CN1912057A - Method of preparing biodiesel oil using nonedible woody oil and waste edible oil through esterification interesterification - Google Patents
Method of preparing biodiesel oil using nonedible woody oil and waste edible oil through esterification interesterification Download PDFInfo
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- CN1912057A CN1912057A CNA2006100200215A CN200610020021A CN1912057A CN 1912057 A CN1912057 A CN 1912057A CN A2006100200215 A CNA2006100200215 A CN A2006100200215A CN 200610020021 A CN200610020021 A CN 200610020021A CN 1912057 A CN1912057 A CN 1912057A
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- 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
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- 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
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Abstract
The invention is a method of using inedible woody oil and waste edible oil to prepare biological diesel oil by esterification and ester exchange, characterized by comprising the process steps of: (1) mixing various purified and dehydrated inedible wood oil and waste edible oil in mass ratio; (2) return flow esterification; (3) filtering and extracting acidic cation exchange resin catalyst; (4) return flow resin exchange reaction at normal pressure and 55-75DEG C; (5) filtering and extracting fatty acid methyl ester, namely biological diesel oil. And it has active effects: (1) able to development and utilization of inedible oil, enlarge range and supply of raw materials of biological diesel oil and reduce costs of raw materials of biological diesel oil; (2) no waste liquor and waste residue production in the course of refining raw materials; (3) catalyst is easy to extract and recyclable; and (4) yield of products up to above 98%.
Description
Technical field
The present invention relates to non-edible woody grease of a kind of usefulness and discarded edible oil method through the esterification preparing biodiesel by ester exchange.
Background technology
Along with the exhaustion day by day of global petroleum resources and the raising of human environmental consciousness, existing many countries are at research, development and application renewable and clean energy resource, to replace oil fuel.Biofuel is by fatty acid methyl ester or the ethyl ester of animal-plant oil through the generation of esterification transesterification reaction, belongs to renewable clean fuel.Its combustionproperty, pollutant emission, cetane value etc. are better than petroleum diesel.Research, the development and application of biofuel are more and more paid close attention to.
At present, the raw material for preparing biofuel both at home and abroad mainly is edible oil such as rapeseed oil, soybean oil, Oleum Gossypii semen, Rice pollard oil, plam oil, peanut oil, Semen Maydis oil, lard and little Oleum Verniciae fordii, Oleum Verniciae fordii, Viscotrol C, discarded edible oil.China belongs to edible oil shortage country, and at present self-produced food plant and animal grease can only satisfy about 60%, about 40% of domestic food oils demand needs import.The annual production of China's Viscotrol C, Oleum Verniciae fordii, little Oleum Verniciae fordii is low, price is high, and the annual production of discarded edible oil is lower, collection is difficult.Therefore, at present China is the raw material production biofuel with these kind greases, certainly exists that there is lack of raw materials, cost is crossed problems such as height, is difficult to realize commercial operations, large-scale production operation.Camphor tree seed, Chinese tallow tree seed on the south China the Yellow River are very abundant, and its oleaginousness reaches more than 40%, also do not obtain rational exploitation and utilization so far.Camphor tree seed oil, Chinese tallow tree Chinese catalpa oil are inedible oil fat, suitable preparation biofuel, belong to the desirable feedstock of preparation biofuel in China.Therefore, utilize camphor tree seed oil, Biodiesel Production from Chinese Tallow Kernel Oil significant in China.
The chemical process of preparation biofuel mainly is an ester-interchange method at present, as liquid soda acid homogeneous catalysis ester-interchange method (ZL98811443.7, CN1382762A, CN1412278A), solid acid alkali catalytic agent catalytic transesterification method (CN1580190A, CN1718679A), ionic-liquid catalyst catalytic transesterification method (CN1696248A, CN1737086A).These methods have the following disadvantages: the acid value of raw oil material requires high (≤1), and raw oil material process refining earlier is to remove free fatty acids wherein; Catalyzer is difficult for reclaiming and regeneration, and reaction product needs through washing, drying; Waste liquid, waste residue can be produced in the production process, the pollution treatment measure need be taked, the production cost height.
The biological method of preparation biofuel has biological enzyme ester-interchange method (ZL03119600.4) at present, and speed of response is slow, and transformation efficiency is on the low side, methyl alcohol easily makes biological enzyme poison and inactivation, and biological enzyme price height also can't be implemented suitability for industrialized production at present.
