CN101112990A - Method for co-production of white carbon black, aluminum oxide and kerogen by kerosene shale - Google Patents
Method for co-production of white carbon black, aluminum oxide and kerogen by kerosene shale Download PDFInfo
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- CN101112990A CN101112990A CNA2007100119720A CN200710011972A CN101112990A CN 101112990 A CN101112990 A CN 101112990A CN A2007100119720 A CNA2007100119720 A CN A2007100119720A CN 200710011972 A CN200710011972 A CN 200710011972A CN 101112990 A CN101112990 A CN 101112990A
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Abstract
The invention relates to a method for preparing white carbon black, alumina and kerogen with oil shale, comprising the steps that: (1) the oil shale is crumbled into grains with a diameter less than 0.84 mm or less; (2) the oil shale, NaOH and water are added into a reactor for reaction for 0.5 to 24 hours at 20 DEG C to 200 DEG C, then filtration is made and a first filtrate and a first filter cake are obtained, then inorganic acid is used to adjust the pH value of the first filtrate and dispersant is added, and the white carbon black is obtain after 0.5 to 24 hours of aging; (3) the first filter cake is mixed with inorganic acid, the acid leaching temperature is 20 DEG C to 100 DEG C and the acid leaching time is 0.5 to 24 hours, then a second filter residues and a second filtrate are obtained upon filtration; (4) aqueous slkali is added into the second filtrate to adjust and control the pH value till precipitate Al(OH)3 is produced, then filtration is made and a third residues Al(OH)3 precipitate and a third filtrate are obtained; the Al(OH)3 precipitate can be used for preparing Al2O3 products with different contents by being sintered at 450 DEG C to 1250 DEG C; (5) the third filtrate can be prepared into Fe2(SO4)3 concentrated solution with different density after being concentrated, then the concentrated solution is further processed and Fe2(SO4)3 product is prepared. The invention has simple technique and low energy consumption.
Description
Technical field
The present invention relates to a kind of utilization and from resinous shale, extract white carbon black and method of alumina, and byproduct---the eco-utilization co-producing white carbon black of kerogenic method, particularly resinous shale, aluminum oxide, ferric oxide, kerogenic method.
Background technology
Resinous shale is called oil shale again, is a kind of natural, impermeable, close-grained black or the flammable fossil oil of brown sheet.Mainly be made up of organism and inorganic mineral, it is female that organism wherein is called oil, is called kerogen again.Inorganics mainly is an inorganic mineral, and according to the difference in the place of production, the otherness of the inorganic mineral in various countries' resinous shale is bigger, and the inorganic mineral in the resinous shale of countries such as the U.S., Russia, Estonia mainly is made of Wingdale.And the mineral substance in the resinous shale of China mainly is to be made of silico-aluminate, and topmost composition is SiO
2And Al
2O
3
Kerogenic composition in the resinous shale is to have the netted family macromolecule material in space, because the source is different, composition differs greatly, but mainly be to constitute, can burn, but can not use organic solvent extraction by elements such as C, H, O, after being heated to certain temperature, kerogen begins to change into bituminous matter, then changes shale oil and combustion gas into, in this process, also will discharge a spot of combination water, second step separated out for volatile matter, and thermal decomposition material will break away from solid particulate, form the available product.
The main of resinous shale utilizes mode to mainly contain destructive distillation extraction shale oil and the two kinds of methods of directly burning.The resinous shale method one-hundred-year history of extracting shale oil by the carbonization decomposition method wherein, technology is comparatively ripe.Distillation process in the world is a lot of now, representative mainly containing: Fushun type retort, Estonia Kiviter gas retort, Brazilian Petrosix gas retort, Estonia Galoter solid heat carrier retort and Canadian Taciuk particle shale retort etc.Though above-mentioned distillation process technology is comparatively ripe, because the ash content of resinous shale own is bigger, causes the gas retort utilization ratio lower, production cost is higher, and a large amount of oil shale residues of generation need a large amount of soils to stack.The direct incendiary of resinous shale utilizes method also because the kerogen heat in the resinous shale is lower, produces a large amount of kerosene shale ashs, contaminate environment.
