CN102465004B - Method of oil upgrading - Google Patents
Method of oil upgrading Download PDFInfo
- Publication number
- CN102465004B CN102465004B CN201010541411.3A CN201010541411A CN102465004B CN 102465004 B CN102465004 B CN 102465004B CN 201010541411 A CN201010541411 A CN 201010541411A CN 102465004 B CN102465004 B CN 102465004B
- Authority
- CN
- China
- Prior art keywords
- oil product
- reaction
- modifying
- hydrogenation deoxidation
- catalyzer
- 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.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明提供一种油品改质的方法，包括：以一铁氧化物作为催化剂，使一油品与氢气进行加氢脱氧反应，其中该铁氧化物包括氧化亚铁(FeO)、二氧化铁(FeO2)、三氧化二铁(Fe2O3)、四氧化三铁(Fe3O4)、或前述的组合。The present invention provides a method for upgrading oil, comprising: using an iron oxide as a catalyst to carry out a hydrodeoxygenation reaction of an oil with hydrogen, wherein the iron oxide comprises ferrous oxide (FeO), ferric dioxide (FeO 2 ), ferric oxide (Fe 2 O 3 ), ferrous oxide (Fe 3 O 4 ), or a combination thereof.
Description
Technical field
The present invention relates to the method for modifying oil product, and relates to a kind of method of carrying out modifying oil product with catalyzer hydrogenation especially.
Background technology
Current modifying oil product method is mainly divided into cracking catalyst and catalyzer hydrogenation.Cracking catalyst is under high-temperature pressure, and the hydrocarbon compound after utilizing catalyst pores to control gasification, to obtain liquid fuel, its rate of recovery is about 25wt.%.And traditional catalyst hydrogenation need be carried out at high temperature under high pressure, such as temperature is about 300 ~ 500 DEG C, and pressure is about 5 ~ 20MPa (being about 50 ~ 200atm).When carrying out modifying oil product with catalyzer hydrogenation, conventional catalyzer comprises precious metal, metallic sulfide etc., but its catalyst recovery is more difficult, and its oil product transformation efficiency is according to the difference using catalyzer and condition, about between 30 to 70wt.%.
Generally speaking, the chemical constitution of raw matter crude oil and waste oil (comprising: waste lubricating oil, useless turbine wet goods) is complicated, oxygen level is high, calorific value low (being about between 3000kcal/kg to 4000kcal/kg), and viscosity too high (being greater than 40cps), be difficult to direct use in commercial, therefore need by modifying oil product process, the recycling of oil product can be carried out further.
But, although the upgrading of raw matter crude oil and waste oil can make waste recycle, and can substitute energy be produced, but because the technique of the upgrading of giving birth to matter crude oil and waste oil need be carried out under high temperature, high pressure, and catalyzer cost is high, oil product transformation efficiency is also desirable not to the utmost, therefore to give birth to matter crude oil or waste oil carries out modifying oil product recycling, is not still commercial acceptable method.
Therefore, pole, this area needs a kind of method of modifying oil product of novelty, reduces temperature, pressure, the catalyzer cost of technique, and improves oil product transformation efficiency, reduces the consumption for the energy sources and equipment investment cost.
Summary of the invention
The object of the present invention is to provide a kind of temperature, pressure, the catalyzer cost that reduce technique, and improve oil product transformation efficiency, reduce the method for the modifying oil product of the consumption for the energy sources and equipment investment cost.
The invention provides a kind of method of modifying oil product, comprising: using a ferriferous oxide as catalyzer, make an oil product and hydrogen carry out hydrogenation deoxidation reaction, wherein this ferriferous oxide comprises iron protoxide (FeO), ferrous oxide (FeO
2), ferric oxide (Fe
2o
3), Z 250 (Fe
3o
4) or aforesaid combination.
The method of modifying oil product provided by the present invention, temperature that can be lower, pressure reach the oil product transformation efficiency of more than 60wt.%.The present invention can toughness is high, chemical constitution is complicated, oxygen level is high, the raw matter crude oil that not easily regenerates or waste oil product carry out upgrading, reduce oil viscosity and density, increase oil product caloic, and improve oil product transformation efficiency.
