondary carbon bond breakage, secondary carbon hydrogen combination reaction and secondary carbon hydrogen ionization reaction, so that the light oil and fuel gas are obtained. The cracking process for producing the light oil and fuel gas from the coal slime has the advantages that the coal slime can be reasonably utilized and converted into fuel, and conversion ratio can reach up to 95%.
Description
Technical field
The present invention relates to a kind of coal slime and produce light oil, combustion gas cracking technology, belong to chemical industry and bioenergy technical field.
Background technology
What do not go out in universe is carbon, and what be full of is hydrogen, and the ordination number of carbon is 6, and nucleidic mass is 12.01115; The ordination number of hydrogen is 1, and nucleidic mass is 1.00797; As can be seen here, differ greatly between the two, but both creation are become many materials again by the Nature, this is also the mankind's several ten thousand years parts of remaining perplexed despite much thought, the essence of carbon is a radiator is also a cartridge, just because of carbon is a cartridge, just makes carbon not go out.
At present, hydrocarbon polymer is all the Nature machinofacture, and can grasp after occurring, known manpower behavior is also do not know its reason, this is also the origin producing so many residuum why, in prior art, carbon dioxide recovery prepares methyl alcohol, coke water gas process can be grasped; Carbon dioxide recovery is prepared methyl alcohol and lead, zinc-base or copper base can be used as catalyzer, and lead, zinc-base or copper base are entirely for what obtain after sulphide ores decomposes, and it is being chemically feasible for decomposing carbon with it; Another kind of method of producing hydrocarbon polymer utilizes this carbonate aqueous solution produced in water of carbon, obtains hydrocarbon polymer by alcoholization.In sum, hydrocarbon polymer must first have been come, by carbon bond brachymemma by few carbon means.In prior art, super acids (fluorine metaantimmonic acid) can decompose carbon bond, but can not control follow-up technique, and the Nature can utilize nature operation chemical combination, so in theory also by synthetic; First go out from carbon solution carbon and study, carbonic acid gas in air is after organic plant absorbs, by the temperature difference in organic plant body, chemical combination becomes the energy needed for plant-growth, in addition, the algae in water is also grown up by carbon, as can be seen here, carbon can decompose by chemical combination under low, middle temperature, and this extremely meets carbon absorbs (energy) decomposition condition in negative pressure and zero.
At present, all productive lifes be unable to do without fuel, therefore result also in the unbalance of fuel, and the utilization of fuel need security, handleability, can handling, extensive, the characteristic such as price is low, nature is full of fuel material, and key is that utilization means are with cognitive, but analyzes from hydrocarbon polymer, hydrogen is ubiquitous at whole earth atmospheric sphere, inexhaustible; And carbon is producing constantly, everywhere, hydrogen can take from air, water etc.; And carbon can be nature carbon, pollution regenerant can be come from.
Namely coal slime is a kind of pollution regenerant, the material that its sewage being coalwashing plant coal washing produces obtains after reclaiming sewage.At home, have up to ten thousand coalwashing plants, the coal slime of these coalwashing plant generations every day has ton up to a million, and coal slime is a kind of source of pollution, therefore needs solution badly.According to statistics, current domestic undressed coal slime has more than one hundred million ton, and the direction of coal slime regeneration is also only limitted to coal drystone material and mixes coal slime, produces the coal-fired electric generation furnace fuel of low calory, but because of problems such as technique, cost, efficiency, causes its expansion limited; In addition, falling behind place, little for coal slime mix coal briquette for daily basic living, although can also use on a small quantity in open ground, may cause poisoning in densely populated part by resident.
Therefore, exploring the rational Land use systems of a kind of coal slime is at present the problem that this area needs solution badly.
Summary of the invention
For solving the problems of the technologies described above, a kind of coal slime is the object of the present invention is to provide to produce light oil, combustion gas cracking technology.
For achieving the above object, the invention provides a kind of coal slime and produce light oil, combustion gas cracking technology, this technique comprises the following steps: the liquid state that described coal slime is in harmonious proportion obtains coal slime solution, then this coal slime solution is carried out multiviscosisty, acidifying, obtains the coal slime solution after multiviscosisty, acidifying;
Bacteria group culture: admix after head mold is mixed with yeast in plant culturing material and cultivate, obtain flora;
Mixing: described coal slime solution after multiviscosisty, acidifying is mixed with flora, obtains mixture;
Fermentation: fermented by the mixture obtained after mixing, obtain biting carbon bacterium, this is bitten carbon bacterium and is separated from carbon support by carbon back;
First time hydrogen composition generation: under the effect of catalytic ionic, water is decomposed, obtains hydrogen composition;
Carbon bonds for the first time: at superpower ammonium ion NH
4 +under the effect of × 4, the carbon bond in described carbon back is truncated; Carbon bond in preferred carbon back is truncated at 150-200 DEG C;
First time nytron reaction: the described hydrogen composition obtained through first time hydrogen composition formation reaction is mixed with the carbon bond be truncated after first time carbon bonds, stirs the lower nytron that occurs and react, obtain crude oil product;
First time ionic hydrocarbonization reaction: described crude oil product are carried out ionic hydrocarbon reaction, obtains contaminated product product;
Second time hydrogen composition generates: under the effect of catalytic ionic, water is decomposed, obtains hydrogen composition; Be decomposed at the temperature of preferably water more than 700 DEG C;
Second time carbon bonds: at superpower ammonium ion NH
4 +under the effect of × 4, the carbon bond in described contaminated product product is truncated; Carbon bond in preferred contaminated product product is truncated at 150-200 DEG C;
Second time nytron reaction: mixed with the carbon bond be truncated after second time carbon bonds by the described hydrogen composition obtained through the formation reaction of second time hydrogen composition, stirs the reaction of lower generation nytron;
Second time ionic hydrocarbonization reaction: the product be obtained by reacting through second time nytron is carried out ionic hydrocarbon reaction, obtains described light oil, combustion gas.
According to technique of the present invention, preferably, the particle diameter of described coal slime is 250-350 order.
According to technique of the present invention, preferably, described coal slime needs to carry out pre-treatment to it before carrying out mediation liquid state, and the object of this pre-treatment mixes wherein each kind of impurity because of open stacking, with the trouble-free operation of proterctive equipment to remove coal slime.This pretreatment process is the technique means of this area routine, and those skilled in the art according to site work needs, can select suitable pre-treatment means, such as, can be screened by netting gear according to the size of coal grain.