Chinese patent CN 1962822 main employings have earlier prepared shale oil and combustible gas to resinous shale through distillation process, shale oil is as product, and combustible gas directly acts as a fuel as next step, the burnt shale that a last distillation process is produced carries out calcination processing and has prepared cement clinker, comprehensive utilization angle from oil shale resources, the eco-utilization that meets resinous shale, but this technology does not also solve the lower shortcoming of gas retort utilization ratio; In addition, the value added of the cement clinker of production is lower, and competitive power is not strong.Among the Chinese patent CN 1872782, mainly utilize the oil shale waste that produces after the destructive distillation to be raw material, preparation balling-up material, through 1000～1300 ℃ of calcination processing, prepared haydite, the utilization of a large amount of oil shale wastes that this method produces after for oil shale distillation has certain application value, though this method is aspect the comprehensive utilization of resinous shale, comparatively unilateral, but the ecology comprehensive utilization of resinous shale is had certain reference value.The using value of the haydite of this method preparation is lower in addition, and product lacks the market competitiveness.Chinese patent CN 1683472 sends in the gas retort after resinous shale is crushed to 8mm～80mm, extracts shale oil and combustion gas, less than the resinous shale of 8mm and the resinous shale lime-ash mixing of materials of destructive distillation generation, supplies with burning in circulating fluid bed boiler, and heat is provided.The lime-ash that mixture produces can further be produced material of construction such as cement, haydite and building block.This technology has certain application value to the comprehensive utilization of oil shale resources.But also exist: what this method adopted carries out first destructive distillation to resinous shale, after utilize the operational path of resinous shale lime-ash, make that the resinous shale that contains a large amount of inorganic minerals is higher for the production cost of gas retort, the utilization ratio of gas retort is lower.The value added that should invent cement, haydite and the building block of producing in addition is lower, lacks the shortcoming of the market competitiveness.
And mainly form SiO wherein at the inorganic mineral in China's oil shale resources by silico-aluminate
2And Al
2O
3Content account for the characteristics more than 60% of resinous shale inorganic mineral.And SiO
2Can prepare the very high white carbon black of value added.When resinous shale extracts white carbon black, can control certain condition and extract aluminum oxide, by filter operation, not only make the organism in the resinous shale---kerogen content increases, and has also reduced inorganic mineral, has promptly reduced the ash content in the resinous shale.By filtering to isolate kerogen, can enter gas retort and extract shale oil, improved the utilization ratio of gas retort, reduced the production cost of shale oil.Materials such as the white carbon black that the present invention extracts, aluminum oxide, added value is higher.The present invention is with scientific, the ecology of comprehensive utilization of oil shale resources comprehensive utilization, for a new approach has been started in efficient, economic, the clean reasonably comprehensive utilization of the oil shale resources that reserves are huge.
Summary of the invention
At the insufficient situation of existing oil shale resources ecology comprehensive utilization technique technology, the invention provides a kind of method of resinous shale eco-utilization, take all factors into consideration resource, environment, economy and society benefit, realize the scientific utilization oil shale resources,, economically and reasonably comprehensive utilization efficient, clean for resinous shale provides effective way.
For realizing such purpose, the present invention with oil shale ore broken with screening in the certain particle size scope, at first react at a certain temperature with certain density NaOH solution, Na takes place
2SiO
3Solution after filtration, makes the SiO in the resinous shale
2Separate with resinous shale.Na
2SiO
3Add a spot of dispersion agent (alcohol compound, polyethylene glycols superpolymer) in the filtrate, and be adjusted to certain pH value with mineral acid (sulfuric acid, hydrochloric acid), handle through the ageing of certain hour, obtain the white carbon black precipitation, drying can obtain the white carbon black product.From resinous shale, isolate SiO
2A filter residue, mix with certain density mineral acid (hydrochloric acid, sulfuric acid, phosphoric acid) again, control certain reaction conditions, can further isolate the Al in the resinous shale
3+And Fe
3+, isolate after filtration again and contain Al
3+And Fe
3+Filtrate and contain the filter cake of a small amount of inorganic mineral.Filtrate wherein can further be extracted aluminum oxide and ferric oxide, and remaining residue since wherein organism---kerogen content is bigger, can enter distillation process and prepare shale oil.