For above and other objects of the present invention, feature and advantage can be become apparent, cited below particularly go out preferred embodiment, be described in detail below:
Embodiment
The invention provides a kind of method of modifying oil product, is mainly the hydrogenation deoxidation reaction that catalyzer carries out oil product with ferriferous oxide.In the preferred embodiment, above-mentioned hydrogenation deoxidation reaction is carried out under subcritical CO 2 fluid exists.
In one embodiment, the oil product carrying out upgrading can be made a living matter crude oil or waste oil, such as: raw pledge cracking oil product, biodiesel, waste lubricating oil, waste edible oil, plastic cracking oil product, tire pyrolysis oil product or aforesaid combination.Wherein, pledge cracking oil product is given birth to such as containing 3 ~ 70wt.% moisture.Method of the present invention is specially adapted to the upgrading of raw matter crude oil, and its oxygen level high (being about 35 to 40wt.%), needs the upgrading that just can carry out oil product at high temperature under high pressure in known technology.Present method also can be applicable to the upgrading of other hypoxic oil product.
Inserted after in metallic reactors by above-mentioned oil product, adding ferriferous oxide is catalyzer.Ferriferous oxide can comprise iron protoxide (FeO), ferrous oxide (FeO
2), ferric oxide (Fe
2o
3), Z 250 (Fe
3o
4) or aforesaid combination.
In one embodiment, catalyzer ferriferous oxide is with after acid dissolve raw material, mineral, Industrial Metal waste, through the magnetite powder of alkali lye precipitation gained.The initial substance of ferriferous oxide is raw material, mineral, Industrial Metal waste, its iron-holder is greater than 35wt.%, and kenel can be elemental iron, ferric oxide as iron protoxide (FeO), ferrous oxide (FeO
2), ferric oxide (Fe
2o
3), Z 250 (Fe
3o
4) or the alloy of ferric oxide and other metal as MFe
2o
4(M is other divalent metal).If starting material is liquid, then directly adjust its pH value with acid, if but it is solid-state, be then crushed to particle and be less than 1mm, make its accelerate dissolution in acid solution, this acid solution can be hydrochloric acid or other strong acid, and pH value is between 0-2.Then, acid solution is filtered to remove insolubles.Then with in alkali lye and above-mentioned acid solution to form neutralizer, now iron ion can form Fe
3o
4.For avoiding strong neutralization reaction, the alkali lye used can be the more weak ammoniacal liquor etc. of alkalescence.Finally filter neutralizer, magnetite powder can be obtained.Detailed method for making about magnetite can with reference to the first to file case TaiWan, China TW201012915 of contriver.But it should be noted, this case ferriferous oxide used is not limited only to the magnetite powder of first to file case.
Compared to catalyzer such as traditional precious metal (such as: platinum) or metallic sulfides, magnetite powder used in the present invention can reduce catalyzer cost, and it is large by specific surface area, the efficiency of hydrogenation can be increased, and its specific heat is good compared with known noble metal catalyzer, heat conduction efficiency can be increased.In addition, magnetite powder, after reacting as catalyzer, also carries out the recovery of magnetite catalyst powder, thus reduces the cost of modifying oil product by the magnetic of magnetite.
In one embodiment, use Z 250 content in magnetite powder to be about 60 to 95%, be preferably about 85 to 95%; The specific surface area of magnetite powder is about 15 to 40m
2/ g, is preferably about 30 to 40m
2/ g; The specific heat of magnetite powder is about 0.1 to 0.4cal/g DEG C; The saturated magnetism intensity of magnetite powder can be greater than about 15emu/g.
In an alternative embodiment of the invention, can also commercially available magnetite powder or other ferriferous oxide as catalyzer, carry out the upgrading of oil product.
Utilize ferriferous oxide catalyst of the present invention to carry out the upgrading of oil product, its product yield can be greater than about 50wt.%, is goodly greater than about 80wt.%, is goodly greater than about 90wt.%.
Also the characteristic of subcritical carbon dioxide expanded liquid can be utilized in the present invention to reduce reactant viscosity.Moreover, because subcritical carbon dioxide expanded liquid can improve the solubleness of hydrogen in oil product, thus can the reaction of accelerated reaction thing and catalyzer, improve the transformation efficiency of modifying oil product, and the temperature reduced needed for reaction and pressure.