According to technique of the present invention, preferably, described mediation liquid state comprises the following steps: described coal slime mixed with distiller liquor, obtains coal slime solution;
More preferably the mass ratio of described coal slime and distiller liquor is 1:1;
Described distiller liquor comprises the aqueous solution containing chlorion, sodium ion, sulfonium ion, magnesium ion, calcium ion, potassium ion, bicarbonate ion, bromide anion, strontium ion, boron ion and fluorion or seawater;
The pH of described mixing solutions is 7.9-8.1.
According to technique of the present invention, preferably, described coal slime solution is after multiviscosisty, and the particle diameter of coal slime particle is 2-4 micron.
According to technique of the present invention, above-mentioned multiviscosisty is ordinary skill in the art means, those skilled in the art can require to select suitable densification process according to site work, in the preferred embodiment of the present invention, scissors high-speed grinder can be adopted by coal slime grain refine to 2-4 micron, producing change of state after grinding impels flowable liquid conversion for not flowable poly-thick state, and the object of multiviscosisty is to be more conducive to phagocytosis.
Coal is macroion cartridge is also high emitter, the generation of carbon need absorb magnetic energy (heat energy) i.e. Quantum Magnetic, need refinement surely can produce reactive force (pressure), this reactive force (pressure) is bound to produce heating power, therefore thermal resistance material is covered outside needing, for alkalescence, it has heat-absorbing action to seawater, and heating power is under the resistance of alkali is inhaled, and namely carbon be not heated.
According to technique of the present invention, preferably, described acidifying comprises the following steps: added by oxalic acid in the coal slime solution after multiviscosisty, the pH value of coal slime solution is adjusted to 3.5-3.8.
The pH value of the coal slime after multiviscosisty is 7.9-8.1, coal slime is in the nature vegetalitas carrier, this carrier is covered with batting hole, halogen in seawater can be filled up batting hole by coal slime after speed lapping, coal slime now becomes not to be with watery, but this pole does not meet the condition of thalline existence, therefore must reduce the pH value of halogen.Lignin polymerization's aggressiveness in coal slime is organism, the pH value reducing halogen needs the material that character of use is identical relatively, connatural with lignin polymerization aggressiveness in acid is oxalic acid, i.e. quinaldine acid, and this is most important, uses other acid will damage lignin polymerization's aggressiveness.Therefore in a preferred embodiment of the invention, getting oxalic acid is that coal slime is adjusted to the pH value environment (pH value 3.5-3.8) of applicable thalline existence using the nutriment as confession thalline by middle mixture.
According to technique of the present invention, preferably, described bacteria group culture comprises the following steps: admix after being mixed with yeast by head mold in plant culturing material and cultivate, and obtains bacterium source; Again cooked rice is admixed in this bacterium source and leave standstill cultivation, after slaking, then add brown sugar water to expand strong flora;
More preferably in the gross weight of head mold and saccharomycetic mixture for 100%, the massfraction of described head mold is 60%-99%, and saccharomycetic massfraction is 1%-40%;
More preferably the mass ratio of described head mold and saccharomycetic mixture and plant culturing material is 1:3;
More preferably the preparation method of described plant culturing material comprises the following steps: be polished into plant slurry after being mixed with water by plant, namely obtains described plant culturing material;
The mass ratio of further preferred described plant and water is 2:1;
Described plant comprises the combination of polygonaceae plant, Folium et Ramulus Mori, almond leaf, rhizome of chuanxiong, the root of herbaceous peony, pineapple, tangerine leaf, smalt cassia bark and Chinese toon branches and leaves;
The particle diameter of described slurry is 120-160 order;
The mass ratio of described polygonaceae plant, Folium et Ramulus Mori, almond leaf, rhizome of chuanxiong, the root of herbaceous peony, pineapple, tangerine leaf, smalt cassia bark and Chinese toon branches and leaves is 1:1:1:1:1:1:1:1:1;
More preferably the temperature that described bacterium source is cultivated is 30-36 DEG C, and relative humidity is more than 80%, and proportioning (mass percent that this proportioning is head mold, yeast accounts for plant culturing material) is 20%-25%;
More preferably the mass ratio of described bacterium source and cooked rice is 10:100-15:100;
More preferably the time of described standing cultivation is 10-14 days;
More preferably the mass ratio in described brown sugar water and bacterium source is 15:100;
Further preferred described brown sugar water is the mass ratio of brown sugar and water is the brown sugar water of 1:50-1:100.
According to technique of the present invention, distiller's yeast is head mold (Rhizopus) distiller's yeast or head mold (Rhizopus) distiller's yeast and saccharomycetic mixture, in described head mold distiller's yeast and saccharomycetic mixture, head mold distiller's yeast is main ingredient, accounts for the 60-99% of mixture total mass.Described head mold distiller's yeast can be commercially available, as: Angel Yeast output, commodity are called Angel head mold distiller's yeast (SAP material number: commercially available distiller's yeast 84000084); Also can be that head mold bacterial classification by being bought commercial channel is seeded in suitable culture medium to cultivate and obtains, the rhizopus that commercial channel buys, as: the head mold 3.866 of commercially available head mold Q303, Chengdu Inst. of Biology, Chinese Academy of Sciences.The substratum of rhizopus can select cereal as substratum, especially rice medium, flour substratum, bran mass etc.Described yeast can be the yeast that can be used for distiller's yeast that commercial channel buys, and comprising: 1308 yeast saccharomyces cerevisiaes etc. of cereuisiae fermentum (as: cereuisiae fermentum K), Hansenula, mycocandida, thecaspore breeding yeast belong, Trichosporon, Chengdu Inst. of Biology, Chinese Academy of Sciences.
