CN1865401A - Method for preparing biological diesel oil using high acid value cottonseed oil - Google Patents
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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
- 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
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Abstract
The invention discloses a biological diesel preparing method from high-acid value cotton seed oil, which comprises the following steps: the first step: adopting concentrated sulfuric acid as catalyst under normal pressure and temperature; injecting certain quantity of carbinol; reacting most of glyceride and a little of aliphatic acid with carbinol; sedimenting and separating glycerin and water; the second step: adopting concentrated sulfuric acid as catalyst under normal pressure and temperature; injecting excessive carbinol; lengthening reacting time to react glyceride and aliphatic acid with carbinol. The invention can utilize cotton oil reasonably, which reduces the environmental pollution in the refinery course.
Description
(1) technical field under
The present invention relates to a kind of method of bio-diesel oil of producing, particularly a kind of method of preparing biological diesel oil using high acid value cottonseed oil.
(2) background technology
Biofuel is a fatty acid methyl ester, can be used as the replacement product of oil fuel-diesel oil, and is renewable and have biological degradability because of its resource, so be named biofuel.Biofuel is mainly with the foots oil of the inferior waste oil of vegetables oil (as Oleum Gossypii semen, rapeseed oil, soybean oil), animal oil (garbage grease of meat processing combine) or instant noodles, catering trade, swill oil, oil-fat plant and to produce the deodorization distillate that produces in the salad oil process be raw material, at a certain temperature, make catalyzer and methyl alcohol (or other lower alcohol) generation alcoholysis reaction (transesterify) with acid, alkali or enzyme, generate corresponding fatty acid methyl ester and glycerine, after separation of glycerin, obtain light phase product--fatty acid methyl ester is biofuel.This research is raw material with high acid value non-edible Oleum Gossypii semen inferior, adopts two step chemical reaction methods, makes catalyzer with the vitriol oil, with methyl alcohol generation alcoholysis transesterification reaction, produces the replacement product-biofuel of petrifaction diesel.This product can add in the 0# diesel oil by a certain percentage to alleviate the diesel oil supply situation of growing tension.
At present domestic and international production method of bio-diesel oil has multiple, mainly based on chemical method.According to production-scale size, production technique has intermittent type and continous way; Can be divided into normal temperature and pressure, medium temperature and medium pressure and High Temperature High Pressure again according to the different of temperature of reaction and pressure.With the normal temperature and pressure is example, its main production process is: with a certain amount of grease that conforms to quality requirements, with the solid KOH is catalyzer, in reactor, be heated to certain temperature with excessive anhydrous methanol, under mechanical agitation transesterification reaction taking place, generates corresponding fatty acid methyl ester and glycerine.Reaction product is after precipitate and separate, and light phase product removes excessive methanol, water elution except that residual soap, glycerine and solid alkali, drying and dehydrating, cooling through evaporation, promptly obtains purified, flaxen transparent liquid fatty acid methyl ester-biofuel at last after filtration.Heavy phase product-glycerine can obtain byproduct-raw glycerine (purity about 80%) behind pickling, washing, distillating carbinol.With the Oleum Gossypii semen is example, and the technological process of production of biofuel as shown in Figure 1.
The aqueous methanol that condensation is reclaimed is divided into anhydrous methanol and water after the rectifying tower fractionation.Anhydrous methanol can be led recirculation use in the production art of bringing back to life.Water can be used as the pickling water of raw glycerine.The vitriolate of tartar that generates behind catalyzer KOH after the use and the sulfuric acid reaction is good agricultural fertilizer.Whole process of production does not produce solid waste basically, and waste liquid, wastewater discharge also seldom belong to environment-friendly type production.Aforementioned production method reaction conditions gentleness (normal temperature, normal pressure), the reaction times is short, and side reaction is few, and conversion rate of products and purity are all higher.
Above-mentioned production technique exists many shortcoming and defect in actual production process, mainly show: the one, see technically, what oil to be the raw material production biofuel no matter with, no matter also production technique is intermittence or continuous, all acid value and the moisture content to stock oil has proposed strict demand, promptly require below the stock oil acid value 1.0mgKOH/g, moisture content is below 0.06%.Because too high moisture content and acid value can prolong the reaction times, the transformation efficiency of fatty acid methyl ester is low, and the soap of generation brings many difficulties for the separation and the washing of reaction product, causes the purity of byproduct glycerine and yield to reduce simultaneously.Therefore a large amount of high acid value grease such as Oleum Gossypii semens can't be utilized effectively at present.The 2nd, exist the problem of striving oil with the people with the low high-quality vegetable oil production biofuel of acid value.If a large amount of high-quality vegetables oil of low acid value is all changed into biofuel, certainly will have influence on people's lives, have influence on social stability.The 3rd, the methyl alcohol that chemical reaction is participated in requirement must be anhydrous methanol.This is feasible in theory, also can accomplish in the laboratory, but large-scale industrial production be difficult to accomplish because methyl alcohol is the extremely strong chemical substance of a kind of wetting ability.Study a kind of novel process, new technology, it has been very urgent that high acid value cottonseed oil inferior is converted into biofuel, and meaning is very great.
(3) summary of the invention
The present invention is in order to remedy the deficiencies in the prior art, and a kind of method that makes the preparing biological diesel oil using high acid value cottonseed oil that high acid value cottonseed oil is utilized effectively is provided.
The present invention is achieved through the following technical solutions:
A kind of method of preparing biological diesel oil using high acid value cottonseed oil, its special character is: the operational path that adopts two step chemical reaction biodiesel synthesis, be the first step at normal temperatures and pressures, with the vitriol oil is catalyzer, inject a certain amount of methyl alcohol, make the acid of most of glyceryl ester and little fat react the G ﹠ W that precipitate and separate produces with methyl alcohol, to reach the purpose of destroying chemical equilibrium, chemical reaction is moved towards the direction that helps generating fatty acid methyl ester; Second step still was catalyzer with the vitriol oil at normal temperatures and pressures still, injected excessive methyl alcohol, and the proper extension reaction times, and still unreacted glyceryl ester and lipid acid and methyl alcohol are reacted, thereby reached the purpose that improves methyl ester conversion rate and yield.
The method of preparing biological diesel oil using high acid value cottonseed oil of the present invention, adopt following steps:
(1) hair cotton oil is pumped in the hydration tank, be heated with stirring to 75～85 ℃, add the light buck of temperature a little more than 2～3 ℃ of water temperatures, oil foot is emitted in precipitation insulation 4～6 hours;
(2) open vacuum pump, make first reactor be in vacuum state, will wash cotton oil sucting reaction still, suck 12～15% heavy methyl alcohol of oil and oily heavy 1% the vitriol oil then;
(3) abolish vacuum, start agitator (rotating speed is 60rpm), keep 60～70 ℃ of temperature in the kettle, reacted 2～3 hours;
(4) stop to stir, precipitate about 2 hours, emit aqueous glycerol;
(5) open vacuum pump, make second reactor be in vacuum state, the material in first reactor is sucked second reactor, suck the 1% heavy vitriol oil (concentration is 98%) of 5～7% heavy methyl alcohol of oil and oil then;
(6) abolish vacuum, start agitator (rotating speed is 60rpm), keep 60～70 ℃ of temperature in the kettle, reacted 2～3 hours; The saponification value and the acid value of sampling chemical examination methyl esters;
(7) make the precipitate and separate device be in vacuum state, the material in second reactor is sucked the precipitate and separate device, precipitate 3～4 hours, emit aqueous glycerol;
(8) make in and washing tank be in vacuum state, during the material in the precipitate and separate device is sucked and washing tank, calculate according to the neutralization value of methyl esters and to add alkali number; Start agitator, during the KOH aqueous solution is sucked and washing tank, reacted about 30 minutes, precipitate 2 hours, emit salt solution;
(9) make water washing tank be in vacuum state, the material in the precipitate and separate device is sucked water washing tank, about 5～7% the temperature that sucks methyl esters weight is that the soft water about 70 ℃ carries out agitator treating, precipitates about 4 hours, emits waste water;
(10) make methyl ester distilled still be in vacuum state, methyl esters in the water washing tank is sucked in the methyl ester distilled still, heat and start agitator, keep 100～120 ℃ of temperature, vacuum tightness 0.8～0.9kpa, drying and dehydrating 2～3 hours, product is biofuel behind cold filtration.
