阅读说明：本技术 简易生物柴油 (Simple biodiesel ) 是由 王军 于 2018-07-20 设计创作，主要内容包括：在自然条件下以生石灰作催化剂、干燥剂,将废油脂通过酯交换反应转化为简易生物柴油,并获得副产品甘油和熟石灰。(Under natural condition, quick lime is used as catalyst and drying agent to convert waste oil into simple biological diesel oil through ester exchange reaction and obtain by-products glycerin and hydrated lime.)

1. The simple biodiesel production by using the waste oil mainly comprises the following steps:

(1) the quantity ratio of the purified and dried waste oil to the methanol or ethanol substances is slightly less than or equal to 1: 3, the mass ratio of the waste oil to the methanol is slightly less than or equal to 9.27: 1-8.4: 1, the volume ratio is 7.92: 1-7.17: 1, the mass ratio of the waste oil to the ethanol is 6.45: 1-5.84: 1, the volume ratio is 5.5: 1-4.98: 1, and the slight excess of the alcohol is favorable for forward transesterification, the conversion rate of the oil is improved, and the quality of simple biodiesel is improved;

(2) quicklime is used as a catalyst and a drying agent to accelerate forward ester exchange and inhibit ester hydrolysis, the quicklime is reasonably added according to 5 percent of water content of industrial methanol and ethanol, and 156g of quicklime is preferably added to each liter of methanol or ethanol;

(3) the ester exchange reaction is 17.8 ℃ lower than the melting point of glycerin, and particularly under the natural condition of 7 ℃, the mixture is uniformly mixed twice a day, about half an hour each time, the liquid is homogeneous after weeks, the ester exchange is basically finished, and the simple biodiesel, the byproduct glycerin and the hydrated lime can be obtained by separation.

2. The process flow of the simple biodiesel is similar to that of the simple biodiesel produced by using vegetable oil except palm oil as a raw material; palm oil or animal oil as raw material can be mediated by diethyl ether, and the amount of diethyl ether is preferably 0.5-1 times of methanol or ethanol volume.

3. In order to prevent solidification and reduction of fluidity, the simple biodiesel is used in winter in the north, 10-30% of cheap methanol or ethanol is added into the finished simple biodiesel to prepare the simple methanol biodiesel or the simple ethanol biodiesel, so that universality and safety of the simple biodiesel are enhanced, and air pollution can be reduced.

The above-mentioned embodiments are only, and are not intended to limit the scope of the present invention, and all equivalent changes made by transesterification of any oil or fat below the boiling point of methanol or ethanol are within the technical scope of the present invention.

The invention relates to of a technology for reasonably developing and utilizing waste oil, in particular to a technology for converting the waste oil into power diesel oil through chemical reaction for scientific utilization.

Background art:

the waste oil refers to deteriorated oil, frying residual oil, vegetable oil extract oil, swill and swill floating oil, animal bone extract oil, oil collected by a smoke exhaust ventilator, sewage and fishing oil and the like. The current mature proposal of the biodiesel is as follows:

() transesterification method:

1. the method is inspired by animal fat hydrolysis, the waste oil is hydrolyzed under the action of lipase or simulated lipase and then undergoes esterification reaction with methanol or ethanol to generate higher fatty acid methyl ester or higher fatty acid ethyl ester, and the biodiesel is prepared by separation.

2. Ester exchange reaction with methanol or ethanol at normal temperature under the action of acid or alkali catalyst to produce higher fatty acid methyl ester or higher fatty acid ethyl ester, separating the mixture, and removing acid or alkali and water to obtain biodiesel oil. Alcoholysis under the condition also has reversibility, and is influenced by the space effect of higher fatty acid, so that the reaction rate and the yield are low, and the energy yield is relatively low. The product needs deacidification or dealkalization treatment, the process flow is complex, and the cost is high.

(II) catalytic cracking of waste oil and fat:

under the action of catalyst, the waste oil and fat is cracked at temp. to obtain C-contained oil₁₉The following various hydrocarbons or hydrocarbon derivatives can be used to obtain fuel oil and fuel gas with different boiling point ranges. The technical process of the scheme is simple, the cost is low, and the reaction rate and the yield are low.

The invention develops a new method, seeks the biodiesel with higher conversion rate, mild reaction conditions, simple process flow and relatively lower cost.

The invention content is as follows:

the technical problems solved by the invention are as follows:

the method for converting waste oil into biodiesel is provided, the waste oil is converted into power fuel oil of a diesel engine according to the chemical properties of ester, and the method has the characteristics of mild reaction conditions, simple process flow, high conversion rate and the like, and has high practical value.

The design idea of the invention is as follows:

the invention aims to solve the problems that fossil energy in China depends on imports and the shortage situation is serious day by day, develop a new method for obtaining motor vehicle fuel, relieve the shortage of energy and guide the correct flow direction of waste oil and fat.

The waste oil mainly comes from edible vegetable oil, rapeseed oil, soybean oil and palm oil are relatively common, and the chemical components of the waste oil are high-grade fatty glyceride, and have the chemical properties of ester.

The boiling point of the raw oil is not fixed but has a higher boiling point range, the boiling point of the small molecular components is above 100 ℃, the melting point of palm oil and animal oil is higher than 24 ℃, the melting point of peanut oil is lower than 10 ℃, and the melting points of other vegetable oils are about-10 ℃. Unsaturated after use of the oilThe melting point of the ingredients is reduced and increased, and the melting point of the waste oil and fat is estimated to be about 0 ℃ according to the common edible oil. The density of crude oil is 0.91-0.944, and the density of waste oil is 0.925 × 10³kgm^-3Insoluble in water and less soluble in lower alcohols; the melting point of glycerol is 17.8 deg.C, boiling point is 290.9 deg.C, and density is 1.264 × 10³kgm^-3(ii) a Methanol boiling point 64.7 deg.C, density 0.79X 10³kgm^-3Boiling point of ethanol is 78.5 ℃, density is 0.789 multiplied by 10³kgm^-3。

The transesterification reaction is a typical reversible reaction, and the product is separated from the reaction system in time or enters into an out-phase state to be beneficial to chemical equilibrium forward transesterification.

Or

The present invention is to put industrial mass production in late autumn, winter and early spring, the reaction temperature is lower than the boiling point of methanol or ethanol, preferably lower than the melting point of glycerin by 17.8 ℃ and higher than the grease solidifying point under natural environment conditions, so that the generated glycerin can be separated out from the reversible reaction equilibrium system in time and enter into heterogeneous phase, the equilibrium forward transesterification is promoted, the conversion rate of the reaction and the utilization rate of raw materials are improved, and the yield is high.

The ester exchange reaction is extremely slow, acid or alkali is needed to be used as a catalyst, acid or alkali is also a catalyst for ester hydrolysis, the ester hydrolysis reaction is much faster than the ester exchange reaction, an acid or alkali solution cannot be used as the catalyst for the ester exchange reaction, an acid catalyst is used as a catalyst for industrial selection of dry hydrogen chloride or phosphorus pentoxide, the hydrogen chloride is used as a catalyst without considering the separation problem, the phosphorus pentoxide is used as a catalyst and still forms a concentrated acid solution due to water absorption to generate phosphoric acid to promote hydrolysis, and after-production separation is also considered, so that a plurality of adverse factors are brought to production, such as high cost, safety in use, equipment safety, difficulty in separation and the like, are brought to hydrolysis reaction, sodium ethoxide is selected in the alkaline catalyst industry, sodium hydroxide is hydrolyzed vigorously to generate alcohol and sodium hydroxide, if water is not consumed completely or a concentrated alkali solution is formed due to strong water absorption of sodium hydroxide to cause ester to be saponified quickly, so that ester exchange reaction is not carried out positively, the sodium hydroxide is not easy to generate a saponification reaction, equipment and production safety latent, sodium hydroxide is added in low carbon alcohol and glycerin, the calcium hydroxide catalyst is used as a low-calcium hydroxide catalyst, calcium hydroxide catalyst is not easy to be added to generate a low-calcium hydroxide catalyst, calcium hydroxide catalyst is not easy to be used as a low-soluble, the hydrolysis reaction is not easy to be used as a low-calcium carbonate-calcium-absorption catalyst, and calcium-.

The main body of the waste oil and fat substance is similar to that of original vegetable oil and fat, the chemical substance, namely high-grade fatty glyceride, is mostly a mixed ester mixture, the relative molecular mass and the average relative molecular mass are difficult to determine, only the complex problem can be simplified, the problems of saving, environmental protection, cost, excessive nucleophilic reagent and the like are considered, the relative molecular mass of stearic acid triglyceride 890 and palmitic acid triglyceride 806 are adopted, the mass ratio of grease to methanol or ethanol is less than or equal to 1: 3, the mass ratio of grease to methanol is slightly less than or equal to 9.27: 1-8.4: 1, the volume ratio is 7.92: 1-7.17: 1, the mass ratio of grease to ethanol is slightly less than or equal to 6.45: 1-5.84: 1, the volume ratio of grease to ethanol is 5.5: 1-4.98: 1, and the slight excess of alcohol is beneficial to forward transesterification, the conversion rate of grease is improved, and the quality of simple biodiesel is improved. The excess of methanol or ethanol should be moderate, otherwise, the glycerin generated by dissolving is in the same phase, which is not beneficial to the forward proceeding of the reaction equilibrium.

The industrial batch production designs the capacity and the quantity of the stainless steel ester exchange reaction kettles according to the production scale, and proposes to manufacture the double-conical ester exchange reaction kettles with large upper parts and small lower parts, and the upper openings of the double-conical ester exchange reaction kettles are butted with raw material preparation equipment, waste oil purification and drying equipment and the like; the lower port is butted with a pressure reduction rough filtration device, a pressure reduction fine filtration device, a molecular filtration device and a simple biodiesel storage tank; according to the volume of the reaction kettle and the volume of the generated glycerin, the middle opening position is designed, and the middle opening position is butted with a decompression fine filtration device, a molecular filtration device and a simple biodiesel storage tank. The reaction kettle can move in a rolling mode to uniformly mix two liquid phases of reactants, and the liquid can move in a centrifugal mode after being completely homogeneous to fully precipitate solids and then be separated by a lower cone; automatically controlling the flow line production according to the program.

The palm oil and the animal oil are solid or semisolid at normal temperature and are difficult to dissolve in low-carbon alcohol, ester exchange reactants are multiphase, the reaction rate is slower, proper mediums are needed to be searched to enable the reactants to be carried out in a homogeneous phase, the oil is difficult to dissolve in the low-carbon alcohol and is easy to dissolve in ether, the low-carbon alcohol and the ether are mutually soluble, although the glycerol is mutually soluble with the low-carbon alcohol but is difficult to dissolve in the ether, the low-carbon alcohol is continuously reduced along with the reaction in the homogeneous phase, the glycerol can continuously separate from a reaction balance system and is free, the normal ester exchange is thoroughly out of phase, the boiling point of the ether is 34.6 ℃, the distillation can be easily carried out to separate from the simple biodiesel, the waste oil and other vegetable oils can also refer to the ether as the medium, and the production period is shortened.

The development prospect of the scheme is as follows:

the method mainly develops waste oil, can develop excess animal and vegetable oil, has wide raw material source of , mild production process conditions, simple process flow, high raw material utilization rate, higher conversion rate and yield, high product added value and adopts C as a component₁₉Or C₂₀Mainly palm oil, if the raw material is C₁₇Mainly, the oxygen-containing combustion of the burner has low oxygen consumption, and the combustion is necessarily sufficient; low corrosion of sulfur-free equipmentThe atmosphere is low in pollution, aromatic hydrocarbon is not contained, the carcinogenicity is low, the fluidity is good, and the service life of equipment with a lubricating effect is long; has good market prospect.

The technical scheme adopted by the invention is as follows:

the scheme for converting the waste oil into the biodiesel comprises the following steps:

, removing impurities from the crude waste oil, filtering to remove suspended solid, decolorizing with activated carbon, deodorizing, filtering to remove activated carbon and adsorbed substance, washing with water to remove water-soluble low-grade fatty aldehyde, ketone, acid, inorganic salt, etc. to avoid corrosion of equipment, separating with liquid separation method to obtain purified waste oil, evaporating or microwave drying at 100 deg.C to remove oil, and purifying the dried waste oil for simple biodiesel production.

And step two, mixing 7.5 times of volume of the waste oil and fat with methanol or 5.2 times of volume of the waste oil and fat with ethanol.

And step three, adding 156g of sealed container into each liter of methanol or ethanol of the fine powdered quicklime and uniformly mixing.

And step four, reacting for several hours in a natural environment at the temperature of 17.8 ℃ lower than the melting point of the glycerol, and separating to obtain liquid, namely the mixture of the biodiesel and the solid.

And step five, separating the solid mixture at the temperature of over 17.8 ℃ to obtain the byproducts of glycerin and hydrated lime.

The specific implementation mode is as follows:

and step , removing impurities from the crude waste oil, purifying and drying.

(1) Collecting enough crude waste oil, and removing suspended matters through rough filtration, reduced pressure fine filtration and molecular filtration;

(2) separating liquid, dewatering, and microwave drying to obtain purified and dried waste oil.

Step two, mixing the waste oil and fat with 7.5: 1 volume of methanol or 5.2: 1 volume of ethanol.

And step three, adding 156g of sealed container into each liter of methanol or ethanol of the fine powdered quicklime and uniformly mixing.

Step four, low-temperature ester exchange separation is carried out to obtain simple biodiesel and byproducts.

(1) Under the natural condition of 7 ℃, uniformly mixing twice a day, about half an hour each time, after weeks, the liquid is homogeneous, and the ester exchange is basically finished;

(2) centrifuging or standing to precipitate solid completely, and separating to obtain liquid and solid;

(3) the liquid is processed by rough filtration under reduced pressure, fine filtration under reduced pressure and molecular filtration to obtain the finished product of simple biodiesel.

And step five, separating the solid mixture to obtain byproducts of glycerin and hydrated lime.

(1) Melting glycerol at a temperature above 17.8 deg.C, and vacuum filtering the solid-liquid mixture to obtain crude glycerol and hydrated lime mixed with glycerol;

(2) the crude glycerol is subjected to pressure reduction fine filtration and molecular level filtration to obtain a byproduct glycerol;

(3) the hydrated lime mixed with the glycerin is washed by water or alcohol to obtain a glycerin solution and hydrated lime as byproducts.

The process flow of the simple biodiesel is similar to that of the simple biodiesel produced by using vegetable oil except palm oil as a raw material; palm oil or animal fat can be used as raw material and mediated by diethyl ether, and the dosage of diethyl ether is 0.5-1 times of methanol or ethanol volume.

In order to prevent solidification and reduction of fluidity, the simple biodiesel is used in winter in the north, 10-30% of cheap methanol or ethanol is added into the finished simple biodiesel to prepare the simple methanol biodiesel or the simple ethanol biodiesel, so that universality and safety of the simple biodiesel are enhanced, and air pollution can be reduced.

The invention has the advantages that the purified and dried waste oil and fat can be directly used for producing high-quality biodiesel, the whole process flow and the production process are in natural environment conditions, the raw materials are cheap and easy to obtain, the weak base is used for catalyzing and dehydrating, the energy consumption is low, the cost is low, and the added value of the product is high; the simple biodiesel has full combustion, high combustion value and large energy output ratio; low pollution and carcinogenicity; an authentic and simple biodiesel.

The above-mentioned embodiments are only, and not intended to limit the scope of the present invention, and all equivalent variations of the fats and oils that are reacted by transesterification under the condition of lower than the boiling point of methanol or ethanol are within the technical scope of the present invention.