Rhizopus and yeast individually can cultivate acquisition, then the two are mixed, such as:
(1) head mold distiller's yeast preparation: get rice medium (cooked rice 2kg, water 6L), after sterilizing cooling, is inoculated in rice medium by the head mold 3.866 accounting for rice dry weight 1%, cultivates about 30h, obtains head mold distiller's yeast for 28-30 DEG C;
(2) yeast culture: getting concentration is 13 ° of B × worts, gets sulfuric acid adjust ph to 4.1-4.5, after sterilizing cooling, inoculates cereuisiae fermentum K by inoculum size 2% and cultivates 20-24h in 28-30 DEG C, remove substratum, obtain yeast;
(3) by head mold distiller's yeast and yeast mixing, obtain distiller's yeast, wherein head mold distiller's yeast accounts for the 60-99% of distiller's yeast total mass.
Head mold distiller's yeast and saccharomycetic cultivation can also adopt the mode of mixed culture.
According to technique of the present invention, leave standstill cultivation cooked rice is admixed in described bacterium source, after slaking, then add brown sugar water to expand in the process of strong flora, temperature all controls as 30-36 DEG C.
According to technique of the present invention, the present invention's head mold used is the unicellular microorganism of phycomycetes, mucorales, Mucoraceae, Rhizopus in classification biologically.
According to technique of the present invention, described polygonaceae plant is draft, mulberry be woody, almond leaf is Folium Pruni, and all containing oxalic acid in above-mentioned substance, it has restraining effect to general pathogenic bacterium.Above-mentioned mulberry is mulberry leaf, and polygonaceae plant is that the whole strain of plant all can be used, and tangerine is leaf, and smalt osmanthus is skin, and Chinese toon is branches and leaves.
According to technique of the present invention, preferably, described mixing is by the coal slime solution after multiviscosisty, acidifying and mixes through the flora that bacteria group culture obtains;
More preferably the described flora obtained through bacteria group culture is 100:12.2 with the quality proportioning of the coal slime solution after multiviscosisty, acidifying.
According to technique of the present invention, preferably, described fermentation is carried out according to following steps: fermented by the mixture obtained after mixing, obtain biting carbon bacterium;
More preferably the temperature of described fermentation is 20-36 DEG C, and humidity is 100%, and the time of fermentation is 21-90 days.
According to technique of the present invention, above-mentioned fermentation need be 20-36 DEG C in temperature, humidity leaves standstill under being the condition of 100%, for biting of flora 21-90 days, is the flora adaptation transitional period in 7 days, and latter 15 days floras turn class kind and become and bite carbon bacterium; In 7 days, with every 15 minutes breeding qualitative change once, within the 7th day, be 672 times for matter mutation (every 15 minutes breeding qualitative change once, then 96 generations of qualitative change every day, within the 7th day, be 672 generations), become adaptive bite carbon bacterium, carbon back can be separated with carbon support by it.
According to technique of the present invention, preferably, the catalytic ionic described in described first time hydrogen composition generation step comprises sulfide mineral and to be heated at 370 DEG C produced ion;
More preferably described catalytic ionic is zine ion or cupric ion.
According to technique of the present invention, preferably, be decomposed at the temperature of water more than 700 DEG C in first time hydrogen composition generation step.
According to technique of the present invention, preferably, superpower ammonium ion NH described in described first time carbon bonds step
4 +the preparation method of × 4 comprises the following steps: at 900-1000 DEG C, and water reacts under the effect of catalytic ionic, obtains NH
4 +× 4;
More preferably described catalytic ionic to be heated produced ion for sulfide mineral at 370 DEG C;
More preferably zine ion or cupric ion.
According to technique of the present invention, superpower ammonium ion NH
4 +the a small amount of nitrogen dissolved in the nitrogen of nitrogen source required in × 4 preparation process in air and water.
According to technique of the present invention, preferably, the carbon bond in carbon back described in first time carbon bonds step is truncated at 150-200 DEG C.
According to technique of the present invention, above-mentioned superpower ammonium ion NH
4 +× 4 prepare by ammonium radical ion is compressed 4 times, the equipment of the present invention to the superpower ammonium ion of preparation is not restricted, and only its preparation method and reaction conditions are limited: namely at 900-1000 DEG C, water is under the effect of catalytic ionic (sulfide mineral be heated at 370 DEG C produced ion) and prepare.
Superpower ammonium ion NH used in a preferred embodiment of this invention
4 +× 4 is that water is made steam, then under the effect of catalytic ionic (sulfide mineral is heated produced ion at 370 DEG C, is preferably zine ion or cupric ion), the water of steam condition is decomposed, obtain hydrogen composition and oxygen composition, then by oxygen component separating, leave hydrogen composition; The hydrogen composition obtained reacts with nitrogen (deriving from a small amount of nitrogen dissolved in nitrogen in air and water) again, obtains above-mentioned superpower ammonium ion NH
4 +× 4.
According to technique of the present invention, preferably, the nytron reaction of described first time specifically comprises the following steps: mixed with the carbon bond be truncated after first time carbon bonds by the hydrogen composition generated by first time hydrogen composition under water-bath, stir with the speed of 10000 revs/min, generation nytron reacts, and obtains crude oil product;
More preferably the mass ratio of described hydrogen and carbon is 1:1.6;
More preferably the temperature of described nytron reaction is 70-80 DEG C, and the reaction times is 10 minutes.
According to technique of the present invention, in described first time nytron reaction process, can produce with the speed high-speed stirring reaction system of 10000 revs/min and throw fast penetration force, pressure, cohesion, and then the carrying out of nytron reaction can be conducive to.
According to technique of the present invention, above-mentioned crude oil product are blue or green black look liquid, and it comprises hydrocarbon polymer, organism, corruption thing, multiclass element polymkeric substance, high molecular polymer, xylogen, oxide compound, hydride, carbide etc.
According to technique of the present invention, described ionic hydrocarbonization reaction is light oil cracking reaction, this reaction is technique means well known in the art, and those skilled in the art can need to select the reaction parameter of described ionic hydrocarbonization reaction, adjust according to site work simultaneously.
In a preferred embodiment of the invention, first time ionic hydrocarbonization reaction divides two sections and carries out: first react at 120 DEG C, then temperature is risen to 130-140 DEG C, and continuation reaction, the reaction times of preferably every section of reaction is 10 minutes.
According to technique of the present invention, preferably, need to carry out fractionation operation after described first time ionic hydrocarbonization reaction, after fractionation operation, obtain contaminated product product.
According to technique of the present invention, preferably, catalytic ionic described in described second time hydrogen composition generation step comprises sulfide mineral and to be heated at 370 DEG C produced ion;
More preferably described catalytic ionic is zine ion or cupric ion.