To enrich inexpensive inedible oil fat is raw material; employing can fully transform glyceride in the glyceride stock and free fatty acids, transformation efficiency height, reaction conditions gentleness, environment amenable biodiesel oil preparing process, is the key that realizes that biodiesel commercialization running, large-scale production are managed.
Summary of the invention
The purpose of this invention is to provide non-edible woody grease of a kind of usefulness and discarded edible oil method through the esterification preparing biodiesel by ester exchange, it is to be raw material to enrich inexpensive non-edible woody grease and discarded edible oil, with acidic cation-exchange resin, foamed porous composite metallic oxide is catalyzer, through the method for esterification preparing biodiesel by ester exchange.
The present invention is achieved like this, and its production craft step is as follows: (1) will press C through the various non-edible woody grease and the discarded edible oil of removal of impurities dehydration
8～12: 0: C
14～24: 0: C
18～24: 1～3=30～40%: 6～10%: 50～64% lipid acid mass ratio allotment;
(2) be that the ratio of 1: 0.12%～.0.34% formulated oil saponification value adds reaction kettle of the esterification with methyl alcohol and formulated oil in the oleyl alcohol mass ratio, the acid cation exchange resin catalyst that adds formulated oil quality 2～6%, under normal pressure and 55～95 ℃ of temperature, backflow esterification 1～3h;
(3) after esterification finished, the product that (1) is obtained filtered to isolate acid cation exchange resin catalyst, and the centrifugation of worry liquid is removed wherein water, obtained esterification formulated oil-carbinol mixture;
(4) esterification formulated oil-carbinol mixture is added transesterification reactor, add the foamed porous composite metallic oxide catalyzer of formulated oil quality 1.5～3.5%, under normal pressure and 55～75 ℃ of temperature, backflow transesterification reaction 2～4h;
(5) after transesterification reaction finishes, the product that (4) are obtained filters to isolate foamed porous composite metallic oxide catalyzer, centrifugation is considered liquid and is obtained methyl alcohol-water-glycerol mixture and methyl alcohol-fatty acid methyl ester admixture, distillating carbinol-water-glycerol mixture distillates the first alcohol and water, obtain glycerine, distillating carbinol-fatty acid methyl ester admixture distillates methyl alcohol, and obtaining fatty acid methyl ester is biofuel.
Non-edible woody grease of the present invention is meant camphor tree seed oil, Chinese tallow tree Chinese catalpa oil.
Acid cation exchange resin catalyst of the present invention is mainly D001 type large hole strong acid styrene system cation exchange resin, D61 type large hole strong acid styrene system cation exchange resin.
Foamed porous composite metallic oxide catalyzer of the present invention is mainly foamed multi-hole type Al-Ca-K complex metal oxides, foamed multi-hole type Mg-Ca-K complex metal oxides, foamed multi-hole type Mg-Al-K complex metal oxides, foamed multi-hole type Al-Ca-Na complex metal oxides, foamed multi-hole type Mg-Ca-Na complex metal oxides.
Foamed porous composite metallic oxide catalyzer of the present invention, the granulation of employing wet-mixed, freezing and sublimation dehydrate, calcining process prepares.
Esterification of the present invention finishes the acid cation exchange resin catalyst that after-filtration goes out, and recycles by confession behind the regenerated from washing.
Transesterification reaction of the present invention finishes the foamed porous composite metallic oxide catalyzer that after-filtration goes out, by wet-mixed granulation, freezing and sublimation dehydrate, calcining process regeneration back is for recycling
Positively effect of the present invention is that (1) is the raw material production biofuel with non-edible woody grease and discarded edible oil, can promote the development and use of these inedible oil fat, enlarges the raw material range and the supply of biofuel, reduces the raw materials cost of biofuel; (2) can fully transform glyceride and free fatty acids in the glyceride stock, reduce acid value requirement, avoid the refinery practice of glyceride stock, no waste liquid, waste residue generation glyceride stock; (3) be catalyzer with acidic cation-exchange resin, foamed porous composite metallic oxide, catalyzer is easy to separate and reproducible utilization, has avoided washing, the drying process of reaction product; There are not waste liquid, waste residue generation in the whole process of production, environmentally friendly; (4) yield of preparation biofuel can reach more than 98%, and the products production cost is lower than the production cost of petroleum diesel, and the product main performance index reaches China 0
#Petroleum diesel standard (GB/T19147-2003), German biofuel standard (DIN E 51606) and U.S.'s biofuel standard (ASTM PS121-99) can be used as fuel oils such as automobile, agricultural machine and boiler.