Contain more free fatty acids (acid value of every 2mgKOH/g oil is about as much as 1% free fatty acids) in the chemical reaction mechanism high acid value cottonseed oil of the present invention with preparing biological diesel oil using high acid value cottonseed oil.Different chemical reactions is taking place in high acid value cottonseed oil in converting the process of fatty acid methyl ester to.What glyceryl ester took place is the alcoholysis transesterification reaction, and promptly the methanol molecules generation transesterification reaction of one mole sweet three ester molecules and three moles generates three moles fatty acid methyl ester molecule and one mole glycerol molecule, the reaction conditions gentleness, speed of response is fast, and side reaction is few, the methyl ester conversion rate height; And lipid acid takes place is esterification, and promptly the methanol molecules generation esterification building-up reactions of one mole fatty acid molecule and a mole generates one mole fatty acid methyl ester molecule and one mole water molecules, long reaction time, and the reaction conditions height, methyl ester conversion rate is low.In the esterification process of lipid acid, because the generation of water is so can not make catalyzer with alkaline matters such as KOH, because the existence of water, basic catalyst can with glyceryl ester and lipid acid generation saponification reaction, the soap that generates is a kind of emulsifying agent, add to the difficulties for the separation and the washing of reaction product, also can reduce the quality (viscosity of methyl esters increases, and fuel value descends) of methyl esters and glycerine.The laboratory little sample testing has also proved absolutely this point.Different according to glyceryl ester and lipid acid and methyl alcohol generation chemical reaction mechanism and speed of response, the present invention successfully adopts the operational path of two step chemical reaction biodiesel synthesis.
The present invention is converted into biofuel with the non-edible Oleum Gossypii semen of the high acid value of poor quality, adopts non-basic catalyst and two step chemical reaction methods to reach the purpose that improves methyl ester conversion rate and yield.Make catalyzer with the vitriol oil, do not have the generation of soap in the reaction process, emulsion can not take place in reaction product.The vitriol oil also has certain decolorization (greasy acid value is high more, quality is poor more, the often dark more and decolouring difficulty of color and luster).Can reduce to moisture level (methanol content 95% gets final product) by anhydrous level to the methyl alcohol that uses, so just can reduce the energy consumption of aqueous methanol in rectifying.Liquid flow is carried out under vacuum state, can reduce the run, drip, leak of liquid substances such as methyl alcohol.This technology also can obtain paying product-glycerine and vitriolate of tartar in addition.
The main economic and technical norms that the present invention reaches:
Feed stock conversion:＞97%; Product yield:＞98%;
Raw glycerine (content 80%) yield: 10-12%;
Vitriolate of tartar yield: 1-2%;
Consume: anhydrous methanol:＜160kg/T; The vitriol oil: 10kg/T;
Solid KOH: 10kg/T; Water vapor (pressure 4*10
5Pa): 350kg/T;
: 15KWh/T; Water coolant: 40m
3/ T (can be recycled).
China is the main in the world cotton big country that produces, national lint yield 6400KT in 2005, and cottonseed quantity is at 9000KT.Cottonseed contains grease 14-25%, can produce hair cotton oil 1350KT.。Squeezing or leach the hair cotton oil obtain the characteristics of himself are arranged from cottonseed: the one, acid value is higher, generally about 8mgKOH/g, have up to 20mgKOH/g; The 2nd, contain the toxic substance gossypol; The 3rd, contain higher pesticide residue.Therefore hair cotton oil must could eat after the alkali refining washing.The refining yield of Oleum Gossypii semen is lower, generally has only 80%, and produces a large amount of alkali waste waters in refining process, has not only wasted resource but also polluted environment.With the high acid value cottonseed oil is that raw material biodiesel synthesis meaning is very great: the one, rationally utilize the cotton oil resource, and help agriculture industrialization, also be an effective way of increasing peasant income; The 2nd, reduced the environmental pollution in the cotton oil refining process; The 3rd, prolonged the industrial chain of grease processing industry, can evade grease processing risk; The 4th, biofuel belongs to oil-fat chemical products, can share resources such as water, electricity, vapour, jar with oil-fat plant; The 5th, this novel energy industry of development biofuel can be cultivated new growth engines, meets the industry policy of country; The 6th, the fatty acid component of sweet three esters of cotton oil mainly is 16 carbon saturated acids and 18 carbon oil acid, constitutes very similarly to the carbochain of diesel oil, be difficult for that in engine oxidation, polymerization, fission etc. take place and pay reaction, this be other grease the advantage that can not compare.2005, national petrifaction diesel output was 8*10
8T, the about 2*10 of market has openings
8T.If 1,000,000 tons high acid value hair cotton oils can be converted into biofuel,, alleviate the under-supply contradiction of petrifaction diesel to a certain extent with the industrial market that forms 5,000,000,000 yuan.