According to technique of the present invention, preferably, be decomposed at the temperature of water more than 700 DEG C in second time hydrogen composition generation step.
According to technique of the present invention, preferably, superpower ammonium ion NH described in described second time carbon bonds step
4 +the preparation method of × 4 comprises the following steps: at 900-1000 DEG C, and water, under the effect of catalytic ionic, obtains NH
4 +× 4;
More preferably described catalytic ionic comprises sulfide mineral and to be heated at 370 DEG C produced ion;
Further preferred described catalytic ionic is zine ion or cupric ion.
According to technique of the present invention, preferably, the carbon bond in carbon back described in second time carbon bonds step is truncated at 150-200 DEG C.
According to technique of the present invention, preferably, described second time nytron reaction specifically comprises the following steps: mixed with the carbon bond be truncated after second time carbon bonds by the hydrogen composition generated by second time hydrogen composition under water-bath, stir with the speed of 10000 revs/min, nytron reaction occurs;
More preferably the mass ratio of described hydrogen and carbon is 1:1.6;
More preferably the temperature of described nytron reaction is 70-80 DEG C, and the reaction times is 10 minutes.
According to technique of the present invention, described ionic hydrocarbonization reaction is light oil cracking reaction, this reaction is technique means well known in the art, and those skilled in the art can need to select the reaction parameter of described ionic hydrocarbonization reaction, adjust according to site work simultaneously.
In a preferred embodiment of the invention, the reaction of second time ionic hydrocarbonization divides three sections and carries out: first react at 120 DEG C, then temperature is risen to 130-140 DEG C and react, then temperature is risen to 141-350 DEG C, proceed reaction, the reaction times of preferably every section of reaction is 10 minutes.
According to technique of the present invention, preferably, need to carry out distillation operation after described second time ionic hydrocarbonization reaction, after distillation operation terminates, obtain described light oil, combustion gas.
Coal slime reasonably can utilize, be converted into fuel by technique of the present invention, and its transformation efficiency is higher, can reach 95%.
Accompanying drawing explanation
Fig. 1 is that coal slime of the present invention produces light oil, combustion gas cracking technology schema;
Fig. 2 is the gas chromatography mass spectrometry figure of sample A, C, D in the embodiment of the present invention;
Fig. 3, Fig. 4 are the gas chromatography mass spectrometry figure of sample A in the embodiment of the present invention;
Fig. 5, Fig. 6 are the gas chromatography mass spectrometry figure of sample C in the embodiment of the present invention;
Fig. 7, Fig. 8 are the gas chromatography mass spectrometry figure of sample D in the embodiment of the present invention.
Embodiment
In order to there be understanding clearly to technical characteristic of the present invention, object and beneficial effect, the beneficial effect of implementation process of the present invention and generation will be explained below by specific embodiment and Figure of description, be intended to help reader to understand essence of the present invention and feature better, but not as can the restriction of practical range to this case.
Coal slime raw material used in the embodiment of the present invention is the coal slime that the black water drop of haw county of Guizhou Province coalwashing plant recovery goes out, and the diameter of this coal slime is 250-350 order, and recording its calorific value is 2700 cards (C content).
Embodiment 1
Present embodiments provide a kind of coal slime and produce light oil, combustion gas cracking technology, this technique comprises the following steps:
(1), arrangement is selected materials: the size according to coal grain carries out pre-treatment by netting gear to coal slime, and the object of pre-treatment mixes wherein each kind of impurity because of open stacking, with the trouble-free operation of proterctive equipment to remove coal slime.
(2), be in harmonious proportion liquid: be that the coal slime after pre-treatment of 1:1 and distiller liquor (seawater) carry out mix with malaxation device and be mixed to liquid state by mass ratio, obtain coal slime solution; The pH value of this coal slime solution is 8.
(3), multiviscosisty: the coal slime solution that step (2) is obtained by scissors high-speed grinder by coal slime grain refine to 2-4 micron-level particle size.
(4), acidifying: added by oxalic acid in the coal slime solution after multiviscosisty, after acidifying, the pH value of coal slime solution is 3.5-3.8.
(5), bacteria group culture: admix after head mold is mixed with yeast in plant culturing material (mass ratio of head mold and saccharomycetic mixture and plant culturing material is 1:3) and cultivate, the temperature of cultivating is 30-36 DEG C, relative humidity is more than 80%, proportioning is 20%-25%, obtains bacterium source; Again this bacterium source is admixed cooked rice (mass ratio of bacterium source and cooked rice is 10:100-15:100) and leave standstill cultivation 10-14 days, after slaking, then to add with the mass ratio of flora be that the brown sugar water (this brown sugar water is the mass ratio of brown sugar and water is the brown sugar water of 1:50-1:100) of 15:100 is to expand strong flora;
In the gross weight of head mold and saccharomycetic mixture for 100%, the massfraction of described head mold is 60%-99%, and saccharomycetic massfraction is 1%-40%;
The preparation method of described plant culturing material comprises the following steps: plant is polished into plant slurry with mass ratio after 2:1 mixes with water again, namely obtains described plant culturing material; The particle diameter of this plant culturing material is 120-160 order; Above-mentioned plant comprises the combination that polygonaceae plant, Folium et Ramulus Mori, almond leaf, rhizome of chuanxiong, the root of herbaceous peony, pineapple, tangerine leaf, smalt cassia bark and Chinese toon branches and leaves take mass ratio as 1:1:1:1:1:1:1:1:1.
(6), mix: be that 12.2:100 mixes by the coal slime solution after multiviscosisty, acidifying and the flora that obtains through bacteria group culture with mass ratio.
(7), fermentation: after the coal slime solution after multiviscosisty, acidifying and the flora mixing that obtains through bacteria group culture, be 20-36 DEG C in temperature, humidity is carry out fermentation 21-90 days under the condition of 100%, obtains biting carbon bacterium; This is bitten carbon bacterium and carbon back can be separated from carbon support.
(8), hydrogen composition generates first time: under the effect of zine ion or cupric ion (for sulfide mineral is heated produced ion at 370 DEG C), be decomposed, obtain hydrogen composition at the temperature of water more than 700 DEG C.