When using subcritical carbonic acid gas to carry out the upgrading of oil product, oil product transformation efficiency increases with temperature, unit time unit catalyst sample size and increases.Therefore, when not improving temperature of reaction, adjustable carbonic acid gas improves the transformation efficiency of oil product to the ratio of hydrogen.Wherein, carbonic acid gas and hydrogen ratio scope are preferably 0.1 to 1.0.If carbonic acid gas and hydrogen ratio are lower than 0.1, then cannot improve hydrogen solubility, if but carbonic acid gas and hydrogen ratio higher than 1.0, then hydrogen in reaction content is too low, causes hydrogenation reaction rate to reduce.
Under the existence of subcritical CO 2 fluid, this hydrogenation deoxidation temperature of reaction is at least about 240 DEG C, better for about 280 to 320 DEG C; Pressure is at least about 5atm, better for about 5 to 50atm; Unit time unit catalyst sample size (WHSV) is at least about 5h
-1, and be preferably about 5 to 20h
-1.Wherein, unit time catalyzer sample size (WHSV) is defined as:
The method of modifying oil product provided by the present invention take ferriferous oxide as the hydrogenation deoxidation reaction that catalyzer carries out oil product.The method of traditional catalyst hydrogenation, need be about 300-500 DEG C, high pressure carries out under being about 5-20MPa (about 50-200atm), and Oil Recovery rate is about between 30-70wt.% at high temperature.But the method for modifying oil product provided by the present invention, temperature that can be lower, pressure reach the oil product transformation efficiency of more than 60wt.%.The present invention can toughness is high, chemical constitution is complicated, oxygen level is high, the raw matter crude oil that not easily regenerates or waste oil product carry out upgrading, reduce oil viscosity and density, increase oil product caloic, and improve oil product transformation efficiency.In an embodiment of the present invention, utilize the characteristic of the thermal conductivity of magnetite powder, high-specific surface area, good stability and tool magnetic, it can be used as the hydrogenation deoxidation catalyst of this reaction, and the application of subcritical carbon dioxide liquid of arranging in pairs or groups, reduce reactant viscosity, improve hydrogen solubility, make reactant can enter rapidly catalytic inner to react, improve reaction efficiency, reduce desired reaction temperature and pressure, and reduce the consumption for the energy sources and cost of investment.
[comparative example 1]
Adjacent for weight ratio 5% methoxy phenol (Guaiacol) and 95% n-tetradecane are placed in metallic reactors, with Pd/ZrO
2for catalyzer, be about the hydrogenation deoxidation reaction carrying out oil product at 280 DEG C in temperature.Wherein, adjacent methoxy phenol is a kind of Main Derivatives of giving birth to lignin substance cracking in pledge, in the embodiment of this case, with its transformation efficiency under different experimental conditions, the basis for estimation of pledge cracked oil kind and operational condition quality is given birth to as catalyzer hydrogenation, in order to the pledge of conduct life in the future cracked oil volume production platform, the reference with operational condition selected by catalyzer.And the carrier acting as hydrogen of 95% n-tetradecane, ZrO
2then as the carrier of catalyst P d.
Hydrogen pressure is about 50atm (temperature is about 25 DEG C) in this experiment, and unit time unit catalyst sample size (WHSV) is about 10h
-1.By GC-MS atlas analysis, can obtain adjacent methoxy phenol transformation efficiency is 99.32%.The primary product of this experiment is benzene.
[embodiment 1]
Adjacent for weight ratio 5% methoxy phenol (Guaiacol) and 95% n-tetradecane are placed in metallic reactors, with magnetite powder for catalyzer, are about the hydrogenation deoxidation reaction carrying out oil product at 280 DEG C in temperature.
In the reaction of this hydrogenation deoxidation, hydrogen pressure is about 50atm (temperature is about 25 DEG C), and unit time unit catalyst sample size (WHSV) is about 10h
-1.By GC-MS atlas analysis, can learn that adjacent methoxy phenol transformation efficiency is 99.97%.
Compared to the noble metal catalyst (Pd/ZrO of comparative example 1
2), the magnetite fine catalyst cost that the present invention uses is lower, and adjacent methoxy phenol transformation efficiency is higher.
[embodiment 2]
Adjacent for weight ratio 5% methoxy phenol (Guaiacol) and 95% n-tetradecane are placed in metallic reactors, take ferric oxide powder as catalyzer, are about the hydrogenation deoxidation reaction carrying out oil product at 280 DEG C in temperature.
In the reaction of this hydrogenation deoxidation, hydrogen pressure is about 50atm (temperature is about 25 DEG C), and unit time unit catalyst sample size (WHSV) is about 10h
-1.By GC-MS atlas analysis, can learn that adjacent methoxy phenol transformation efficiency is 99.14%.
Compared to the noble metal catalyst (Pd/ZrO of comparative example 1
2), the ferric oxide powder catalyzer cost that the present invention uses is lower, but still has good adjacent methoxy phenol transformation efficiency.
[embodiment 3]
Adjacent for weight ratio 5% methoxy phenol (Guaiacol) and 95% n-tetradecane are placed in metallic reactors, with iron protoxide powder for catalyzer, are about the hydrogenation deoxidation reaction carrying out oil product at 280 DEG C in temperature.
In the reaction of this hydrogenation deoxidation, hydrogen pressure is about 50atm (temperature is about 25 DEG C), and unit time unit catalyst sample size (WHSV) is about 10h
-1.By GC-MS atlas analysis, can learn that adjacent methoxy phenol transformation efficiency is 52.87%.
[embodiment 4]
Adjacent for weight ratio 5% methoxy phenol (Guaiacol) and 95% n-tetradecane are placed in metallic reactors, react with the hydrogenation deoxidation that magnetite powder carries out oil product for catalyzer, and carry out four factors, the field cause for gossip of three levels tests, and studies the impact of each parameter for adjacent methoxy phenol transformation efficiency.Its reaction conditions is as follows: temperature is respectively at 240,280,320 DEG C; Hydrogen pressure respectively 5,25,50atm (temperature is about 25 DEG C); Unit time unit catalyst sample size (WHSV) respectively 5,10,20h
-1; Carbonic acid gas is than the sample size difference 0,0.5,0.9 of hydrogen.Experimental result can refer to table 1.
Table 1,
Utilize above-mentioned 9 groups of experiments, can know the dependency of adjacent methoxy phenol transformation efficiency by inference, most important person is temperature, and being secondly carbon dioxide ratio, moreover being time unit of unit catalyzer sample size, is finally pressure.Wherein, adjacent methoxy phenol transformation efficiency increases with temperature, unit time unit catalyst sample size and increases, but carbonic acid gas and pressure then have an optimum range.Wherein, carbonic acid gas and hydrogen ratio scope are preferably 0.1 to 0.9.That is in order to reach the object reducing temperature of reaction, the ratio of carbonic acid gas and hydrogen is even more important.
From the present embodiment result, by the interpolation of carbonic acid gas, and the regulation and control of temperature and catalyzer usage quantity, can by total pressure drop to 5atm, adjacent methoxy phenol transformation efficiency can reach more than 99%.It can thus be appreciated that, the advantage of subcritical carbonic acid gas comprises: to the bulking effect of organic solution, the solubleness promoting hydrogen in liquid phase, the viscosity reducing liquid itself, lifting material rate of diffusion, therefore the speed of reaction of oil hydrogenation deoxidation can be promoted, and reduce pressure and the temperature of operation, and reduce running cost.
[embodiment 5]
Adjacent for weight ratio 5% methoxy phenol (Guaiacol) and 95% n-tetradecane are placed in metallic reactors, react with the hydrogenation deoxidation that magnetite powder carries out oil product for catalyzer, reaction conditions is embodiment 4, obtained optimal conversion condition is tested by field cause for gossip, temperature is 320 DEG C, pressure is 25atm, and sample size (WHSV) is 5h
-1, CO
2/ H
2=1, transformation efficiency is 99.95%, collocation CO
2use, the stagnation pressure of 1/2 can be reduced, reduce 3/4 hydrogen usage quantity, reach identical transformation efficiency.
[embodiment 6]
Adjacent for weight ratio 5% methoxy phenol (Guaiacol) and 95% n-tetradecane are placed in metallic reactors, take ferric oxide powder as the hydrogenation deoxidation reaction that catalyzer carries out oil product, reaction conditions is embodiment 4, obtained optimal conversion condition is tested by field cause for gossip, temperature is 320 DEG C, pressure is 25atm, and sample size (WHSV) is 5h
-1, CO
2/ H
2=1, transformation efficiency is 98.27%, collocation CO
2use, the stagnation pressure of 1/2 can be reduced, reduce 3/4 hydrogen usage quantity, reach identical transformation efficiency.
[embodiment 7]
Adjacent for weight ratio 5% methoxy phenol (Guaiacol) and 95% n-tetradecane are placed in metallic reactors, react with the hydrogenation deoxidation that iron protoxide powder carries out oil product for catalyzer, reaction conditions is embodiment 4, obtained optimal conversion condition is tested by field cause for gossip, temperature is 320 DEG C, pressure is 25atm, and sample size (WHSV) is 5h
-1, CO
2/ H
2=1, transformation efficiency is 98.27%, collocation CO
2use, the stagnation pressure of 1/2 can be reduced, reduce 3/4 hydrogen usage quantity, reach identical transformation efficiency.
In the present invention, utilize ferriferous oxide to be catalyzer as iron protoxide, ferric oxide, magnetite, deposit in case at subcritical carbonic acid gas, modifying oil product is carried out to raw matter crude oil or waste oil product.Catalyzer cost used in the present invention is lower, and temperature of reaction, pressure condition are lower, but modifying oil product efficiency is high, therefore can reduce the cost of modifying oil product.
Although the present invention discloses as above with several preferred embodiment; so itself and be not used to limit the present invention; have in any art and usually know the knowledgeable; without departing from the spirit and scope of the present invention; when doing arbitrary change and retouching, therefore protection scope of the present invention is as the criterion when the scope defined depending on accompanying claims.
Claims (10)
1. a method for modifying oil product, comprising:
Using a ferriferous oxide as catalyzer, make an oil product and hydrogen carry out hydrogenation deoxidation reaction, wherein said ferriferous oxide is iron protoxide, ferrous oxide, ferric oxide, Z 250 or aforesaid combination;
Wherein this ferriferous oxide is with after acid dissolve raw material, mineral, Industrial Metal waste, and through the magnetite powder of alkali lye precipitation gained, and in this magnetite powder, Z 250 content is 60 to 95%, and the specific surface area of this magnetite powder is 15 to 40m
2/ g, the specific heat of this magnetite powder is 0.1 to 0.4cal/g DEG C.
2. the method for modifying oil product as claimed in claim 1, wherein this oil product comprises raw pledge cracking oil product, biodiesel, waste lubricating oil, waste edible oil, plastic cracking oil product, tire pyrolysis oil product or aforesaid combination.
3. the method for modifying oil product as claimed in claim 1, wherein the reaction of this hydrogenation deoxidation carries out in CO 2 fluid.
4. the method for modifying oil product as claimed in claim 3, wherein this CO 2 fluid and this hydrogen ratio scope are 0.1 to 1.0.
5. the method for modifying oil product as claimed in claim 3, wherein this hydrogenation deoxidation temperature of reaction is not less than 240 DEG C.
6. the method for modifying oil product as claimed in claim 5, wherein this hydrogenation deoxidation temperature of reaction is between 240 to 320 DEG C.
7. the method for modifying oil product as claimed in claim 3, the pressure of wherein this hydrogenation deoxidation reaction is not less than 5atm.
8. the method for modifying oil product as claimed in claim 7, the pressure of wherein this hydrogenation deoxidation reaction carries out under 5 to 50atm.
9. the method for modifying oil product as claimed in claim 3, the unit time unit catalyst sample size of wherein this hydrogenation deoxidation reaction is not less than 5h
-1.
10. the method for modifying oil product as claimed in claim 9, the unit time unit catalyst sample size of wherein this hydrogenation deoxidation reaction is 5 to 20h
-1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010541411.3A CN102465004B (en) | 2010-11-10 | 2010-11-10 | Method of oil upgrading |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010541411.3A CN102465004B (en) | 2010-11-10 | 2010-11-10 | Method of oil upgrading |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102465004A CN102465004A (en) | 2012-05-23 |
| CN102465004B true CN102465004B (en) | 2014-12-24 |
Family
ID=46069134
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010541411.3A Active CN102465004B (en) | 2010-11-10 | 2010-11-10 | Method of oil upgrading |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102465004B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109797002A (en) * | 2019-01-28 | 2019-05-24 | 武汉纺织大学 | A kind of steel scrap ROLLING OIL recycling processing method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2960459A (en) * | 1958-12-08 | 1960-11-15 | Sun Oil Co | Hydrocracking of hydrocarbon oils with spent cracking catalyst containing ferric oxide |
| CN1255407A (en) * | 1998-11-30 | 2000-06-07 | 碳氢技术股份有限公司 | Dispersion anion-modified and phosphorus supporting ferric oxide catalyst |
| CN101003014A (en) * | 2006-12-18 | 2007-07-25 | 北京三聚环保新材料有限公司 | High activity deoxidant, and its preparing method |
| CN101724428A (en) * | 2008-10-17 | 2010-06-09 | 财团法人工业技术研究院 | Method for modifying oil product and method for preparing magnetite powder |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8026401B2 (en) * | 2007-12-20 | 2011-09-27 | Syntroleum Corporation | Hydrodeoxygenation process |
-
2010
- 2010-11-10 CN CN201010541411.3A patent/CN102465004B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2960459A (en) * | 1958-12-08 | 1960-11-15 | Sun Oil Co | Hydrocracking of hydrocarbon oils with spent cracking catalyst containing ferric oxide |
| CN1255407A (en) * | 1998-11-30 | 2000-06-07 | 碳氢技术股份有限公司 | Dispersion anion-modified and phosphorus supporting ferric oxide catalyst |
| CN101003014A (en) * | 2006-12-18 | 2007-07-25 | 北京三聚环保新材料有限公司 | High activity deoxidant, and its preparing method |
| CN101724428A (en) * | 2008-10-17 | 2010-06-09 | 财团法人工业技术研究院 | Method for modifying oil product and method for preparing magnetite powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102465004A (en) | 2012-05-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Quah et al. | Magnetic biochar derived from waste palm kernel shell for biodiesel production via sulfonation | |
| Resasco et al. | Distributed processes for biomass conversion could aid UN Sustainable Development Goals | |
| Malins et al. | Bio-oil from thermo-chemical hydro-liquefaction of wet sewage sludge | |
| Rahimzadeh et al. | Potential of acid-activated bentonite and SO3H-functionalized MWCNTs for biodiesel production from residual olive oil under biorefinery scheme | |
| Li et al. | Effect of bioleaching on hydrogen-rich gas production by steam gasification of sewage sludge | |
| CN107324331A (en) | A kind of method that utilization agricultural shell discarded object prepares activated carbon from activated sludge | |
| CN102965203A (en) | Method for preparing biodiesel through catalysis of natural biomass solid acid catalyst | |
| Yao et al. | The production of hydrogen through steam reforming of bio-oil model compounds recovering waste heat from blast furnace slag: Thermodynamic study | |
| Shen et al. | Pyrolysis of cellulose with cathode materials recovered from spent binary and ternary lithium-ion batteries | |
| Huo et al. | Efficient hydrothermal conversion of cellulose into methane over porous Ni catalyst | |
| Ma et al. | Valorization of wheat straw: Rapid reduction of CuO into Cu and production of organic acids under mild hydrothermal conditions | |
| Tian et al. | Revealing the roles of carbonized humic acid in biohydrogen production | |
| CN102465004B (en) | Method of oil upgrading | |
| Yang et al. | Electrochemical catalytic coal gasification: A novel method | |
| Wang et al. | A novel method for producing hydrogen from water with Fe enhanced by HS− under mild hydrothermal conditions | |
| CN108046234B (en) | Improve the charcoal method for fine finishing of anaerobic organism reaction efficiency | |
| TWI414592B (en) | Method for refining oil | |
| CN102503801A (en) | Method for producing formic acid from glycerol by hydrothermal oxidation | |
| CN105038853A (en) | Method for utilizing FCC slurry and coal to co-refine oil | |
| CN104694166B (en) | A kind of classification pyrolysis gasification system and its application, the processing method of tanning waste | |
| CN103484141B (en) | Method for preparing bio-oil through online deoxygenation and hydrogenation of biomass thermal cracking liquification | |
| CN109294612A (en) | A method of add hydrogen to prepare fuel oil altogether using sawdust and mink cell focus | |
| Zhang et al. | Synergistic magnetic Cu-Fe catalysts on N-doped biochar for efficient alkali lignin catalytic depolymerization into monophenols | |
| CN102093913B (en) | Method for coprocessing glycerol and heavy oil in hydrothermal mode to simultaneously obtain lactic acid and light oil | |
| CN103484506B (en) | A kind of method utilizing excess sludge anaerobic fermentation to produce butyric acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |