CN105038836B - Coal slime produces light oil processed, combustion gas cracking technology - Google Patents
Coal slime produces light oil processed, combustion gas cracking technology Download PDFInfo
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Abstract
Light oil processed, combustion gas cracking technology are produced the present invention relates to a kind of coal slime.The technique comprises the following steps：Coal slime mediation liquid is obtained into coal slime solution, the coal slime solution is thickened, is acidified, the coal slime solution after viscosified, acidifying is obtained；Bacteria group culture, the coal slime solution after viscosified, acidifying is mixed with flora, mixture is obtained, then the mixture is fermented, and obtains biting carbon bacterium；In the presence of catalytic ionic, water is decomposed, and obtains hydrogen composition；In superpower ammonium ion NH4 +In the presence of × 4, it is carbon-based in carbon key be truncated；Hydrogen composition is mixed with the carbon key being truncated again, stirring is lower to occur the reaction of first time nytron, and the reaction of first time ionic hydrocarbonization obtains contaminated product product；Generated again through second of hydrogen composition, second carbon bonds, second of nytron reaction, second of ionic hydrocarbonization are reacted, and obtain the light oil, combustion gas.The present invention technique can by coal slime reasonably using, be converted into fuel, its conversion ratio is up to 95%.
Description
Technical field
Light oil processed, combustion gas cracking technology are produced the present invention relates to a kind of coal slime, belongs to chemical industry and bioenergy technical field.
Background technology
What is do not gone out in universe is carbon, and what is be full of is hydrogen, and the atomic number of carbon is 6, and atomic weight is 12.01115；Hydrogen
Atomic number is 1, and atomic weight is 1.00797；As can be seen here, differ greatly between the two, but the Nature again creates both
Into many materials, this is also that the essence of carbon is that an emitter is also an absorber in place of the mankind remain perplexed despite much thought for tens of thousands of years,
Just because of carbon is an absorber, just carbon is not gone out.
At present, hydrocarbon is the Nature machine-building, and occur after can grasp, knowable manpower behavior is also
Its reason is not known, this is also the origin for producing so many residue why, in the prior art, carbon dioxide recovery prepares first
Alcohol, coke water gas process can be grasped；Carbon dioxide recovery, which prepares methanol, can use lead, zinc-base or copper-based be used as to urge
Agent, lead, zinc-base or it is copper-based be all what is obtained after sulphide ore is thermally decomposed, with its decompose carbon be feasible in chemistry；It is another
The method that kind produces hydrocarbon is the carbonate aqueous solution produced by utilizing carbon in itself in water, and hydrocarbonization is obtained by alcoholization
Compound.In summary, hydrocarbon must first pass through few carbon means to complete, i.e., truncate carbon key.In the prior art, super acids
(fluorine metaantimmonic acid) can decompose carbon key, but can not control follow-up technique, and the Nature can utilize nature process chemical combination, then reason
By it is upper also can be by artificial synthesized；First go out to study from carbon solution carbon, after the carbon dioxide in air absorbs through organic plant, pass through
The temperature difference in organic plant body, chemical combination turns into the energy needed for plant growth, in addition, the algae in water grows up also by carbon,
As can be seen here, carbon can be decomposed chemical combination under low, middle temperature, and this extremely meets decomposition condition of the carbon in negative pressure and zero absorption (energy).
At present, all production and living too busy to get away fuel, therefore also result in the unbalance of fuel, and the utilization of fuel
Security, handleability, controllability, extensive, the low characteristic of price are needed, nature is full of fuel material, and key exists
In with means with it is cognitive, but analyzed from hydrocarbon, hydrogen be in whole earth atmospheric thermodynamics it is ubiquitous, it is inexhaustible
It is nexhaustible；And carbon is being produced constantly, everywhere, hydrogen can take from sky gas and water etc.；And carbon can be nature carbon, it can come from
In pollution regenerant.
Coal slime is a kind of thing for polluting regenerant, being obtained after its recovered sewage of sewage produced for coal washing plant coal washing
Matter.At home, there are up to ten thousand coal washing plants, the coal slime that these coal washing plants are produced daily there are tons up to a million, and coal slime is a kind of pollution sources,
Therefore urgent need to resolve.According to statistics, domestic undressed coal slime has more than one hundred million tons at present, and the direction of coal slime regeneration is also only limitted to coal and done
Stone material mixes coal slime, produces the coal-fired electric generation furnace fuel of low-calorie, but the problems such as because of technique, cost, efficiency, causes
Its expansion is limited；In addition, falling behind place, resident is by the small coal briquette of coal slime mix for daily basic living, although open
Ground can also be used on a small quantity, but be likely to result in poisoning in densely populated part.
Therefore, the problem of a kind of rational Land use systems of coal slime are this area urgent need to resolve is explored at present.
The content of the invention
In order to solve the above technical problems, producing light oil processed, combustion gas cracking technology it is an object of the invention to provide a kind of coal slime.
To reach above-mentioned purpose, the present invention provides a kind of coal slime and produces light oil processed, combustion gas cracking technology, and the technique includes following
Step：Coal slime mediation liquid is obtained into coal slime solution, then the coal slime solution is thickened, is acidified, viscosified, acid is obtained
Coal slime solution after change；
Bacteria group culture：Admix and cultivated in plant compost after head mold is mixed with saccharomycete, obtain flora；
Mixing：Coal slime solution after the viscosified, acidifying is mixed with flora, mixture is obtained；
Fermentation：The mixture obtained after mixing is fermented, obtains biting carbon bacterium, this bites carbon bacterium by carbon-based from carbon carrier
On separate；
First time hydrogen composition is generated：In the presence of catalytic ionic, water is decomposed, obtain hydrogen composition；
First time carbon bonds：In superpower ammonium ion NH4 +In the presence of × 4, make it is described it is carbon-based in carbon key be truncated；It is excellent
Select it is carbon-based in carbon key be truncated at 150-200 DEG C；
First time nytron reacts：By the hydrogen composition obtained through first time hydrogen composition reaction of formation and through for the first time
The carbon key being truncated after carbon bonds is mixed, and stirring is lower to occur nytron reaction, obtains crude oil product；
First time ionic hydrocarbonization is reacted：The crude oil product are subjected to ionic hydrocarbon reaction, contaminated product product are obtained；
Second of hydrogen composition generation：In the presence of catalytic ionic, water is decomposed, obtain hydrogen composition；It is preferred that water is 700
It is decomposed at a temperature of more than DEG C；
Second of carbon bonds：In superpower ammonium ion NH4 +In the presence of × 4, it is truncated the carbon key in the contaminated product product；
It is preferred that the carbon key in contaminated product product is truncated at 150-200 DEG C；
Second of nytron reaction：By the hydrogen composition obtained through second of hydrogen composition reaction of formation and through second
The carbon key being truncated after carbon bonds is mixed, and stirring is lower to occur nytron reaction；
Second of ionic hydrocarbonization reaction：The product obtained through second of nytron reaction is subjected to ionic hydrocarbonization anti-
Should, obtain the light oil, combustion gas.
According to technique of the present invention, it is preferable that the particle diameter of the coal slime is 250-350 mesh.
According to technique of the present invention, it is preferable that the coal slime needs to carry out preceding place to it before mediation liquid is carried out
Reason, the purpose of the pre-treatment is to mix various impurity therein because of open stack to remove coal slime, with protection equipment
Trouble-free operation.The pretreatment process is this area conventional technology, and those skilled in the art can be according to field operation need
Will, suitable pre-treatment means are selected, for example, can be screened according to the size of coal grain by netting gear.
According to technique of the present invention, it is preferable that the mediation liquid comprises the following steps：By the coal slime with reconciling
Liquid is mixed, and obtains coal slime solution；
The mass ratio of more preferably described coal slime and distiller liquor is 1:1；
The distiller liquor includes containing chlorion, sodium ion, sulphion, magnesium ion, calcium ion, potassium ion, bicarbonate radical
Ion, bromide ion, strontium ion, the aqueous solution or seawater of boron ion and fluorine ion；
The pH of the mixed solution is 7.9-8.1.
According to technique of the present invention, it is preferable that after the coal slime solution is viscosified, the particle diameter of coal slime particle is 2-4
Micron.
According to technique of the present invention, above-mentioned thickening is ordinary skill in the art means, and those skilled in the art can
, can be high using scissors in the preferred embodiment of the present invention to be required to select suitable densification process according to field operation
Coal slime particle is refined to 2-4 microns by fast grinder, after grinding produce state change promote flowable liquid to be converted into can not
The poly- thick state of flowing, the purpose of thickening is to be more conducive to phagocytosis.
Coal is that macroion absorber is also high emitter, and the generation of carbon need to absorb magnetic energy (heat energy) i.e. Quantum Magnetic, needs refinement
Surely power (pressure) can be acted, the active force (pressure) is bound to produce heating power, it is therefore desirable to overcoating thermal resistance material, seawater is
It has heat-absorbing action to alkalescence, and heating power is in the case where the resistance of alkali is inhaled, and carbon is not heated.
According to technique of the present invention, it is preferable that the acidifying comprises the following steps：By oxalic acid add it is viscosified after
In coal slime solution, the pH value of coal slime solution is adjusted to 3.5-3.8.
The pH value of coal slime after thickening is 7.9-8.1, and coal slime is in the nature vegetalitas carrier, and the carrier is covered with batting hole, coal
Halogen in seawater can be filled up batting hole by mud after speed lapping, and coal slime now is into without watery, but this pole is not met
The condition of thalline existence, therefore the pH value of halogen must be reduced.Lignin polymerization's aggressiveness in coal slime is organic matter, reduces halogen
Relative need to use in property identical material, acid connatural with lignin polymerization aggressiveness of pH value be oxalic acid, i.e. quinaldine acid,
This is most important, and lignin polymerization's aggressiveness will be damaged using other acid.Therefore in a preferred embodiment of the invention,
Take oxalic acid that coal slime is adjusted into the pH environment (pH value 3.5-3.8) survived to suitable thalline to be used as supporting for thalline for middle mixture
Material.
According to technique of the present invention, it is preferable that the bacteria group culture comprises the following steps：Head mold is mixed with saccharomycete
Admix and cultivated in plant compost after conjunction, obtain bacterium source；The bacterium source is admixed into cooked rice again and stands cultivation, after curing, then
Brown sugar water is added to expand strong flora；
More preferably counted using the gross weight of head mold and the mixture of saccharomycete as 100%, the mass fraction of the head mold is
60%-99%, the mass fraction of saccharomycete is 1%-40%；
The mixture of more preferably described head mold and saccharomycete is 1 with the mass ratio of plant compost:3；
The preparation method of more preferably described plant compost comprises the following steps：It is polished into after plant is mixed with water
Plant slurry, that is, obtain the plant compost；
The mass ratio of the further preferred plant and water is 2:1；
The plant includes 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
The combination of branches and leaves；
The particle diameter of the slurry is 120-160 mesh；
The polygonaceae plant, Folium et Ramulus Mori, almond leaf, rhizome of chuanxiong, the root of herbaceous peony, pineapple, tangerine leaf, the matter of smalt cassia bark and Chinese toon branches and leaves
Amount is than being 1:1:1:1:1:1:1:1:1；
The temperature of more preferably described bacterium source culture is 30-36 DEG C, and relative humidity is more than 80%, and (proportioning is root to proportioning
Mould, saccharomycete accounts for the mass percent of plant compost) it is 20%-25%；
The mass ratio of more preferably described bacterium source and cooked rice is 10:100-15:100；
The more preferably described time for standing cultivation is 10-14 days；
More preferably described brown sugar water and the mass ratio of bacterium source are 15:100；
The further preferred brown sugar water is that the mass ratio of brown sugar and water is 1:50-1:100 brown sugar water.
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 ferment
Head mold distiller's yeast is key component in the mixture of female bacterium, the mixture of the head mold distiller's yeast and saccharomycete, accounts for mixture gross mass
60-99%.The head mold distiller's yeast can be it is commercially available, such as：Angel Yeast output, trade name Angel head mold distiller's yeast (SAP
Material number:84000084) commercially available distiller's yeast；Can also be that suitable training is seeded to by the head mold strain for buying commercial channel
Support what culture in base was obtained, the rhizopus that commercial channel is bought, such as：Commercially available head mold Q303, Chinese Academy of Sciences's Chengdu biology are ground
Study carefully head mold 3.866.The culture medium of rhizopus can select cereal to be trained as culture medium, especially rice medium, flour
Support base, bran mass etc..The saccharomycete can be the saccharomycete available for distiller's yeast that commercial channel is bought, including：Beer
Brewer yeast is (such as：Brewer's yeast K), Hansenula, candida, ascospore breeding saccharomyces, Trichosporon, China
Academy of sciences's Chengdu biological study 1308 saccharomyces cerevisiaes etc..
Rhizopus and saccharomycete can individually cultivate acquisition, then mix the two, for example：
(1) prepared by head mold distiller's yeast：Rice medium (cooked rice 2kg, water 6L) is taken, after sterilizing cooling, rice dry weight will be accounted for
1% head mold 3.866 is inoculated in rice medium, and 28-30 DEG C is cultivated 30h or so, obtains head mold distiller's yeast；
(2) Yeast Cultivation：It is 13 ° of B × brewer's worts to take concentration, takes sulphur acid for adjusting pH value to 4.1-4.5, after sterilizing cooling,
20-24h is cultivated in 28-30 DEG C by the inoculation brewer's yeast K of inoculum concentration 2%, culture medium is removed, obtains saccharomycete；
(3) head mold distiller's yeast and saccharomycete are mixed, obtains distiller's yeast, wherein head mold distiller's yeast accounts for the 60-99% of distiller's yeast gross mass.
The culture of head mold distiller's yeast and saccharomycete can also be by the way of mixed culture.
According to technique of the present invention, cultivation is stood the bacterium source is admixed into cooked rice, after curing, brown sugar is added
During water is to expand strong flora, temperature is controlled as 30-36 DEG C.
According to technique of the present invention, head mold used in the present invention is Phycomycetes, Mucor in classification biologically
Mesh, Mucoraceae, the unicellular microorganism of rhizopus.
According to technique of the present invention, the polygonaceae plant be draft, mulberry be woody, almond leaf is Folium Pruni, above-mentioned
Contain oxalic acid in material, it has inhibitory action to general pathogenic bacteria.Above-mentioned mulberry is mulberry leaf, and polygonaceae plant is the whole strain of plant
With with tangerine is leaf, and smalt osmanthus is skin, and Chinese toon is branches and leaves.
According to technique of the present invention, it is preferable that the mixing is by the coal slime solution after viscosified, acidifying and through bacterium
The flora that group's culture is obtained is mixed；
The quality proportioning of coal slime solution after the more preferably described flora obtained through bacteria group culture and viscosified, acidifying is
100:12.2。
According to technique of the present invention, it is preferable that the fermentation is followed the steps below：It will obtain after mixing
To mixture fermented, obtain biting carbon bacterium；
The temperature of more preferably 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 to be 20-36 DEG C in temperature, humidity is quiet under conditions of 100%
Put, for adapting to the transitional period in biting of flora 21-90 days, 7 days for flora, rear 15 days floras turn class kind and turned into bite carbon bacterium；In 7 days,
With breeding qualitative change in every 15 minutes once, it is within the 7th day that 672 second generation matter mutation (breed qualitative change once in every 15 minutes, then daily qualitative change
96 second generations, the 7th day are 672 second generations), carbon bacterium is bitten into adaptive, it can be separated carbon-based with carbon carrier.
According to technique of the present invention, it is preferable that the catalytic ionic described in the first time hydrogen composition generation step
Ion produced by being heated including sulfide mine at 370 DEG C；
More preferably described catalytic ionic is zinc ion or copper ion.
According to technique of the present invention, it is preferable that temperature of the first time hydrogen composition generation step reclaimed water more than 700 DEG C
Under be decomposed.
According to technique of the present invention, it is preferable that superpower ammonium ion NH described in the first time carbon bonds step4 +
× 4 preparation method comprises the following steps：At 900-1000 DEG C, water reacts in the presence of catalytic ionic, obtains NH4 +×
4；
More preferably described catalytic ionic is the ion produced by sulfide mine is heated at 370 DEG C；
More preferably zinc ion or copper ion.
According to technique of the present invention, superpower ammonium ion NH4 +Nitrogen source required in × 4 preparation process is in air
Nitrogen and water in a small amount of nitrogen for dissolving.
According to technique of the present invention, it is preferable that the carbon key in carbon-based described in first time carbon bonds step exists
150-200 DEG C is truncated.
According to technique of the present invention, above-mentioned superpower ammonium ion NH4 +× 4 be by the way that ammonium ion is compressed into 4 times of preparations
Obtain, the present invention is not restricted to the equipment for preparing superpower ammonium ion, and only its preparation method and reaction condition are limited
System：At i.e. 900-1000 DEG C, water is made in the presence of catalytic ionic (sulfide mine heated produced ion at 370 DEG C)
It is standby to obtain.
Superpower ammonium ion NH used in a preferred embodiment of this invention4 +× 4 be that water is made into steam, then in catalysis
In the presence of ion (sulfide mine heated produced ion, preferably zinc ion or copper ion at 370 DEG C), make vaporous
The water of state is decomposed, and obtains hydrogen composition and oxygen composition, then oxygen composition is separated, and leaves hydrogen composition；Obtained hydrogen composition is again and nitrogen
Gas (deriving from a small amount of nitrogen dissolved in nitrogen and water in air) is reacted, and obtains above-mentioned superpower ammonium ion NH4 +×4。
According to technique of the present invention, it is preferable that the first time nytron reaction specifically includes following steps：Water
The hydrogen composition generated by first time hydrogen composition is mixed with the carbon key being truncated after first time carbon bonds under bath, with
10000 revs/min of speed stirring, occurs nytron reaction, obtains crude oil product；
The mass ratio of more preferably described hydrogen and carbon is 1:1.6；
The temperature of more preferably described nytron reaction is 70-80 DEG C, and the reaction time is 10 minutes.
According to technique of the present invention, in the first time nytron course of reaction, with 10000 revs/min of speed
Degree high-speed stirred reaction system can produce the fast penetration force of throwing, pressure, cohesion, and then the progress that nytron can be conducive to react.
According to technique of the present invention, above-mentioned crude oil product in blue or green black color liquid, its comprising hydrocarbon, organic matter,
Septage, many dvielement polymer, high molecular polymer, lignin, oxide, hydride, carbide etc..
According to technique of the present invention, the ionic hydrocarbonization reaction is light oil cracking reaction, and the reaction is ability
Technological means known to domain, while those skilled in the art can need what is reacted the ionic hydrocarbonization according to field operation
Response parameter is selected, adjusted.
In a preferred embodiment of the invention, first time ionic hydrocarbonization reaction is divided to two sections of progress：First at 120 DEG C
Reaction, then rises to 130-140 DEG C by temperature, continues to react, the reaction time of preferably every section reaction is 10 minutes.
According to technique of the present invention, it is preferable that need to be fractionated after first time ionic hydrocarbonization reaction
Contaminated product product are obtained after operation, fractionation operation.
According to technique of the present invention, it is preferable that catalytic ionic bag described in second of the hydrogen composition generation step
Include the ion produced by sulfide mine is heated at 370 DEG C；
More preferably described catalytic ionic is zinc ion or copper ion.
According to technique of the present invention, it is preferable that temperature of second of hydrogen composition generation step reclaimed water more than 700 DEG C
Under be decomposed.
According to technique of the present invention, it is preferable that superpower ammonium ion NH described in second of carbon bonds step4 +
× 4 preparation method comprises the following steps：At 900-1000 DEG C, water obtains NH in the presence of catalytic ionic4 +×4；
More preferably described catalytic ionic includes the ion produced by sulfide mine is heated at 370 DEG C；
The further preferred catalytic ionic is zinc ion or copper ion.
According to technique of the present invention, it is preferable that the carbon key in carbon-based described in second of carbon bonds step exists
150-200 DEG C is truncated.
According to technique of the present invention, it is preferable that second of nytron reaction specifically includes following steps：Water
It will be mixed under bath by the hydrogen composition of second of hydrogen composition generation with the carbon key being truncated after second of carbon bonds, with
10000 revs/min of speed stirring, occurs nytron reaction；
The mass ratio of more preferably described hydrogen and carbon is 1:1.6；
The temperature of more preferably described nytron reaction is 70-80 DEG C, and the reaction time is 10 minutes.
According to technique of the present invention, the ionic hydrocarbonization reaction is light oil cracking reaction, and the reaction is ability
Technological means known to domain, while those skilled in the art can need what is reacted the ionic hydrocarbonization according to field operation
Response parameter is selected, adjusted.
In a preferred embodiment of the invention, second of ionic hydrocarbonization reaction point, three sections of progress：First at 120 DEG C
Reaction, then rises to 130-140 DEG C by temperature and is reacted, then temperature is risen into 141-350 DEG C, proceeds reaction, preferably
The reaction time of every section of reaction is 10 minutes.
According to technique of the present invention, it is preferable that need to carry out rectifying after second of ionic hydrocarbonization reaction
Operation, distillation operation obtains the light oil, combustion gas after terminating.
The present invention technique can by coal slime reasonably using, be converted into fuel, its conversion ratio is higher, can reach
95%.
Brief description of the drawings
Fig. 1 is that coal slime of the present invention produces light oil processed, combustion gas cracking technology flow chart；
Fig. 2 is the gas chromatography mass spectrometry figure of sample A, C, D in the embodiment of the present invention；
The gas chromatography mass spectrometry figure that Fig. 3, Fig. 4 are sample A in the embodiment of the present invention；
The gas chromatography mass spectrometry figure that Fig. 5, Fig. 6 are sample C in the embodiment of the present invention；
The gas chromatography mass spectrometry figure that Fig. 7, Fig. 8 are sample D in the embodiment of the present invention.
Embodiment
, below will be by specific in order to which technical characteristic, purpose and beneficial effect to the present invention are more clearly understood from
Embodiment and Figure of description explain the present invention implementation process and produce beneficial effect, it is intended to help reader
More fully understand the present invention essence and feature, but not as to this case can practical range restriction.
Used coal slime raw material leaches for the black water that haw county of Guizhou Province coal washing plant is reclaimed in the embodiment of the present invention
Coal slime, a diameter of 250-350 mesh of the coal slime, it is 2700 cards (C content) to measure its calorific value.
Embodiment 1
Present embodiments provide a kind of coal slime and produce light oil processed, combustion gas cracking technology, the technique comprises the following steps：
(1) sorting, is arranged：Pre-treatment is carried out to coal slime by netting gear according to the size of coal grain, the purpose of pre-treatment be for
Removing coal slime mixes various impurity therein because of open stack, with the trouble-free operation of protection equipment.
(2), mediation liquid：It is 1 by mass ratio:1 coal slime after pre-treatment is entered with distiller liquor (seawater) with malaxation device
Row mix is mixed to liquid, obtains coal slime solution；The pH value of the coal slime solution is 8.
(3), it is thickened：Coal slime particle is refined to 2-4 by the coal slime solution that step (2) is obtained by scissors high-speed grinder
Micron-level particle size.
(4), it is acidified：By oxalic acid add it is viscosified after coal slime solution in, after acidifying the pH value of coal slime solution be 3.5-
3.8。
(5), bacteria group culture：Plant compost (the mixture of head mold and saccharomycete is admixed after head mold is mixed with saccharomycete
Mass ratio with plant compost is 1:3) cultivated in, the temperature of culture is 30-36 DEG C, and relative humidity is more than 80%,
Match as 20%-25%, obtain bacterium source；The bacterium source is admixed into cooked rice again, and (mass ratio of bacterium source and cooked rice is 10:100-
15:100) cultivation 10-14 days are stood, after curing, the mass ratio added with flora is 15:(brown sugar water is 100 brown sugar water
The mass ratio of brown sugar and water is 1:50-1:100 brown sugar water) to expand strong flora；
Counted using the gross weight of head mold and the mixture of saccharomycete as 100%, the mass fraction of the head mold is 60%-
99%, the mass fraction of saccharomycete is 1%-40%；
The preparation method of the plant compost comprises the following steps：By plant and water using mass ratio as 2:1 is mixed
It is polished into plant slurry again afterwards, that is, obtains the plant compost；The particle diameter of the plant compost is 120-160 mesh；On
Plant is stated including 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 with quality
Than for 1:1:1:1:1:1:1:1:1 combination.
(6), mix：The flora obtained by the coal slime solution after viscosified, acidifying and through bacteria group culture using mass ratio as
12.2:100 are mixed.
(7), ferment：After coal slime solution after viscosified, acidifying and the flora mixing obtained through bacteria group culture, it is in temperature
20-36 DEG C, humidity be 100% under conditions of carry out fermentation 21-90 days, obtain biting carbon bacterium；This bites carbon bacterium can be by carbon-based from carbon
Separated on carrier.
(8), first time hydrogen composition is generated：(it is produced by sulfide mine is heated at 370 DEG C in zinc ion or copper ion
Ion) in the presence of, water more than 700 DEG C at a temperature of be decomposed, obtain hydrogen composition.
(9), first time carbon bonds：In superpower ammonium ion NH4 +In the presence of × 4, it is described it is fermented obtain it is carbon-based in
Carbon key be truncated at 150-200 DEG C；
The superpower ammonium ion NH4 +× 4 preparation method comprises the following steps：At 900-1000 DEG C, water in zinc ion or
In the presence of copper ion (ion produced by being heated for sulfide mine at 370 DEG C), NH is obtained4 +×4。
(10), first time nytron reacts：Under water-bath by the hydrogen composition obtained by first time hydrogen composition reaction of formation with
The carbon key being truncated after first time carbon bonds is using mass ratio as 1:1.6 are mixed, and are stirred with 10000 revs/min of speed,
Nytron occurs at 70-80 DEG C to react 10 minutes, crude oil product are obtained.
(11), first time ionic hydrocarbonization is reacted：It is hydrocarbon by the progress of obtained crude oil product is reacted through first time nytron
Ion reaction.
The reaction of first time ionic hydrocarbonization is reacted 10 minutes first at 120 DEG C, and temperature then is risen into 130-140 DEG C,
Continue to react 10 minutes.
(12), it is fractionated：First time ionic hydrocarbonization is reacted to obtained product to be fractionated, contaminated product product are obtained.
(13), second of hydrogen composition generation：In zinc ion or copper ion (produced by being heated for sulfide mine at 370 DEG C
Ion) in the presence of, water more than 700 DEG C at a temperature of be decomposed, obtain hydrogen composition.
(14), second of carbon bonds：In superpower ammonium ion NH4 +In the presence of × 4, it is described be fractionated into after obtained contaminated product
Carbon key in product is truncated at 150-200 DEG C；
The superpower ammonium ion NH4 +× 4 preparation method comprises the following steps：At 900-1000 DEG C, water in zinc ion or
In the presence of copper ion (ion produced by being heated for sulfide mine at 370 DEG C), NH is obtained4 +×4。
(15), second of nytron reaction：By by the hydrogen composition of second of hydrogen composition generation and through second under water-bath
The carbon key being truncated after carbon bonds is using mass ratio as 1:1.6 are mixed, and are stirred with 10000 revs/min of speed, 70-80 DEG C
Generation nytron reacts 10 minutes.
(16), second of ionic hydrocarbonization reaction：By the product obtained through the reaction of second nytron carry out it is hydrocarbon from
Sonization is reacted.
Second of ionic hydrocarbonization reaction is reacted 10 minutes first at 120 DEG C, and temperature then is risen into 130-140 DEG C,
Reaction 10 minutes, then temperature is risen to 141-350 DEG C, continue to react 10 minutes.
(17), rectifying：Need to carry out distillation operation after second of ionic hydrocarbonization reaction, the distillation operation includes
Following steps：The product that second of ionic hydrocarbonization reaction is obtained carries out rectifying, obtains the light oil, combustion gas.
It is as shown in Figure 1 that coal slime of the present invention produces light oil processed, combustion gas cracking technology flow chart.
The product and product relevant parameter obtained after fractionation and rectifying is as shown in table 1 below：
Table 1 be fractionated and rectifying after obtained product and product relevant parameter
Analyze example
This analysis example provides the analysis test experiments of the hydrocarbon products prepared by above-described embodiment 1, tool
Body includes following items：
Sample explanation：Comprising oil slick, emulsion layer and four, the sample on stratum, numbering is A, B, C, D respectively；A, B points of sample
Not Wei temperature of the hydrocarbon products that prepare of embodiment 1 below 120 DEG C carry out being fractionated obtained upper strata and lower floor
Distillate；Sample C, D are respectively that temperature of the hydrocarbon products that prepare of embodiment 1 more than 130 DEG C is fractionated
Obtained upper strata and lower floor's distillate；This analysis experiment takes upper strata oil product to carry out analysis survey only for oil slick part with centrifugal process
Examination, sample B seldom, analysis is not given because of oil slick.
Analysis method：
Using the C in ASTM D5291 standard analysis samples A, C, D upper oil phases, H element content；
Using the content of the S elements in ASTM D5453 standard analysis samples A, C, D upper oil phases；
Using the content of the N element in ASTM D5762 standard analysis samples A, C, D upper oil phases；
Using high temperature GC simulation way of distillation analytical distillation Temperature Distributions (ASTM D2887)；
Carbon structure characteristic is analyzed using FT-NMR nuclear magnetic resonance spectrometrys：Ca (aromatic carbon), Cp (paraffin carbon), Cn (cycloalkanes
Carbon)；
Composition in sample A, C, D upper oil phase is differentiated using CC/MSD gas chromatography mass spectrometries method respectively；
Monocyclic, bicyclic and three ring above aromatic hydrocarbon contents (ASTM D6591) are analyzed using HPLC methods.
The analysis result of above-mentioned analysis project as shown in table 2- tables 8, wherein, sample A, C, D gas chromatography mass spectrometry figure are such as
Shown in Fig. 2-Fig. 8；
C, H in sample A, C, D upper oil phase of table 2, S, N element content
| A | C | D | |
| C, carbon content (wt%) | 84.61 | 86.88 | 86.63 |
| H, hydrogen content (wt%) | 11.37 | 12.22 | 12.43 |
| S, sulfur content (wt%) | 0.28 | 0.19 | 0.17 |
| N, nitrogen content (ppmw) | 155 | 100 | 110 |
Sample A, C, D the vapo(u)rizing temperature distributed data of table 3
| 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 |
| Final boiling point (FBP, DEG C) | 503.4 | 527.7 | 525.2 |
Aromatic carbon, paraffin carbon, the content of cycloalkanes carbon in sample A, C, D upper oil phase of table 4
| A | C | D | |
| Ca aromatic carbons, 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 |
Monocyclic, bicyclic and three ring above aromatic hydrocarbon contents in sample A, C, D upper oil phase of table 5
| A | C | D | |
| Saturated hydrocarbons, wt% | - | - | 68.5 |
| Mononuclear aromatic, wt% | - | - | 19.3 |
| Di-aromatics, wt% | - | - | 6.2 |
| Polycyclic aromatic hydrocarbons (PAH), wt% | - | - | 6.1 |
| Total aromatic hydrocarbon, wt% | - | - | 31.5 |
The sample A vapo(u)rizing temperature distributed datas of table 6
The sample C vapo(u)rizing temperature distributed datas of table 7
| 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 | Final 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 |
The sample D vapo(u)rizing temperature distributed datas of table 8
The present invention using 100kg coal slimes as raw material, through 1 hour it is secondary react repeatedly, every time with up to (120 DEG C) and 130 after temperature
DEG C, operate 1 time within every 10 minutes, every 10 minutes 16.67kg that feed intake can produce 15.8kg oil products every time.Therefore, using the present invention
Technique can by coal slime reasonably using, be converted into fuel, its conversion ratio is higher, can reach 95%.
Carbon can be converted into the energy in a short time by the present invention, and analysis provided by the present invention can be clearly confirmed that, be used
The technique of the present invention can obtain in coal slime absolutely carbon；From mass spectrogram Fig. 2-8, the technique through the present invention,
Carbon bond structure is essentially identical, while this can confirm that carbon key truncated process can be realized by artificial means again.
In summary, carbon is reclaimed by artificial means, the technique of decomposition carbon is feasible.Preliminary statistical result shows, mesh
Preceding global year discharge carbon amounts has reached 10,000,000,000 tons, equivalent to 10,000,000,000 tons energy of the energy is converted into if reclaimed, in carbon
Carbon or carbon in conversion process, addition hydrogen or other various elements are needed in order to be translated into the energy (hydrocarbon), and
Hydrogen is immanent in atmospheric thermodynamics, not only facilitates but also easily obtains, for example can be by the purified hydrogen from water, then by hydrogen and carbon knot
Close generation nytron reaction and can be prepared by the energy (hydrocarbon).In addition, the present invention carries out the carbon resource of manual emission
Rationally utilize, be converted into hydrocarbon, while also reducing the discharge of carbon dioxide, and then alleviate greenhouse effects.
Claims (35)
1. a kind of coal slime produces light oil processed, combustion gas cracking technology, wherein, the technique comprises the following steps：
Coal slime mediation liquid is obtained into coal slime solution, then the coal slime solution is thickened, is acidified, viscosified, acid is obtained
Coal slime solution after change；
Bacteria group culture：Admix and cultivated in plant compost after head mold is mixed with saccharomycete, obtain flora；
Mixing：Coal slime solution after the viscosified, acidifying is mixed with flora, mixture is obtained；
Fermentation：The mixture obtained after mixing is fermented, obtains biting carbon bacterium, this is bitten carbon bacterium and divided carbon-based from carbon carrier
Separate out and；
First time hydrogen composition is generated：In the presence of catalytic ionic, water is decomposed, obtain hydrogen composition；First time carbon bonds：
In superpower ammonium ion NH4 +In the presence of × 4, make it is described it is carbon-based in carbon key be truncated；
First time nytron reacts：By the hydrogen composition obtained through first time hydrogen composition reaction of formation and through first time carbon key
The carbon key being truncated after fracture is mixed, and stirring is lower to occur nytron reaction, obtains crude oil product；
First time ionic hydrocarbonization is reacted：The crude oil product are subjected to ionic hydrocarbon reaction, contaminated product product are obtained；
Second of hydrogen composition generation：In the presence of catalytic ionic, water is decomposed, obtain hydrogen composition；Second of carbon bonds：
In superpower ammonium ion NH4 +In the presence of × 4, it is truncated the carbon key in the contaminated product product；
Second of nytron reaction：By the hydrogen composition obtained through second of hydrogen composition reaction of formation and through second of carbon key
The carbon key being truncated after fracture is mixed, and stirring is lower to occur nytron reaction；
Second of ionic hydrocarbonization reaction：The product obtained through second of nytron reaction is subjected to ionic hydrocarbon reaction,
Obtain the light oil, combustion gas；
Superpower ammonium ion NH described in the first time carbon bonds, second of carbon bonds step4 +× 4 preparation method includes
Following steps：At 900-1000 DEG C, water reacts in the presence of catalytic ionic, obtains NH4 +×4。
2. technique according to claim 1, wherein, the particle diameter of the coal slime is 250-350 mesh.
3. technique according to claim 1, wherein, after the coal slime solution is viscosified, the particle diameter of coal slime is 2-4 microns.
4. technique according to claim 1, wherein, in first time hydrogen composition generating process, the water is more than 700 DEG C
At a temperature of be decomposed.
5. technique according to claim 1, wherein, during first time carbon bonds, it is described it is carbon-based in carbon key exist
150-200 DEG C is truncated.
6. technique according to claim 1, wherein, need to carry out fractionation behaviour after first time ionic hydrocarbonization reaction
Make, contaminated product product are obtained after fractionation.
7. technique according to claim 1, wherein, in second of hydrogen composition generating process, the water is more than 700 DEG C
At a temperature of be decomposed.
8. technique according to claim 1, wherein, during second of carbon bonds, the carbon key in contaminated product product exists
150-200 DEG C is truncated.
9. technique according to claim 1, wherein, need to carry out distillation operation after second of ionic hydrocarbonization reaction,
The light oil, combustion gas are obtained after rectifying.
10. technique according to claim 1, wherein, the mediation liquid comprises the following steps：By the coal slime with reconciling
Liquid is mixed, and obtains coal slime solution.
11. technique according to claim 10, wherein, the mass ratio of the coal slime and distiller liquor is 1:1.
12. the technique according to claim 10 or 11, wherein, the distiller liquor include containing chlorion, sodium ion, sulphur from
Son, magnesium ion, calcium ion, potassium ion, bicarbonate ion, bromide ion, strontium ion, the aqueous solution or the sea of boron ion and fluorine ion
Water.
13. technique according to claim 1, wherein, the acidifying comprises the following steps：By oxalic acid add it is viscosified after
In coal slime solution, the pH value of coal slime solution is adjusted to 3.5-3.8.
14. technique according to claim 1, wherein, the bacteria group culture comprises the following steps：Head mold is mixed with saccharomycete
Admix and cultivated in plant compost after conjunction, obtain bacterium source；The bacterium source is admixed into cooked rice again and stands cultivation, after curing, then
Brown sugar water is added to expand strong flora.
15. technique according to claim 14, wherein, counted using the gross weight of head mold and the mixture of saccharomycete as 100%,
The mass fraction of the head mold is 60%-99%, and the mass fraction of saccharomycete is 1%-40%.
16. technique according to claim 14, wherein, the mixture of the head mold and saccharomycete and the matter of plant compost
Amount is than being 1:3.
17. technique according to claim 14, wherein, the preparation method of the plant compost comprises the following steps：Will
Plant is polished into plant slurry again after being mixed with water, that is, obtains the plant compost.
18. technique according to claim 17, wherein, the mass ratio of the plant and water is 2:1；The plant includes knotweed
Section plant, Folium et Ramulus Mori, almond leaf, rhizome of chuanxiong, the root of herbaceous peony, pineapple, tangerine leaf, the combination of smalt cassia bark and Chinese toon branches and leaves；The slurry
Particle diameter is 120-160 mesh；The 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
The mass ratio of branches and leaves is 1:1:1:1:1:1:1:1:1.
19. technique according to claim 14, wherein, the temperature of the bacterium source culture is 30-36 DEG C, and relative humidity is
More than 80%, match as 20%-25%, and the proportioning is that head mold, saccharomycete account for the mass percent of plant compost.
20. technique according to claim 14, wherein, the mass ratio of the bacterium source and cooked rice is 10:100-15:100.
21. technique according to claim 14, wherein, the time for standing cultivation is 10-14 days.
22. technique according to claim 14, wherein, the mass ratio of the brown sugar water and bacterium source is 15:100.
23. technique according to claim 22, wherein, the brown sugar water is that the mass ratio of brown sugar and water is 1:50-1:100
Brown sugar water.
24. technique according to claim 1, wherein, the quality of the flora and the coal slime solution after viscosified, acidifying is matched somebody with somebody
Than for 100:12.2.
25. technique according to claim 1, wherein, the temperature of the fermentation is 20-36 DEG C, and humidity is 100%, fermentation
Time be 21-90 days.
26. technique according to claim 1, wherein, the first time hydrogen composition generation, second of hydrogen composition generation step
Described in catalytic ionic include sulfide mine and be heated at 370 DEG C produced ion.
27. technique according to claim 26, wherein, the catalytic ionic is zinc ion or copper ion.
28. technique according to claim 1, wherein, the superpower ammonium ion NH4 +Catalysis used in × 4 preparation process
Ion includes the ion produced by sulfide mine is heated at 370 DEG C.
29. technique according to claim 28, wherein, the catalytic ionic is zinc ion or copper ion.
30. the technique according to claim 1 or 26, wherein, the first time nytron reaction specifically includes following step
Suddenly：The hydrogen composition generated by first time hydrogen composition and the carbon key being truncated after first time carbon bonds are mixed under water-bath
Close, stirred with 10000 revs/min of speed, occur nytron reaction, obtain crude oil product.
31. technique according to claim 30, wherein, the mass ratio of the hydrogen and carbon is 1:1.6.
32. technique according to claim 30, wherein, the temperature of the nytron reaction is 70-80 DEG C, reaction time
For 10 minutes.
33. the technique according to claim 1 or 26, wherein, second of nytron reaction specifically includes following step
Suddenly：It will be mixed under water-bath by the hydrogen composition of second of hydrogen composition generation and the carbon key being truncated after second of carbon bonds
Close, stirred with 10000 revs/min of speed, occur nytron reaction.
34. technique according to claim 33, wherein, the mass ratio of the hydrogen and carbon is 1:1.6.
35. technique according to claim 33, wherein, the temperature of the nytron reaction is 70-80 DEG C, reaction time
For 10 minutes.
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