Concrete technology of the present invention is: resinous shale (kerogen content is 10～40%, and inorganic mineral content is 60%～90%) is broken and be screened to granularity≤0.84mm, (SiO
2Content is 10%～60%, Al
2O
3Content is 10～30%), resinous shale and NaOH, water are mixed, make SiO
2: NaOH (mol ratio) is 1: 1～1: 10, and the amount that adds entry is 1～100 times of resinous shale, under 20～200 ℃, stir speed (S.S.) is 100～2000 rev/mins, reacts 0.5～24 hour, is cooled to room temperature, carry out the first time and filter, obtain first-time filtrate and a filter residue.First-time filtrate is Na
2SiO
3The aqueous solution, a filter residue is and extracts SiO
2After resinous shale.With mineral acid (HCl or H
2SO
4) first-time filtrate is adjusted pH to 1.0～11.0, and in first-time filtrate, add 0.01%～20% dispersion agent (alcohol compound and polyethylene glycols superpolymer), after stirring 0.5～6.0 under 0～100 ℃, ageing is 0.5～24 hour under the room temperature, obtain white precipitate, filter, drying promptly obtains white carbon black.Purity reaches more than 90%.
Mineral acid (the H that in a filter cake, adds 1～10 times 10%～50%
2SO
4, HCl or H
3PO
4) solution, stir after 1～10 hour, filter, obtain secondary filtrate and secondary filter residue.Be mainly in the secondary filter residue and remove Al
3+And Fe
3+Resinous shale, kerogen content has reached more than 60%, can send into gas retort and carry out carbonization decomposition and prepare shale oil or other treatment process.Add mineral alkali (NaOH or KOH) in the secondary filtrate, control certain pH value, make Al wherein
3+Be converted into and obtain Al (OH)
3Precipitation is filtered, and obtains filter residue three times---Al (OH)
3Precipitation, and three filtrates.Wherein three filter residues can carry out sintering in 450 ℃～1250 ℃ temperature ranges, prepare α-or γ-Al
2O
3Powder.Three times filtrate can obtain Fe through concentrating
2(SO
4)
3Concentrated solution is further to prepare Fe
2(SO
4)
3Raw material.
Advantage of the present invention:
1. succinct, the resinous shale that adapts to the silico-aluminate of different content of the technology of the present invention, the resinous shale raw material sources are extensive.
2. the present invention is owing to adopted reverse resinous shale comprehensive utilization process, promptly pass through earlier inorganic mineral in the resinous shale, be converted into value added high product (white carbon black and aluminum oxide), thereby reduced the content of the inorganic mineral in the resinous shale, improved the content of kerogen in resinous shale, extract in the technology of shale oil through dry distillation thereby thoroughly solved resinous shale, produce the problem of a large amount of resinous shale lime-ash, solved the problem of environmental pollution and land occupation; On the other hand, also open up the new approach that utilizes resinous shale to prepare white carbon black and aluminum oxide, solved the raw material supply problem of white carbon black and alumina industry.
3. the white carbon black of the present invention's preparation owing to adopted new technology, has been explored new preparation condition, has added dispersion agent, thereby has prepared the white carbon black of Nano grade, and size distribution is comparatively even, and specific surface area is bigger.Once more,, improved kerogenic content in the resinous shale, thereby the comprehensive utilization new model that realizes the coproduction of fecund product provides gordian technique because the present invention combines the technology of preparing of white carbon black and aluminum oxide.
4. energy consumption of the present invention is low, liquid, the equal reusable edible of slag in the process engineering.Even enter the secondary filter residue in the distillation process at last, the inorganic mineral slag that produces after destructive distillation also can turn back to the extraction that initial material carries out white carbon black and aluminum oxide once more.
Below be the kerosene shale ash chemical constitution (massfraction %) of the main shale oil plant of China:
| SiO 2 | Al 2O 3 | Fe 2O 3 | CaO | MgO | K 2O+Na 2O |
| 55～65 | 18～26 | 7～11 | 0.5～1.5 | 1～2 | 0.7～3 |
Description of drawings
Fig. 1 is a process flow sheet of the present invention
Embodiment
Embodiment 1:
Take by weighing 15 gram resinous shale, granularity≤0.124mm contains 48.14%SiO in the resinous shale
2, 15.01% Al
2O
3, Fe
2O
35.86%, kerogen content is 21.6%.Respectively resinous shale, 10.0g NaOH are joined in the 250mL there-necked flask, continue to add 30.0mL H
2O, elevated temperature to 100 ℃ starts electric mixer simultaneously and stirs, and continues reaction 8 hours.Reaction mixture is filtered, obtain first-time filtrate and a filter cake.Wherein add 1.0g macromolecule dispersing agent ethanol in the first-time filtrate, at normal temperatures, with magnetic stirring apparatus carry out agitator on one side, one side is the ageing process of dripping hydrochloric acid adjustment pH value slowly, when pH about 10, stop to add hydrochloric acid when beginning to produce white precipitate, continue ageing and stir after 2 hours, stop to stir, standing over night, filter, drying products is white carbon black 7.2g, SiO
2Content is 93.3%.Liquid after the filtration is used for the ageing process of follow-up preparation white carbon black, realizes no generation of waste.
Secondary filter cake and 30% H
2SO
4Mix, be heated to 50 ℃, stirred 1 hour, filtration obtains secondary filtrate and secondary filter cake, the water washing twice of secondary filter cake with volume, and drying promptly gets kerogen content to the end and is 64.5% resinous shale 2.8g.Secondary filtrate adds 30% NaOH solution, till no longer white flocks, leaves standstill 2 hours, filters, and promptly obtains Al (OH)
3Three filter cakes and three filtrates.Three times filter cake can wash with water, drying, and 450 ℃ of sintering obtain 2.02g Al at last
2O
3Three filtrates obtain containing Fe through concentrating
2(SO
4)
3, Al
2(SO
4)
3Crystal, these materials are important chemical productss, and value added is also higher.
Embodiment 2:
Take by weighing 15 gram resinous shale, granularity 0.124mm ~ 0.178mm contains 48.14% SiO in the resinous shale
2For, 15.01% Al
2O
3, 5.86% Fe
2O
3, kerogen content is 21.6%.Join in the 250mL there-necked flask with 10.0g NaOH, continue to add 30.0mL H
2O, elevated temperature to 100 ℃ starts electric mixer simultaneously and stirs, and continues reaction 8 hours.Reaction mixture is filtered, obtain first-time filtrate and a filter cake.Wherein add 1.0g dispersion agent polyoxyethylene glycol in the first-time filtrate, at normal temperatures, with magnetic stirring apparatus carry out agitator on one side, one side is the ageing process of dripping hydrochloric acid adjustment pH value slowly, when beginning to produce white precipitate, pH stops to add hydrochloric acid about 10, continue ageing and stir after 2 hours, stop to stir standing over night, filter, with 2 times water washings 2 times, drying products is white carbon black 6.3g, SiO
2Content is 94.5%.Liquid after the filtration is used for the ageing process of follow-up preparation white carbon black, realizes no generation of waste.