(9), first time carbon bonds: at superpower ammonium ion NH
4 +under the effect of × 4, the carbon bond in the described carbon back obtained through fermenting is truncated at 150-200 DEG C;
Described superpower ammonium ion NH
4 +the preparation method of × 4 comprises the following steps: at 900-1000 DEG C, and water, under the effect of zine ion or cupric ion (for sulfide mineral is heated produced ion at 370 DEG C), obtains NH
4 +× 4.
(10), first time nytron reaction: be that 1:1.6 mix with the carbon bond be truncated after first time carbon bonds with mass ratio by the hydrogen composition obtained by first time hydrogen composition formation reaction under water-bath, stir with the speed of 10000 revs/min, there is nytron at 70-80 DEG C and react 10 minutes, obtain crude oil product.
(11), first time ionic hydrocarbonization reaction: by through first time the crude oil product that are obtained by reacting of nytron carry out ionic hydrocarbon reaction.
First first time ionic hydrocarbonization reaction reacts 10 minutes at 120 DEG C, then temperature is risen to 130-140 DEG C, continues reaction 10 minutes.
(12), fractionation: the product be obtained by reacting by first time ionic hydrocarbon carries out fractionation, obtains contaminated product product.
(13), second time hydrogen composition generates: under the effect of zine ion or cupric ion (for sulfide mineral is heated produced ion at 370 DEG C), is decomposed, obtains hydrogen composition at the temperature of water more than 700 DEG C.
(14), second time carbon bonds: at superpower ammonium ion NH
4 +under the effect of × 4, the carbon bond in the described contaminated product product obtained after fractionation is truncated at 150-200 DEG C;
Described superpower ammonium ion NH
4 +the preparation method of × 4 comprises the following steps: at 900-1000 DEG C, and water, under the effect of zine ion or cupric ion (for sulfide mineral is heated produced ion at 370 DEG C), obtains NH
4 +× 4.
(15), second time nytron reaction: be that 1:1.6 mix with the carbon bond be truncated after second time carbon bonds with mass ratio by the hydrogen composition generated by second time hydrogen composition under water-bath, stir with the speed of 10000 revs/min, 70-80 DEG C there is nytron and reacts 10 minutes.
(16), second time ionic hydrocarbonization reaction: the product be obtained by reacting through second time nytron is carried out ionic hydrocarbon reaction.
First the reaction of second time ionic hydrocarbonization reacts 10 minutes at 120 DEG C, then temperature is risen to 130-140 DEG C, reacts 10 minutes, then temperature is risen to 141-350 DEG C, continue reaction 10 minutes.
(17), rectifying: need to carry out distillation operation after described second time ionic hydrocarbonization reaction, this distillation operation comprises the following steps: the product that second time ionic hydrocarbon is obtained by reacting is carried out rectifying, obtains described light oil, combustion gas.
Coal slime of the present invention produces light oil, combustion gas cracking technology schema as shown in Figure 1.
The product obtained after fractionation and rectifying and product correlation parameter as shown in table 1 below:
The product obtained after table 1 fractionation and rectifying and product correlation parameter
Analyze example
This analysis example provides the analytical test experiment of the hydrocarbon products prepared by above-described embodiment 1, specifically comprises following items:
Sample illustrates: four, the sample comprising oil slick, emulsion layer and stratum, is numbered A, B, C, D respectively; Sample A, B are respectively the temperature of hydrocarbon products below 120 DEG C that embodiment 1 prepares and carry out upper strata that fractionation obtains and lower floor's overhead product; Sample C, D are respectively the temperature of hydrocarbon products more than 130 DEG C that embodiment 1 prepares and carry out upper strata that fractionation obtains and lower floor's overhead product; This analysis experiment is only got upper strata oil product for oil slick part with centrifuging and is carried out analytical test, sample B because of oil slick little, do not give analysis.
Analytical procedure:
Adopt C, the H element content in ASTMD5291 standard analysis samples A, C, D upper oil phase;
Adopt the content of the S element in ASTMD5453 standard analysis samples A, C, D upper oil phase;
Adopt the content of the N element in ASTMD5762 standard analysis samples A, C, D upper oil phase;
Adopt high temperature GC simulation distil method analytical distillation temperature distribution (ASTMD2887);
FT-NMR nuclear magnetic resonance spectrometry is adopted to analyze carbon structure characteristic: Ca (aromatic carbon), Cp (paraffin carbon), Cn (cycloalkanes carbon);
Employing CC/MSD gas chromatography mass spectrometry method differentiates the composition in sample A, C, D upper oil phase respectively;
HPLC method is adopted to analyze monocycle, dicyclo and the above aromatic hydrocarbon content of three rings (ASTMD6591).