(4) description of drawings
The present invention is further illustrated below in conjunction with accompanying drawing.
Fig. 1 is the technological process of production of prior art of the present invention;
Fig. 2 is the technological process of production of the present invention;
Fig. 3 pays the technological process of production that the product aqueous glycerol is purified for the present invention;
Fig. 4 pays the technological process of production that the product aqueous methanol is purified for the present invention.
(5) embodiment
Example 1, high acidity Oleum Gossypii semen are produced biofuel
1. main raw material and medicine: this real estate hair cotton oil, actual measurement acid value 38mg KOH/g; Anhydrous methanol, the vitriol oil, KOH are all the analytical pure level.
2. operation steps:
● get hair cotton oil 400g in beaker, be heated to 75 ℃, the hot water that adds 78 ℃ stirred 30 minutes, precipitated 4 hours, emitted oil foot with separating funnel.
● water intaking is washed cotton oil 200g in conical beaker, adds anhydrous methanol 30g, vitriol oil 2mil.On water-bath, keep 65～70 ℃ of temperature, do not stop to shake.Reacted 3 hours.
● mixture is poured in the separating funnel, left standstill 2 hours.Emit aqueous glycerol.Again light part is mutually changed in the conical beaker.
● in conical beaker, add anhydrous methanol 10g, vitriol oil 2mil.When reacting 2 once more.Repeat aforesaid operations.
● in light phase methyl esters, add the KOH saturated aqueous solution, make it to be neutral.Stirred 15 minutes, and precipitated 2 hours, emit salt solution.
● reusable heat water washing 1 to 2 time, emit waste water.
● methyl esters is put into baking oven, dries 2 hours down at 105～110 ℃.Take out cooling and with promptly obtaining the cottonseed biofuel behind the filter paper filtering.
● the technological process of production of the purification of aqueous glycerol, aqueous methanol is respectively as shown in Figure 3, Figure 4.
The product quality indicator that present technique reaches
| Sequence number | The quality index title | CN | GM |
| 01 | Density in the time of 15 ℃ (g/ml) | min.0.880 max.0.900 | min.0.875 max.0.900 |
| 02 | Kinetic viscosity (mm in the time of 40 ℃ 2/s) | min.3.5 max.5.3 | min.3.5 max.5.0 |
| 03 | Flash-point P.M (℃) | min.112 | min.110 |
| 04 | Cold filter clogging temperature (℃) | max.-5 | max.-20 |
| 05 | Sulphur content (w, %) | max.0.01 | max.0.01 |
| 06 | Carbon residue (w, %) | max.0.08 | max.0.05 |
| 07 | Cetane value | min.46 | min.49 |
| 08 | Ash oontent (w, %) | max.0.05 | max.0.03 |
| 09 | Moisture content (mg/kg) | max.350 | max.300 |
| 10 | Total impurities content (mg/kg) | max.50 | max.20 |
| 11 | Neutralization value (mg KOH/g) | max.0.6 | max.0.5 |
| 12 | Methanol content (w, %) | max.0.4 | max.0.3 |
| 13 | Mono-glycerides (w, %) | max.0.8 | max.0.8 |
| 14 | Two sweet esters (w, %) | max.0.5 | max.0.4 |
| 15 | Triglyceride (w, %) | max.0.5 | max.0.4 |
| 15 | Free glycerol (w, %) | max.0.02 | max.0.02 |
| 16 | Total glycerine (w, %) | max.0.3 | max.0.25 |
| 17 | Iodine number (g iodine/100g) | max.115 | max.115 |
| 18 | Phosphorus content (mg/kg) | max.30 | max.10 |
| 19 | Alkali metal content (mg/kg) | max.20 | max.5 |
Annotate: CN represents the biofuel quality standard that present technique reaches in the table; GM represents German DIN51606:1997 biofuel standard.
Example 2, middle acidity Oleum Gossypii semen are produced biofuel
1. main raw material and medicine: this real estate hair cotton oil, actual measurement acid value 5.6mg KOH/g; Anhydrous methanol, the vitriol oil, KOH are all the analytical pure level.
2. operation steps is as shown in Figure 2:
● hair cotton oil is pumped in the hydration tank for 500 kilograms, be heated with stirring to 85 ℃, add the light buck of temperature a little more than 87 ℃ of water temperatures, oil foot is emitted in precipitation insulation 6 hours;
● open vacuum pump, make first reactor be in vacuum state, will wash cotton oil sucting reaction still, suck 12～15% heavy methyl alcohol of oil and oily heavy 1% the vitriol oil then;
● abolish vacuum, start agitator (rotating speed is 60rpm), keep 60～70 ℃ of temperature in the kettle, reacted 3 hours;
● stop to stir, precipitate 2 hours, emit aqueous glycerol;
● open vacuum pump, make second reactor be in vacuum state, the material in first reactor is sucked second reactor, suck the 35 kilograms heavy methyl alcohol of oil and heavy 5 kilograms the vitriol oil (concentration is 98%) of oil then;
● abolish vacuum, start agitator (rotating speed is 60rpm), keep 60～70 ℃ of temperature in the kettle, reacted 3 hours; The saponification value and the acid value of sampling chemical examination methyl esters;
● make the precipitate and separate device be in vacuum state, the material in second reactor is sucked the precipitate and separate device, precipitate 4 hours, emit aqueous glycerol;
● in making and washing tank be in vacuum state, during the material in the precipitate and separate device is sucked and washing tank, calculate according to the neutralization value of methyl esters and to add alkali number; Start agitator, during the KOH aqueous solution is sucked and washing tank, reacted 30 minutes, precipitate 2 hours, emit salt solution;
● make water washing tank be in vacuum state, the material in the precipitate and separate device is sucked water washing tank, about 5～7% the temperature that sucks methyl esters weight is that the soft water about 70 ℃ carries out agitator treating, precipitates about 4 hours, emits waste water;
● make methyl ester distilled still be in vacuum state, methyl esters in the water washing tank is sucked in the methyl ester distilled still, heat and start agitator, keep 100～110 ℃ of temperature, vacuum tightness 0.8～0.9kpa, drying and dehydrating 3 hours, product are biofuel behind cold filtration.
Claims (2)
1. the method for a preparing biological diesel oil using high acid value cottonseed oil, it is characterized in that: the operational path that adopts two step chemical reaction biodiesel synthesis, be the first step at normal temperatures and pressures, with the vitriol oil is catalyzer, inject a certain amount of methyl alcohol, make the acid of most of glyceryl ester and little fat react the G ﹠ W that precipitate and separate produces with methyl alcohol, to reach the purpose of destroying chemical equilibrium, chemical reaction is moved towards the direction that helps generating fatty acid methyl ester; Second step still was catalyzer with the vitriol oil at normal temperatures and pressures still, injected excessive methyl alcohol, and the proper extension reaction times, and still unreacted glyceryl ester and lipid acid and methyl alcohol are reacted, thereby reached the purpose that improves methyl ester conversion rate and yield.
2. the method for preparing biological diesel oil using high acid value cottonseed oil according to claim 1 is characterized in that: adopt following steps:
(1) hair cotton oil is pumped in the hydration tank, be heated with stirring to 75～85 ℃, add the light buck of temperature a little more than 2～3 ℃ of water temperatures, oil foot is emitted in precipitation insulation 4～6 hours;
(2) open vacuum pump, make first reactor be in vacuum state, will wash cotton oil sucting reaction still, suck 12～15% heavy methyl alcohol of oil and oily heavy 1% the vitriol oil then;
(3) abolish vacuum, start agitator, keep 60～70 ℃ of temperature in the kettle, reacted 2～3 hours;
(4) stop to stir, precipitate about 2 hours, emit aqueous glycerol;
(5) open vacuum pump, make second reactor be in vacuum state, the material in first reactor is sucked second reactor, suck the 1% heavy vitriol oil (concentration is 98%) of 5～7% heavy methyl alcohol of oil and oil then;
(6) abolish vacuum, start agitator, keep 60～70 ℃ of temperature in the kettle, reacted 2～3 hours; The saponification value and the acid value of sampling chemical examination methyl esters;
(7) make the precipitate and separate device be in vacuum state, the material in second reactor is sucked the precipitate and separate device, precipitate 3～4 hours, emit aqueous glycerol;
(8) make in and washing tank be in vacuum state, during the material in the precipitate and separate device is sucked and washing tank, calculate according to the neutralization value of methyl esters and to add alkali number; Start agitator, during the KOH aqueous solution is sucked and washing tank, reacted about 30 minutes, precipitate 2 hours, emit salt solution;
(9) make water washing tank be in vacuum state, the material in the precipitate and separate device is sucked water washing tank, about 5～7% the temperature that sucks methyl esters weight is that the soft water about 70 ℃ carries out agitator treating, precipitates about 4 hours, emits waste water;
(10) make methyl ester distilled still be in vacuum state, methyl esters in the water washing tank is sucked in the methyl ester distilled still, heat and start agitator, keep 100～120 ℃ of temperature, vacuum tightness 0.8～0.9kpa, drying and dehydrating 2～3 hours, product is biofuel behind cold filtration.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006100449266A CN1865401A (en) | 2006-06-19 | 2006-06-19 | Method for preparing biological diesel oil using high acid value cottonseed oil |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006100449266A CN1865401A (en) | 2006-06-19 | 2006-06-19 | Method for preparing biological diesel oil using high acid value cottonseed oil |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508904A (en) * | 2009-03-24 | 2009-08-19 | 河南华泰粮油机械工程有限公司 | Method for producing biodiesel |
| CN101842471A (en) * | 2007-10-30 | 2010-09-22 | 拜尔技术服务有限责任公司 | The continuation method that is used for heterogenically catalyzed esterification of fatty acids |
| CN102206554A (en) * | 2010-03-31 | 2011-10-05 | 江苏恒顺达生物能源有限公司 | Method for preparing biodiesel |
| CN102071108B (en) * | 2009-11-24 | 2012-09-12 | 中国石油化工股份有限公司 | Preparation method of biodiesel |
| CN102041177B (en) * | 2009-10-18 | 2013-01-16 | 陕西春光生物能源开发有限公司 | Method for preparing biodiesel |
| CN111149796A (en) * | 2019-12-31 | 2020-05-15 | 苏州丰倍生物科技有限公司 | Pesticide solvent and preparation method and application thereof |
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2006
- 2006-06-19 CN CNA2006100449266A patent/CN1865401A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101842471A (en) * | 2007-10-30 | 2010-09-22 | 拜尔技术服务有限责任公司 | The continuation method that is used for heterogenically catalyzed esterification of fatty acids |
| CN101842471B (en) * | 2007-10-30 | 2014-12-10 | 罗门哈斯化学品有限责任公司 | Continuous method for the heterogenically catalyzed esterification of fatty acids |
| CN101508904A (en) * | 2009-03-24 | 2009-08-19 | 河南华泰粮油机械工程有限公司 | Method for producing biodiesel |
| CN102041177B (en) * | 2009-10-18 | 2013-01-16 | 陕西春光生物能源开发有限公司 | Method for preparing biodiesel |
| CN102071108B (en) * | 2009-11-24 | 2012-09-12 | 中国石油化工股份有限公司 | Preparation method of biodiesel |
| CN102206554A (en) * | 2010-03-31 | 2011-10-05 | 江苏恒顺达生物能源有限公司 | Method for preparing biodiesel |
| CN102206554B (en) * | 2010-03-31 | 2013-07-24 | 江苏恒顺达生物能源有限公司 | Method for preparing biodiesel |
| CN111149796A (en) * | 2019-12-31 | 2020-05-15 | 苏州丰倍生物科技有限公司 | Pesticide solvent and preparation method and application thereof |
| CN111149796B (en) * | 2019-12-31 | 2021-10-22 | 苏州丰倍生物科技有限公司 | Pesticide solvent and preparation method and application thereof |
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