Secondary filter cake and 20% H
2SO
4Mix, be heated to 40 ℃, stirred 2 hours, filtration obtains secondary filtrate and secondary filter cake, and the secondary filter cake is used with the water washing of volume 2 times, and drying promptly gets kerogen content to the end and be 61.55% resinous shale 2.7g.Secondary filtrate adds 20% NaOH solution, till no longer white flocks, leaves standstill 2 hours, filters, and promptly obtains Al (OH)
3Three filter cakes and three filtrates.Three times filter cake can wash with water, drying, and 1250 ℃ of sintering obtain 2.02g Al at last
2O
3Three filtrates obtain containing Fe through concentrating
2(SO
4)
3, Al
2(SO
4)
3Crystal, these materials are important chemical productss, and value added is also higher.
Embodiment 3:
Take by weighing 15 gram resinous shale, granularity 0.25mm～0.42mm contains 48.14%SiO in the resinous shale
2, 15.01% Al
2O
3, Fe
2O
35.86%, kerogen content is 21.6%.Join in the 250mL there-necked flask with 10.0g NaOH, continue toward 50.0mL H
2O, elevated temperature to 100 ℃ starts electric mixer simultaneously and stirs, and continues reaction 16 hours.Reaction mixture is filtered, obtain first-time filtrate and a filter cake.Wherein add 1.0mL dispersion agent polyoxyethylene glycol in the first-time filtrate, at normal temperatures, stir with magnetic stirring apparatus on one side,, when pH begins to produce white precipitate, stop to add hydrochloric acid about 7.0 Yi Bian slowly drip the ageing process that sulfuric acid is adjusted the pH value, continuing ageing stirred after 2 hours, stop to stir, standing over night is filtered, drying products is white carbon black 5.5g, SiO
2Content is 92.4%.Liquid after the filtration is used for the ageing process of follow-up preparation white carbon black, realizes no generation of waste.
The H of secondary filter cake and 100mL 10%
2SO
4Mix, be heated to 80 ℃, stirred 1 hour, filtration obtains secondary filtrate and secondary filter cake, the water washing twice of secondary filter cake with volume, and drying promptly gets kerogen content to the end and is 58.3% resinous shale 3.4g.Secondary filtrate adds 20% NaOH solution, till no longer white flocks, leaves standstill 2 hours, filters, and promptly obtains Al (OH)
3Three filter cakes and three filtrates.Three times filter cake can wash with water, drying, and 450 ℃ of sintering obtain 2.1gAl at last
2O
3Three filtrates obtain containing Fe through concentrating
2(SO
4)
3, Al
2(SO
4)
3Crystal, these materials are important chemical productss, and value added is also higher.
Embodiment 4:
Take by weighing 15 gram resinous shale, granularity 0.42mm ~ 0.84mm contains 48.14%SiO in the resinous shale
2, 15.01% Al
2O
3, Fe
2O
35.86%, kerogen content be 21.6% and 10.0g NaOH join in the 250mL there-necked flask, continue toward 15.0mLH
2O, elevated temperature to 50 ℃ starts electric mixer simultaneously and stirs, and continues reaction 12 hours.Reaction mixture is filtered, obtain first-time filtrate and a filter cake.Wherein add 1.0g dispersion agent ethanol in the first-time filtrate, at normal temperatures, on one side carry out agitator with magnetic stirring apparatus, the ageing process of dripping hydrochloric acid adjustment pH value slowly stops to add hydrochloric acid when pH begins to produce white precipitate about 7.5 on one side, continuing ageing stirred after 2 hours, stop to stir, standing over night is filtered, drying products is white carbon black 6.4g, SiO
2Content is 91.6%.Liquid after the filtration is used for the ageing process of follow-up preparation white carbon black, realizes no generation of waste.
Secondary filter cake and 20% H
2SO
4Mix, be heated to 60 ℃, stirred 2 hours, filtration obtains secondary filtrate and secondary filter cake, the water washing twice of secondary filter cake with volume, and drying promptly gets kerogen content to the end and is 58.5% resinous shale 3.2g.Secondary filtrate adds 30% NaOH solution, till no longer white flocks, leaves standstill 2 hours, filters, and promptly obtains Al (OH)
3Three filter cakes and three filtrates.Three times filter cake can wash with water, drying, and 450 ℃ of sintering obtain 1.8g Al at last
2O
3Three filtrates obtain containing Fe through concentrating
2(SO
4)
3, Al
2(SO
4)
3Crystal, these materials are important chemical productss, and value added is also higher.
Claims (4)
1. one kind with resinous shale co-producing white carbon black, aluminum oxide and kerogenic method, it is characterized in that may further comprise the steps:
(1) fragmentation: resinous shale is crushed to below the particle diameter 0.84mm;
(2) alkali is molten: resinous shale, NaOH, water are joined in the reactor, make resinous shale: NaOH: the mass ratio of water is 1: 0.1～10: 0.1～10, under 20 ℃～200 ℃, reacted 0.5～24 hour, filter, obtain first-time filtrate and a filter cake, it is 3.0～11.0 that first-time filtrate is adjusted the pH value with mineral acid, adds 0.01%～20% dispersion agent, ageing 0.5～24 hour, obtain white carbon black, wherein mineral acid is hydrochloric acid or sulfuric acid; Dispersion agent is alcohol compound or polyethylene glycols superpolymer;
(3) acidleach a: filter cake is mixed with mineral acid, mineral acid is sulfuric acid, hydrochloric acid or phosphoric acid, make a filter cake (butt): the mass ratio of mineral acid is 1: 1～1: 10, the concentration of mineral acid is 10%～50%, the temperature of acidleach is 20 ℃～100 ℃, leaching time is 0.5～24 hour, filters and obtains secondary filter residue and secondary filtrate, and wherein the secondary filter residue prepares the raw material of shale oil as carbonization decomposition;
(4) extraction of aluminum oxide: in secondary filtrate, add alkaline solution, adjust and control the pH value of solution, to producing Al (OH)
3Precipitation is filtered, and obtains three filter residue-Al (OH)
3Precipitation and three filtrates, Al (OH)
3Be deposited in 450 ℃～1250 ℃ following sintering, sintering time is 1～10 hour, the Al of preparation different content
2O
3Product;
(5) concentrate: three filtrates are prepared the Fe of different concns through concentrating
2(SO
4)
3Concentrated solution goes out Fe with the further processing and preparing of concentrated solution
2(SO
4)
3Product.
2. according to claim 1 with resinous shale co-producing white carbon black, aluminum oxide and kerogenic method, it is characterized in that the dispersion agent that adds in the process of above-mentioned preparation white carbon black is alcohol compound or macromolecular compound, be specially alcohol compound and comprise propyl carbinol, Pentyl alcohol, n-hexyl alcohol; The polyethylene glycols superpolymer is mainly polyoxyethylene glycol-2000, polyoxyethylene glycol-4000, polyoxyethylene glycol-6000, polyoxyethylene glycol-8000, polyoxyethylene glycol-10000.
3. according to claim 1 with resinous shale co-producing white carbon black, aluminum oxide and kerogenic method, it is characterized in that the acidleach process adds mineral acid, is hydrochloric acid, sulfuric acid and phosphoric acid.
4. according to claim 1 with resinous shale co-producing white carbon black, aluminum oxide and kerogenic method, it is characterized in that in the alumina extraction process that the alkali of adding is sodium hydroxide or potassium hydroxide.