The analytical results of above-mentioned analysis project is as shown in table 2-table 8, and wherein, the gas chromatography mass spectrometry figure of sample A, C, D is as shown in Fig. 2-Fig. 8;
C, H in table 2 sample A, C, D upper oil phase, S, N element content
| A | C | D | |
| C, carbon content (wt%) | 84.61 | 86.88 | 86.63 |
| H, hydrogen richness (wt%) | 11.37 | 12.22 | 12.43 |
| S, sulphur content (wt%) | 0.28 | 0.19 | 0.17 |
| N, nitrogen content (ppmw) | 155 | 100 | 110 |
Table 3 sample A, C, D distillation temperature distributed data
| A | C | D | |
| Initial boiling point (IBP, DEG C) | 224.6 | 233.8 | 232.7 |
| 5％ | 271.8 | 287.4 | 286.9 |
| 10％ | 292.2 | 307.3 | 307.0 |
| 20％ | 313.7 | 329.6 | 329.2 |
| 30％ | 328.5 | 344.1 | 343.8 |
| 40％ | 340.5 | 356.5 | 356.2 |
| 50％ | 352.8 | 368.1 | 367.9 |
| 60％ | 366.1 | 380.5 | 380.3 |
| 70％ | 383.2 | 396.7 | 396.4 |
| 80％ | 410.0 | 417.3 | 417.0 |
| 90％ | 434.8 | 439.4 | 439.1 |
| 95％ | 449.6 | 457.7 | 457.3 |
| Full boiling point (FBP, DEG C) | 503.4 | 527.7 | 525.2 |
The content of aromatic carbon, paraffin carbon, cycloalkanes carbon in table 4 sample A, C, D upper oil phase
| A | C | D | |
| Ca aromatic carbon, wt% | 24.6 | 17.7 | 18.4 |
| Cp paraffin carbon, wt% | 38.5 | 44.7 | 42.9 |
| Cn cycloalkanes carbon, wt% | 36.9 | 37.6 | 38.7 |
Monocycle, dicyclo and the above aromatic hydrocarbon content of three rings in table 5 sample A, C, D upper oil phase
| A | C | D | |
| Stable hydrocarbon, wt% | - | - | 68.5 |
| Mononuclear aromatics, wt% | - | - | 19.3 |
| Di-aromatics, wt% | - | - | 6.2 |
| Polynuclear aromatics, wt% | - | - | 6.1 |
| Total aromatic hydrocarbon, wt% | - | - | 31.5 |
Table 6 sample A distillation temperature distributed data
Table 7 sample C distillation temperature distributed data
| Reclaim | Boiling point/DEG C | Reclaim | Boiling point/DEG C | Reclaim | Boiling point/DEG C | Reclaim | Boiling point/DEG C |
| Quality % | Quality % | Quality % | Quality % | ||||
| Initial boiling point | 233.8 | 26.0 | 338.2 | 52.0 | 370.6 | 78.0 | 412.9 |
| 1.0 | 247.2 | 27.0 | 339.8 | 53.0 | 371.6 | 79.0 | 415.2 |
| 2.0 | 262.5 | 28.0 | 341.2 | 54.0 | 372.8 | 80.0 | 417.3 |
| 3.0 | 272.5 | 29.0 | 342.6 | 55.0 | 374.1 | 81.0 | 419.4 |
| 4.0 | 280.9 | 30.0 | 344.1 | 56.0 | 375.3 | 82.0 | 421.3 |
| 5.0 | 287.4 | 31.0 | 345.3 | 57.0 | 376.6 | 83.0 | 423.5 |
| 6.0 | 292.5 | 32.0 | 346.6 | 58.0 | 377.8 | 84.0 | 425.6 |
| 7.0 | 296.8 | 33.0 | 347.8 | 59.0 | 379.1 | 85.0 | 427.7 |
| 8.0 | 300.9 | 34.0 | 349.2 | 60.0 | 380.5 | 86.0 | 429.9 |
| 9.0 | 304.5 | 35.0 | 350.3 | 61.0 | 382.0 | 87.0 | 432.3 |
| 10.0 | 307.3 | 36.0 | 351.7 | 62.0 | 383.3 | 88.0 | 434.8 |
| 11.0 | 310.3 | 37.0 | 352.8 | 63.0 | 384.8 | 89.0 | 436.8 |
| 12.0 | 313.0 | 38.0 | 354.0 | 64.0 | 386.3 | 90.0 | 439.4 |
| 13.0 | 315.4 | 39.0 | 355.2 | 65.0 | 387.9 | 91.0 | 442.3 |
| 14.0 | 317.6 | 40.0 | 356.5 | 66.0 | 389.5 | 92.0 | 445.0 |
| 15.0 | 319.8 | 41.0 | 357.7 | 67.0 | 391.4 | 93.0 | 448.5 |
| 16.0 | 321.9 | 42.0 | 358.9 | 68.0 | 393.0 | 94.0 | 452.5 |
| 17.0 | 323.8 | 43.0 | 359.9 | 69.0 | 394.8 | 95.0 | 457.7 |
| 18.0 | 325.9 | 44.0 | 361.0 | 70.0 | 396.7 | 96.0 | 463.7 |
| 19.0 | 327.8 | 45.0 | 362.2 | 71.0 | 398.7 | 97.0 | 471.5 |
| 20.0 | 329.6 | 46.0 | 363.4 | 72.0 | 400.6 | 98.0 | 482.0 |
| 21.0 | 330.9 | 47.0 | 364.6 | 73.0 | 402.5 | 99.0 | 500.3 |
| 22.0 | 332.3 | 48.0 | 365.7 | 74.0 | 404.7 | Full boiling point | 527.7 |
| 23.0 | 333.7 | 49.0 | 366.9 | 75.0 | 406.6 | ||
| 24.0 | 335.3 | 50.0 | 368.1 | 76.0 | 408.7 | ||
| 25.0 | 336.8 | 51.0 | 369.4 | 77.0 | 410.8 |
Table 8 sample D distillation temperature distributed data
The present invention, reacts through 1 hour secondary for raw material repeatedly with 100kg coal slime, and at every turn to reach temperature rear (120 DEG C) and 130 DEG C, operation in every 10 minutes 1 time, the every 10 minutes 16.67kg that feed intake, can produce 15.8kg oil product at every turn.Therefore, adopt technique of the present invention coal slime reasonably can be utilized, be converted into fuel, its transformation efficiency is higher, can reach 95%.
Carbon can be converted into the energy by the present invention at short notice, can know confirmation by analysis provided by the invention, uses technique of the present invention can to obtain in coal slime absolutely carbon; From mass spectrum Fig. 2-8, through technique of the present invention, carbon bond structure is substantially identical, and this can confirm that again carbon bond truncated process can be realized by artificial means simultaneously.
In sum, it is feasible for being reclaimed carbon by artificial means, decomposed the technique of carbon.Preliminary statistical result shows, current whole world year discharge carbon amounts has reached 10,000,000,000 tons, be converted into the energy be equivalent to 10,000,000,000 tons of energy if reclaimed, carbon or carbon in the conversion process of carbon, need to add hydrogen or other various elements to be translated into the energy (hydrocarbon polymer), and hydrogen is immanent at atmospheric sphere, not only convenient but also easily obtain, such as can by purified hydrogen from water, then hydrogen is combined with carbon nytron occurs reacts and can obtain the energy (hydrocarbon polymer).In addition, the carbon resource of manual emission is carried out Appropriate application by the present invention, is converted into hydrocarbon polymer, also reduces the discharge of carbonic acid gas simultaneously, and then alleviates Greenhouse effect.