Biofuel product performance index and China 0 that the present invention produces
#Petroleum diesel standard, German biofuel standard and U.S.'s biofuel standard are compared as follows:
| Test item | Unit | Detected value of the present invention | China 0 #The petroleum diesel standard | Germany's biofuel standard | U.S.'s biofuel standard |
| Methyl esters content sulfur content methanol content free glycerol content acidity moisture ash content mechanical admixture density (20 ℃) kinematic viscosity (20 ℃) | ％(m/m) ％(m/m) ％(m/m) ％(m/m) mgKOH/100ml ％(v/v) ％(m/m) ％(m/m) g/ml mm2/s | 98.2 0.01 0.13 0.01 0.15 0.02% 0.008 does not have 0.876 4.62 | The no 0.820-0.845 3.0-8.0 in≤0.035 vestige≤0.01 | ≥97 ≤0.01 ≤0.3 ≤0.02 ≤0.5 0.05％ ≤0.01 ≤0.02 0.875-0.900 (15℃) 3.5-5.0(40 ℃) | ≤0.05 ≤0.5 ≤0.02 ≤0.5 0.05％ ≤0.01 ≤0.02 0.860-0.900 (15℃) 1.9-6.0(40 ℃) |
| Cetane number condensation point cold filter plugging point flash-point (remaining silent) boiling range: 90% distillates boiling range: 95% distillates copper corrosion | CN ℃ ℃ ℃ of ℃ ℃ level (50 ℃, 3h) | 49 -1 0 143 289 356 1a | ≥45 ≤0 ≤4 ≥55 ≤355 ≤365 ≤1 | ≥49 ≤0 ≥100 ≤1 | ≥47 ≤0 ≥130 ≤360 ≤360 ≤1 |
Embodiment
The present invention will be further described by following examples.
Embodiment one
(1) learnt from else's experience 1 kilogram of the camphor tree seed oil of removal of impurities dehydration is pressed C
8～12: 0: C
14～24: 0: C
18～24: 1～3=30%: 6%: 64% lipid acid mass ratio makes it mix with and discarded edible oil oily through the Chinese tallow tree Chinese catalpa of removal of impurities dehydration;
(2) be 1 in the oleyl alcohol mass ratio: the ratio of .0.34% formulated oil saponification value adds reaction kettle of the esterification with methyl alcohol and formulated oil, the D001 type large hole strong acid styrene system cation exchange resin catalyzer that adds formulated oil quality 6%, under normal pressure and 55 ℃ of temperature, backflow esterification 3h;
(3) after esterification finished, the product that (1) is obtained filtered to isolate D001 type large hole strong acid styrene system cation exchange resin catalyzer, and the centrifugation of worry liquid is removed wherein water, obtained esterification formulated oil-carbinol mixture;
(4) esterification formulated oil-carbinol mixture is added transesterification reactor, add the foamed multi-hole type Al-Ca-K O composite metallic oxide catalyst of formulated oil quality 3.5%, under normal pressure and 55 ℃ of temperature, backflow transesterification reaction 4h;
(5) after transesterification reaction finishes, the product that (4) are obtained filters to isolate foamed multi-hole type Al-Ca-K O composite metallic oxide catalyst, centrifugation is considered liquid and is obtained methyl alcohol-water-glycerol mixture and methyl alcohol-fatty acid methyl ester admixture, distillating carbinol-water-glycerol mixture distillates the first alcohol and water, obtain 0.31 kilogram of purity 99% glycerine, yield is 9.3%, distillating carbinol-fatty acid methyl ester admixture distillates methyl alcohol, obtaining purity 98.21% fatty acid methyl ester is 3.27 kilograms of biofuel, and yield is 98.2%.