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|---|---|---|---|
| CN2007100119720A CN101112990B (en) | 2007-07-05 | 2007-07-05 | Method for co-production of white carbon black, aluminum oxide and kerogen by kerosene shale |
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|---|---|---|---|
| CN2007100119720A CN101112990B (en) | 2007-07-05 | 2007-07-05 | Method for co-production of white carbon black, aluminum oxide and kerogen by kerosene shale |
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| CN101112990B CN101112990B (en) | 2010-09-08 |
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Cited By (8)
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| CN101723397B (en) * | 2009-11-27 | 2011-04-06 | 抚顺矿业集团有限责任公司 | Method for preparing zeolite molecular sieve by using oil shale residues |
| CN102701220A (en) * | 2012-05-22 | 2012-10-03 | 韩钊武 | Method for preparing white carbon black by oxygen-free high-temperature calcination and thermal activation of coal gangue |
| CN102910635A (en) * | 2012-10-17 | 2013-02-06 | 安徽科技学院 | Method for preparing high-quality nano-grade white carbon black by using sulfuric acid precipitation method |
| CN102976339A (en) * | 2012-11-05 | 2013-03-20 | 安徽科技学院 | Process for preparing high-dispersibility white carbon black through hydrochloric acid precipitation method |
| CN103395793A (en) * | 2013-07-22 | 2013-11-20 | 沈阳鑫博工业技术发展有限公司 | Method for preparing aluminum oxide and white carbon black by utilizing oil shale ash |
| CN103435079A (en) * | 2013-09-04 | 2013-12-11 | 化工部长沙设计研究院 | Technology for producing aluminium oxide by decomposing mineral containing aluminosilicate at low temperature |
| CN110836836A (en) * | 2018-08-17 | 2020-02-25 | 中国石油化工股份有限公司 | Kerogen elastic modulus testing method |
| CN112456504A (en) * | 2020-12-24 | 2021-03-09 | 西北师范大学 | Preparation method of oil shale semicoke-based white carbon black |
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|---|---|---|---|---|
| CN1094696A (en) * | 1994-03-28 | 1994-11-09 | 余有宏 | A kind of new production process of precipitated silica |
| CA2433448A1 (en) * | 2000-12-31 | 2002-07-11 | Ati-Aluminum Technologies Israel Ltd. | Production of aluminum compounds and silica from ores |
| CN1117029C (en) * | 2001-05-25 | 2003-08-06 | 吉林大学 | Preparation of nanometer SiO2 pipe and nanometer Al2O3 crystal |
| CN100457628C (en) * | 2006-06-02 | 2009-02-04 | 李禹� | Method of extracting aluminium oxide from fly ash and simultaneously producing white carbon black |
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|---|---|---|---|---|
| CN101723397B (en) * | 2009-11-27 | 2011-04-06 | 抚顺矿业集团有限责任公司 | Method for preparing zeolite molecular sieve by using oil shale residues |
| CN102701220A (en) * | 2012-05-22 | 2012-10-03 | 韩钊武 | Method for preparing white carbon black by oxygen-free high-temperature calcination and thermal activation of coal gangue |
| CN102910635A (en) * | 2012-10-17 | 2013-02-06 | 安徽科技学院 | Method for preparing high-quality nano-grade white carbon black by using sulfuric acid precipitation method |
| CN102976339A (en) * | 2012-11-05 | 2013-03-20 | 安徽科技学院 | Process for preparing high-dispersibility white carbon black through hydrochloric acid precipitation method |
| CN103395793A (en) * | 2013-07-22 | 2013-11-20 | 沈阳鑫博工业技术发展有限公司 | Method for preparing aluminum oxide and white carbon black by utilizing oil shale ash |
| CN103435079A (en) * | 2013-09-04 | 2013-12-11 | 化工部长沙设计研究院 | Technology for producing aluminium oxide by decomposing mineral containing aluminosilicate at low temperature |
| CN103435079B (en) * | 2013-09-04 | 2015-03-18 | 化工部长沙设计研究院 | Technology for producing aluminium oxide by decomposing mineral containing aluminosilicate at low temperature |
| CN110836836A (en) * | 2018-08-17 | 2020-02-25 | 中国石油化工股份有限公司 | Kerogen elastic modulus testing method |
| CN110836836B (en) * | 2018-08-17 | 2022-08-16 | 中国石油化工股份有限公司 | Kerogen elastic modulus testing method |
| CN112456504A (en) * | 2020-12-24 | 2021-03-09 | 西北师范大学 | Preparation method of oil shale semicoke-based white carbon black |
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