Claims (10)
1. coal slime produces light oil, a combustion gas cracking technology, and wherein, this technique comprises the following steps:
The liquid state that described coal slime is in harmonious proportion obtains coal slime solution, then this coal slime solution is carried out multiviscosisty, acidifying, obtains the coal slime solution after multiviscosisty, acidifying;
The particle diameter of preferred described coal slime is 250-350 order;
Also preferred described coal slime solution is after multiviscosisty, and the particle diameter of coal slime is 2-4 micron;
Bacteria group culture: admix after head mold is mixed with yeast in plant culturing material and cultivate, obtain flora;
Mixing: described coal slime solution after multiviscosisty, acidifying is mixed with flora, obtains mixture;
Fermentation: fermented by the mixture obtained after mixing, obtain biting carbon bacterium, this is bitten carbon bacterium and is separated from carbon support by carbon back;
First time hydrogen composition generation: under the effect of catalytic ionic, water is decomposed, obtains hydrogen composition; Be decomposed at the temperature of preferably water more than 700 DEG C;
Carbon bonds for the first time: at superpower ammonium ion NH
4 +under the effect of × 4, the carbon bond in described carbon back is truncated; Carbon bond in preferred carbon back is truncated at 150-200 DEG C;
First time nytron reaction: the described hydrogen composition obtained through first time hydrogen composition formation reaction is mixed with the carbon bond be truncated after first time carbon bonds, stirs the lower nytron that occurs and react, obtain crude oil product;
First time ionic hydrocarbonization reaction: described crude oil product are carried out ionic hydrocarbon reaction, obtains contaminated product product;
Preferably need to carry out fractionation operation after described first time ionic hydrocarbonization reaction, after fractionation, obtain contaminated product product;
Second time hydrogen composition generates: under the effect of catalytic ionic, water is decomposed, obtains hydrogen composition; Be decomposed at the temperature of preferably water more than 700 DEG C;
Second time carbon bonds: at superpower ammonium ion NH
4 +under the effect of × 4, the carbon bond in described contaminated product product is truncated; Carbon bond in preferred contaminated product product is truncated at 150-200 DEG C;
Second time nytron reaction: mixed with the carbon bond be truncated after second time carbon bonds by the described hydrogen composition obtained through the formation reaction of second time hydrogen composition, stirs the reaction of lower generation nytron;
Second time ionic hydrocarbonization reaction: the product be obtained by reacting through second time nytron is carried out ionic hydrocarbon reaction, obtains described light oil, combustion gas;
Preferably need to carry out distillation operation after the reaction of second time ionic hydrocarbonization, after rectifying, obtain described light oil, combustion gas.
2. technique according to claim 1, wherein, described mediation liquid state comprises the following steps: described coal slime mixed with distiller liquor, obtains coal slime solution;
The mass ratio of preferred described coal slime and distiller liquor is 1:1;
Also preferred described distiller liquor comprises the aqueous solution containing chlorion, sodium ion, sulfonium ion, magnesium ion, calcium ion, potassium ion, bicarbonate ion, bromide anion, strontium ion, boron ion and fluorion or seawater.
3. technique according to claim 1, wherein, described acidifying comprises the following steps: added by oxalic acid in the coal slime solution after multiviscosisty, the pH value of coal slime solution is adjusted to 3.5-3.8.
4. technique according to claim 1, wherein, described bacteria group culture comprises the following steps: admix after being mixed with yeast by head mold in plant culturing material and cultivate, and obtains bacterium source; Again cooked rice is admixed in this bacterium source and leave standstill cultivation, after slaking, then add brown sugar water to expand strong flora;
Preferably in the gross weight of head mold and saccharomycetic mixture for 100%, the massfraction of described head mold is 60%-99%, and saccharomycetic massfraction is 1%-40%;
Also the mass ratio of preferred described head mold and saccharomycetic mixture and plant culturing material is 1:3;
Also the preparation method of preferred described plant culturing material comprises the following steps: be polished into plant slurry again after being mixed with water by plant, namely obtains described plant culturing material;
More preferably the mass ratio of described plant and water is 2:1; Described plant comprises the combination of polygonaceae plant, Folium et Ramulus Mori, almond leaf, rhizome of chuanxiong, the root of herbaceous peony, pineapple, tangerine leaf, smalt cassia bark and Chinese toon branches and leaves; The particle diameter of described slurry is 120-160 order; The mass ratio of described polygonaceae plant, Folium et Ramulus Mori, almond leaf, rhizome of chuanxiong, the root of herbaceous peony, pineapple, tangerine leaf, smalt cassia bark and Chinese toon branches and leaves is 1:1:1:1:1:1:1:1:1;
The temperature that also preferred described bacterium source is cultivated is 30-36 DEG C, and relative humidity is more than 80%, and proportioning is 20%-25%;
Also the mass ratio of preferred described bacterium source and cooked rice is 10:100-15:100;
Also the time of preferred described standing cultivation is 10-14 days;
Also the mass ratio in preferred described brown sugar water and bacterium source is 15:100; More preferably described brown sugar water is the mass ratio of brown sugar and water is the brown sugar water of 1:50-1:100.
5. technique according to claim 1, wherein, described mixing is mixed the coal slime solution after multiviscosisty, acidifying and flora;
Preferred described flora is 100:12.2 with the quality proportioning of the coal slime solution after multiviscosisty, acidifying.
6. technique according to claim 1, wherein, described fermentation is carried out according to following steps: fermented by the mixture obtained after mixing, obtain biting carbon bacterium;
The temperature of preferred described fermentation is 20-36 DEG C, and humidity is 100%, and the time of fermentation is 21-90 days.
7. technique according to claim 1, wherein, described first time hydrogen composition generate, the catalytic ionic described in second time hydrogen composition generation step comprises sulfide mineral and to be heated at 370 DEG C produced ion; Preferably, described catalytic ionic is zine ion or cupric ion.
8. technique according to claim 1, wherein, described first time carbon bonds, superpower ammonium ion NH described in second time carbon bonds step
4 +the preparation method of × 4 comprises the following steps: at 900-1000 DEG C, and water reacts under the effect of catalytic ionic, obtains NH
4 +× 4;
Preferred described catalytic ionic comprises sulfide mineral and to be heated at 370 DEG C produced ion;
More preferably, described catalytic ionic is zine ion or cupric ion.