Embodiment two
(1) learnt from else's experience 1 kilogram of the camphor tree seed oil of removal of impurities dehydration is pressed C
8～12: 0: C
14～24: 0: C
18～24: 1～3=35%: 8%: 57% lipid acid mass ratio makes it mix with and discarded edible oil oily through the Chinese tallow tree Chinese catalpa of removal of impurities dehydration;
(2) be 1 in the oleyl alcohol mass ratio: the ratio of .0.24% formulated oil saponification value adds reaction kettle of the esterification with methyl alcohol and formulated oil, the D61 type large hole strong acid styrene system cation exchange resin catalyzer that adds formulated oil quality 4%, under normal pressure and 75 ℃ of temperature, backflow esterification 2h;
(3) after esterification finished, the product that (1) is obtained filtered to isolate D61 type large hole strong acid styrene system cation exchange resin catalyzer, and the centrifugation of worry liquid is removed wherein water, obtained esterification formulated oil-carbinol mixture;
(4) esterification formulated oil-carbinol mixture is added transesterification reactor, add the foamed multi-hole type Mg-Al-K O composite metallic oxide catalyst of formulated oil quality 2.5%, under normal pressure and 65 ℃ of temperature, backflow transesterification reaction 3h;
(5) after transesterification reaction finishes, the product that (4) are obtained filters to isolate foamed multi-hole type Mg-Al-K O composite metallic oxide catalyst, centrifugation is considered liquid and is obtained methyl alcohol-water-glycerol mixture and methyl alcohol-fatty acid methyl ester admixture, distillating carbinol-water-glycerol mixture distillates the first alcohol and water, obtain 0.27 kilogram of purity 99.3% glycerine, yield is 9.4%, distillating carbinol-fatty acid methyl ester admixture distillates methyl alcohol, obtaining purity 98.27% fatty acid methyl ester is 2.82 kilograms of biofuel, and yield is 98.6%.
Embodiment three
(1) learnt from else's experience 1 kilogram of the camphor tree seed oil of removal of impurities dehydration is pressed C
8～12: 0: C
14～24: 0: C
18～24: 1～3=40%: 10%: 50% lipid acid mass ratio makes it mix with and discarded edible oil oily through the Chinese tallow tree Chinese catalpa of removal of impurities dehydration;
(2) be 1 in the oleyl alcohol mass ratio: the ratio of .0.12% formulated oil saponification value adds reaction kettle of the esterification with methyl alcohol and formulated oil, the D001 type large hole strong acid styrene system cation exchange resin catalyzer that adds formulated oil quality 2%, under normal pressure and 95 ℃ of temperature, backflow esterification 1h;
(3) after esterification finished, the product that (1) is obtained filtered to isolate D001 type large hole strong acid styrene system cation exchange resin catalyzer, and the centrifugation of worry liquid is removed wherein water, obtained esterification formulated oil-carbinol mixture;
(4) esterification formulated oil-carbinol mixture is added transesterification reactor, add the foamed multi-hole type Mg-Ca-K O composite metallic oxide catalyst of formulated oil quality 1.5%, under normal pressure and 75 ℃ of temperature, backflow transesterification reaction 3h;
(5) after transesterification reaction finishes, the product that (4) are obtained filters to isolate foamed multi-hole type Mg-Ca-K O composite metallic oxide catalyst, centrifugation is considered liquid and is obtained methyl alcohol-water-glycerol mixture and methyl alcohol-fatty acid methyl ester admixture, distillating carbinol-water-glycerol mixture distillates the first alcohol and water, obtain 0.23 kilogram of purity 99.2% glycerine, yield is 9.2%, distillating carbinol-fatty acid methyl ester admixture distillates methyl alcohol, obtaining purity 98.25% fatty acid methyl ester is 2.46 kilograms of biofuel, and yield is 98.4%.
Embodiment four
(1) learnt from else's experience 1 kilogram of the camphor tree seed oil of removal of impurities dehydration is pressed C
8～12: 0: C
14～24: 0: C
18～24: 1～3=30%: 6%: 64% lipid acid mass ratio makes it mix with and discarded edible oil oily through the Chinese tallow tree Chinese catalpa of removal of impurities dehydration;
(2) be 1 in the oleyl alcohol mass ratio: the ratio of .0.18% formulated oil saponification value adds reaction kettle of the esterification with methyl alcohol and formulated oil, the D61 type large hole strong acid styrene system cation exchange resin catalyzer that adds formulated oil quality 5%, under normal pressure and 65 ℃ of temperature, backflow esterification 2.5h;
(3) after esterification finished, the product that (1) is obtained filtered to isolate D61 type large hole strong acid styrene system cation exchange resin catalyzer, and the centrifugation of worry liquid is removed wherein water, obtained esterification formulated oil-carbinol mixture;
(4) esterification formulated oil-carbinol mixture is added transesterification reactor, add the foamed multi-hole type Al-Ca-Na O composite metallic oxide catalyst of formulated oil quality 3%, under normal pressure and 60 ℃ of temperature, backflow transesterification reaction 3.5h;
(5) after transesterification reaction finishes, the product that (4) are obtained filters to isolate foamed multi-hole type Al-Ca-K O composite metallic oxide catalyst, centrifugation is considered liquid and is obtained methyl alcohol-water-glycerol mixture and methyl alcohol-fatty acid methyl ester admixture, distillating carbinol-water-glycerol mixture distillates the first alcohol and water, obtain 0.30 kilogram of purity 99.2% glycerine, yield is 9.0%, distillating carbinol-fatty acid methyl ester admixture distillates methyl alcohol, obtaining purity 98.23% fatty acid methyl ester is 3.26 kilograms of biofuel, and yield is 98.0%.
Embodiment five
(1) learnt from else's experience 1 kilogram of the camphor tree seed oil of removal of impurities dehydration is pressed C
8～12: 0: C
14～24: 0: C
18～24: 1～3=35%: 8%: 57% lipid acid mass ratio makes it mix with and discarded edible oil oily through the Chinese tallow tree Chinese catalpa of removal of impurities dehydration;
(2) be 1 in the oleyl alcohol mass ratio: the ratio of .0.3% formulated oil saponification value adds reaction kettle of the esterification with methyl alcohol and formulated oil, the D001 type large hole strong acid styrene system cation exchange resin catalyzer that adds formulated oil quality 3%, under normal pressure and 85 ℃ of temperature, backflow esterification 1.5h;
(3) after esterification finished, the product that (1) is obtained filtered to isolate D001 type large hole strong acid styrene system cation exchange resin catalyzer, and the centrifugation of worry liquid is removed wherein water, obtained esterification formulated oil-carbinol mixture;
(4) esterification formulated oil-carbinol mixture is added transesterification reactor, add the foamed multi-hole type Mg-Ca-Na O composite metallic oxide catalyst of formulated oil quality 2%, under normal pressure and 70 ℃ of temperature, backflow transesterification reaction 2.5h;
(5) after transesterification reaction finishes, the product that (4) are obtained filters to isolate foamed multi-hole type Mg-Ca-Na O composite metallic oxide catalyst, centrifugation is considered liquid and is obtained methyl alcohol-water-glycerol mixture and methyl alcohol-fatty acid methyl ester admixture, distillating carbinol-water-glycerol mixture distillates the first alcohol and water, obtain 0.26 kilogram of purity 99.4% glycerine, yield is 9.1%, distillating carbinol-fatty acid methyl ester admixture distillates methyl alcohol, obtaining purity 98.28% fatty acid methyl ester is 2.81 kilograms of biofuel, and yield is 98.3%.
Claims (4)
1, non-edible woody grease of a kind of usefulness and discarded edible oil is characterized in that through the method for esterification preparing biodiesel by ester exchange its production craft step is as follows:
(1) will press C through the various non-edible woody grease and the discarded edible oil of removal of impurities dehydration
8～12: 0: C
14～24: 0: C
18～24: 1～3=30～40%: 6～10%: 50～64% lipid acid mass ratio allotment;
(2) be that the ratio of 1: 0.12%～.0.34% formulated oil saponification value adds reaction kettle of the esterification with methyl alcohol and formulated oil in the oleyl alcohol mass ratio, the acid cation exchange resin catalyst that adds formulated oil quality 2～6%, under normal pressure and 55～95 ℃ of temperature, backflow esterification 1～3h;
(3) after esterification finished, the product that step 1 is obtained filtered to isolate acid cation exchange resin catalyst, removed wherein water with considering the liquid centrifugation, obtained esterification formulated oil-carbinol mixture;
(4) esterification formulated oil-carbinol mixture is added transesterification reactor, add the foamed porous composite metallic oxide catalyzer of formulated oil quality 1.5～3.5%, under normal pressure and 55～75 ℃ of temperature, backflow transesterification reaction 2～4h;
(5) after transesterification reaction finishes, the product that step 4 is obtained filters to isolate foamed porous composite metallic oxide catalyzer, centrifugation is considered liquid and is obtained methanol-water-glycerol mixture and methyl alcohol-fatty acid methyl ester admixture, distillating carbinol-water-glycerol mixture distillates the first alcohol and water, obtain glycerine, distillating carbinol-fatty acid methyl ester admixture distillates methyl alcohol, and obtaining fatty acid methyl ester is biofuel.
2, non-edible woody grease of usefulness according to claim 1 and discarded edible oil is characterized in that through the method for esterification preparing biodiesel by ester exchange described non-edible woody grease is meant camphor tree seed oil, Chinese tallow tree Chinese catalpa oil.
3, non-edible woody grease of usefulness according to claim 1 and discarded edible oil is characterized in that through the method for esterification preparing biodiesel by ester exchange described acid cation exchange resin catalyst is mainly D001 type large hole strong acid styrene system cation exchange resin, D61 type large hole strong acid styrene system cation exchange resin.
4, non-edible woody grease of usefulness according to claim 1 and discarded edible oil is characterized in that through the method for esterification preparing biodiesel by ester exchange described foamed porous composite metallic oxide catalyzer is mainly foamed multi-hole type Al-Ca-K complex metal oxides, foamed multi-hole type Mg-Ca-K complex metal oxides, foamed multi-hole type Mg-Al-K complex metal oxides, foamed multi-hole type Al-Ca-Na complex metal oxides, foamed multi-hole type Mg-Ca-Na complex metal oxides.
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|---|---|---|---|
| CNA2006100200215A CN1912057A (en) | 2006-08-16 | 2006-08-16 | Method of preparing biodiesel oil using nonedible woody oil and waste edible oil through esterification interesterification |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235314B (en) * | 2007-01-31 | 2011-08-10 | 中国石油化工股份有限公司 | Biological diesel oil and preparation method thereof |
| CN102500283A (en) * | 2011-11-21 | 2012-06-20 | 山东理工大学 | Membrane catalytic reactor |
| CN104120038A (en) * | 2013-04-25 | 2014-10-29 | 中国石油化工股份有限公司 | Method for reducing oil acid value |
| CN104164304A (en) * | 2014-08-22 | 2014-11-26 | 北京科技大学 | Novel method for preparing biodiesel under catalysis of modified resin |
| CN106008770A (en) * | 2016-07-28 | 2016-10-12 | 中国石油大学(华东) | Preparation method of environment-friendly expanded polystyrene material |
| CN110903912A (en) * | 2019-11-29 | 2020-03-24 | 华东理工大学 | Aryl grease and preparation method and application thereof |
-
2006
- 2006-08-16 CN CNA2006100200215A patent/CN1912057A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235314B (en) * | 2007-01-31 | 2011-08-10 | 中国石油化工股份有限公司 | Biological diesel oil and preparation method thereof |
| CN102500283A (en) * | 2011-11-21 | 2012-06-20 | 山东理工大学 | Membrane catalytic reactor |
| CN104120038A (en) * | 2013-04-25 | 2014-10-29 | 中国石油化工股份有限公司 | Method for reducing oil acid value |
| CN104164304A (en) * | 2014-08-22 | 2014-11-26 | 北京科技大学 | Novel method for preparing biodiesel under catalysis of modified resin |
| CN104164304B (en) * | 2014-08-22 | 2016-08-10 | 北京科技大学 | A kind of modified resin catalysis prepares the new method of biodiesel |
| CN106008770A (en) * | 2016-07-28 | 2016-10-12 | 中国石油大学(华东) | Preparation method of environment-friendly expanded polystyrene material |
| CN106008770B (en) * | 2016-07-28 | 2018-05-08 | 中国石油大学(华东) | A kind of preparation method of environment-friendly type expanded polystyrene material |
| CN110903912A (en) * | 2019-11-29 | 2020-03-24 | 华东理工大学 | Aryl grease and preparation method and application thereof |
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