9. the technique according to claim 1,7 or 8, wherein, the nytron reaction of described first time specifically comprises the following steps: mixed with the carbon bond be truncated after first time carbon bonds by the hydrogen composition generated by first time hydrogen composition under water-bath, stir with the speed of 10000 revs/min, generation nytron reacts, and obtains crude oil product;
The mass ratio of preferred described hydrogen and carbon is 1:1.6;
Also the temperature of preferred described nytron reaction is 70-80 DEG C, and the reaction times is 10 minutes.
10. the technique according to claim 1,7 or 8, wherein, described second time nytron reaction specifically comprises the following steps: mixed with the carbon bond be truncated after second time carbon bonds by the hydrogen composition generated by second time hydrogen composition under water-bath, stir with the speed of 10000 revs/min, nytron reaction occurs;
The mass ratio of preferred described hydrogen and carbon is 1:1.6;
Also the temperature of preferred described nytron reaction is 70-80 DEG C, and the reaction times is 10 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510520991.0A CN105038836B (en) | 2015-08-21 | 2015-08-21 | Coal slime produces light oil processed, combustion gas cracking technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510520991.0A CN105038836B (en) | 2015-08-21 | 2015-08-21 | Coal slime produces light oil processed, combustion gas cracking technology |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105038836A true CN105038836A (en) | 2015-11-11 |
| CN105038836B CN105038836B (en) | 2017-10-20 |
Family
ID=54445811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510520991.0A Active CN105038836B (en) | 2015-08-21 | 2015-08-21 | Coal slime produces light oil processed, combustion gas cracking technology |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105038836B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019051280A1 (en) * | 2017-09-07 | 2019-03-14 | Mcfinney, Llc | Methods for biological processing of hydrocarbon-containing substances and system for realization thereof |
| US12084618B2 (en) | 2023-05-23 | 2024-09-10 | Mcfinney, Llc | Methods for biological processing of hydrocarbon-containing substances and system for realization thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4076612A (en) * | 1973-12-07 | 1978-02-28 | Rio Tinto (Rhodesia) Limited | Process for obtaining liquid fuel-oil and/or gaseous hydrocarbons from solid carbonaceous feed stocks |
| US4132627A (en) * | 1977-12-06 | 1979-01-02 | Leas Arnold M | Integrated coal conversion process |
| CN1640988A (en) * | 2004-01-12 | 2005-07-20 | 煤炭科学研究总院北京煤化工研究分院 | Method for preparing coal tar by coal pyrolysis |
-
2015
- 2015-08-21 CN CN201510520991.0A patent/CN105038836B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4076612A (en) * | 1973-12-07 | 1978-02-28 | Rio Tinto (Rhodesia) Limited | Process for obtaining liquid fuel-oil and/or gaseous hydrocarbons from solid carbonaceous feed stocks |
| US4132627A (en) * | 1977-12-06 | 1979-01-02 | Leas Arnold M | Integrated coal conversion process |
| CN1640988A (en) * | 2004-01-12 | 2005-07-20 | 煤炭科学研究总院北京煤化工研究分院 | Method for preparing coal tar by coal pyrolysis |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019051280A1 (en) * | 2017-09-07 | 2019-03-14 | Mcfinney, Llc | Methods for biological processing of hydrocarbon-containing substances and system for realization thereof |
| US11104850B2 (en) | 2017-09-07 | 2021-08-31 | Mcfinney, Llc | Methods for biological processing of hydrocarbon-containing substances and system for realization thereof |
| US11655420B2 (en) | 2017-09-07 | 2023-05-23 | Mcfinney, Llc | Methods for biological processing of hydrocarbon-containing substances and system for realization thereof |
| US12084618B2 (en) | 2023-05-23 | 2024-09-10 | Mcfinney, Llc | Methods for biological processing of hydrocarbon-containing substances and system for realization thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105038836B (en) | 2017-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109809403B (en) | Preparation method and application of biogas residue-based activated carbon with high adsorption performance | |
| CN106148224B (en) | A kind of straw degradative acidification microbial inoculum and its manufacturing method | |
| CN101264879B (en) | Method for preparing biomass conductive charcoal | |
| CN106278526A (en) | A kind of preparation method of microbial organic fertilizer | |
| CN102701838B (en) | Microbial organic fertilizer by using papermaking sludge as raw material and preparation method thereof | |
| CN105830796A (en) | Dalbergia odorifera seedling culture substrate and preparation method thereof | |
| CN104370582A (en) | Organic garbage odorless aerobic composting method | |
| CN105036822A (en) | Method for preparing specific fertilizer for afforestation | |
| CN113617792B (en) | Method for treating kitchen garbage by hydrothermal carbonization technology | |
| CN104109550A (en) | Method and system for preparing biological oil by antibiotic bacteria residue | |
| CN106865523A (en) | A kind of preparation method and applications of the improvement hydro-thermal charcoal of alleviation rice field ammonia volatilization discharge | |
| US11795484B2 (en) | Method for preparing crude polysaccharide based on fermentation of corn stover and dried bean curd residue by Cordyceps militaris | |
| CN103060245B (en) | Compound microorganism bacterium agent of biological coalbed methane prepared by coal bed organic impurities and application thereof | |
| CN102816723B (en) | Palm oil byproduct biological humic acid, production method thereof and biological humic acid conversion agent used in production method | |
| CN104878045A (en) | Method for producing methane through two-phase mixing anaerobic fermentation of steam-exploded straw and cow dung | |
| CN106350504A (en) | Straw low temperature degradation acidification microbial agent and preparation method and application thereof | |
| CN102174583A (en) | Method for producing biological humic acid by mixed fermentation | |
| CN105038836B (en) | Coal slime produces light oil processed, combustion gas cracking technology | |
| CN112980893A (en) | Method for anaerobic fermentation of lignocellulose biomass through combined pretreatment of biogas slurry and kitchen waste | |
| CN103146776B (en) | Method for producing indigo pigment with bacillus subtilis | |
| CN104478183B (en) | A kind of method utilizing energy grass and anaerobic fermentation technology combination treatment municipal sludge | |
| CN105420281A (en) | Method for efficient production of biogas from straw | |
| CN109950057A (en) | A kind of utilization relates to the method that heavy metal biological matter prepares dynamical super capacitor material | |
| CN114015663A (en) | Composition for producing laccase, fermentation substrate and method for producing laccase by using fermentation substrate | |
| CN101088965B (en) | City refuse re-fermenting process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |