TWI499667B - Method for producing biodiesel and the apparatus and the product thereof - Google Patents

Description

Method for preparing biodiesel, preparation device thereof and product thereof

The present invention relates to a method for preparing biodiesel and a preparation device thereof, in particular, after destroying biomass containing biomass (biomass), directly converting the crude mixture obtained by destroying the biomass as a reactant to carry out transesterification reaction. The biodiesel is formed.

The patent application of the Republic of China No. 097135046 discloses a method for producing biodiesel. The main steps are: after mixing vegetable oil, animal oil and methanol, the ultrafine wave oscillating machine is evenly refined, and the molecules are evenly mixed. The mixture of the mixer and the high-speed vortex is treated by transesterification to produce glycerin and methanol, and the mixed water and high-speed centrifuge are used to separate impurities, water, high-purity methanol, and finally heated to obtain the biomass. Diesel.

Patent Application No. 099115609 of the Republic of China discloses an integrated algae-based biodiesel and algae fermentation and reuse technology, wherein the microalgae formed by the photoreactor are placed in a device for extracting oil and fat for action of extracting oil and fat. After the oil extraction operation, the oil contained in the microalgae can be obtained, and the extracted oil can be converted into biodiesel.

In addition, after the algae body is dried first, and then the algae oil is extracted to prepare the subsequent biodiesel, it is also a common technology.

However, the above-mentioned technology only needs to extract the oil of biomass such as microalgae, or directly use vegetable oil or animal oil as raw materials for preparing raw diesel, but these techniques are not only cumbersome, but also easily cause loss of algae in the extraction process. And the cost is high and does not meet economic benefits.

For the sake of the job, the Applicant has carefully designed and researched the above-mentioned techniques, and has carefully designed and researched the method of preparing biodiesel, its preparation device and its Product, the following is a brief description of the case.

The object of the present invention is to provide a method for preparing biodiesel and a preparation device thereof, in particular, by transesterifying a crude mixture obtained by directly destroying biomass as a reactant to obtain biodiesel.

In order to achieve the above object, the present invention provides a method for preparing biodiesel, comprising: providing an algal body; destroying the algae to obtain a mixture of algae; and dissolving the algae mixture with a catalyst, an alcohol And co-solvent mixing to form the biodiesel.

In order to achieve the above object, the present invention provides a device for preparing biodiesel comprising: a first unit for mixing a broken algae mixture with a catalyst, an alcohol and a cosolvent to form the biodiesel; .

In order to achieve the above object, the present invention provides a method for preparing a biodiesel comprising: providing a mixture of a broken algae; and performing a transesterification reaction using the algae-breaking mixture as a reactant to form the biodiesel.

In order to achieve the above object, the present invention provides a mixture containing a raw diesel oil, comprising: a broken algae mixture obtained by destroying an algal body, wherein the algae-breaking mixture is a reactant of a transesterification reaction, The biodiesel is obtained by the transesterification reaction.

To achieve the above object, the present invention provides a method for producing biodiesel, comprising: providing a biomass, wherein the biomass comprises at least one fat; obtaining a crude mixture of the biomass; and using the crude mixture as A reactant is subjected to a transesterification reaction to form the biodiesel.

Here, the term "crude mixture" as used in the present invention refers to a mixture in which no components are removed from the cells after destruction of the cells in the biomass. Specifically, the "cracking algae mixture" is a mixture of any components, that is, a "crude mixture" of algae, after the algae of the algae is destroyed.

In addition, the term "destruction" as used in the present invention refers to an action of destroying the cell membrane and/or cell wall of a cell and releasing the cell contents to the cell membrane and/or outside the cell wall. The term "cosolvent" as used in the present invention means an organic solvent which is miscible with fats and oils.

For ease of explanation, the present invention can be further understood by the following examples.

The apparatus and method of the present invention will be fully understood from the following description of the embodiments and can be made by those skilled in the art. However, the implementation of this case is not limited to the following examples.

Please refer to the first figure, which is a flow chart of a method for preparing biodiesel according to the present invention. In the first figure, the source of the algal body may be supplied from a mixture of dry algae powder and a liquid (step 11), or may be taken from a wet algae body (step 12). Wherein, the liquid may be water or other suitable one, and whether the dry algal flour is mixed with the liquid or the wet algae body, the liquid content thereof may be adjusted according to requirements.

Then, the dry algal flour is mixed with the liquid, or the wet algae body is destroyed by the algae destruction step (step 13) to destroy the algae body, so that the cell contents containing the oil and fat in the algae body are released to The cell membrane and the outside of the cell wall form a mixture of broken algae (step 14). The algae-breaking mixture is then mixed with a catalyst, an alcohol, and a co-solvent (step 15), followed by a transesterification reaction (step 16). That is, the algae-breaking mixture is directly used as a reactant of the transesterification reaction. Thereafter, the mixture containing the biodiesel is formed by the transesterification reaction of the transesterification reaction (step 17). In some cases, the algae-inducing mixture may be first adjusted to the amount of liquid contained therein, and then the transesterification reaction is carried out to optimize the reaction.

In some embodiments, the dry algal flour may be mixed with water, the alcohol, and/or the cosolvent, and then the algae body is destroyed to form the algae mixture; and the wet algae body may also be After mixing with water, the alcohol and/or the co-solvent, the algae are destroyed to form the algae-breaking mixture. In these embodiments, the algae-breaking mixture is added to the catalyst in a subsequent step 15, and the alcohol and/or the co-solvent is added or not added as needed. In addition, in some embodiments, the algae system in the dry algal flour is already a grinder, and step 13 may also be skipped as appropriate. The destruction action described in step 13 may be biological destruction (such as decomposition by an enzyme), destruction by a chemical substance, or destruction of a physical method (such as destruction by a microwave device/method or ultrasonic oscillating device/method). ).

The catalyst of the present invention may be a transesterification enzyme, an acid catalyst, an alkaline catalyst or a combination thereof in any ratio. Wherein, the transesterification enzyme may be a lipase, and the lipolytic enzyme may be immobilized on a carrier as needed to make it an immobilized lipolytic enzyme. The acidic catalyst may be sulfuric acid (Sulfuric acid; H ₂ SO ₄ ), phosphoric acid (Hhosphoric acid; H ₃ PO ₄ ) or hydrochloric acid (Hydrochloric acid; HCl), etc., and the basic catalyst may be a homogeneous alkaline touch. Medium, such as sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium methoxide (NaOCH ₃ ), potassium methoxide (KOCH ₃ ), sodium amide (NaNH) ₂ ) Sodium hydride (NaH), Potassium amide (KNH ₂ ) or Potassium hydride (KH), etc., may also be a heterogeneous alkaline catalyst, such as calcium oxide (CaO) , Magnesium oxide (MgO) or Strontium oxide (SrO).

In addition, the alcohol is usually a short-chain alcohol, and the short-chain alcohol is selected from the group consisting of methanol, monoethanol, monopropanol, monobutanol, monopentanol or a combination thereof in any ratio, and the cosolvent can be specifically selected. From a mixture of n-hexane, mono-acetone, monochloroform, petroleum ether or any ratio thereof.

The invention of the present invention will be described below by way of specific examples.

Table 1 adjusts the transesterification reaction solution in the transesterification reaction solution by using the dry algae powder having an oil content of 63.2 wt% as a raw material and using the immobilized lipolytic enzyme as a catalyst for the transesterification reaction. The yield of biodiesel obtained after the individual content of alkane, methanol and water.

Among them, the n-hexane content listed in the condition A is the n-hexane addition amount (mL) per gram of dry algae powder, and the methanol addition amount per gram of the dry algae powder is fixed to 1.08 mL, and the reaction solution does not contain water. The methanol content listed in Condition B is the methanol addition amount (mL) per gram of dry algae powder, and the n-hexane content per gram of dry algae powder is fixed at 3.97 mL, and the reaction solution does not contain water. The water content listed in Condition C is the water addition amount (mL) per gram of dry algae powder, and the n-hexane and methanol contents per gram of dry algae powder are fixed at 3.97 mL and 1.08 mL, respectively. In addition, conditions A, B and C were all based on ultrasonic vibration as a method of breaking algae, and the content of immobilized lipolytic enzyme per gram of dry algae powder was 0.6 g, and the reaction temperature/reaction speed/reaction time were 40 respectively. °C, 600 rpm / 48 hours. The yield (%) of the raw diesel in Table 1 refers to the total weight of the crude oil of the original dry algae powder divided by the total weight of the raw diesel produced at the end of the reaction.

It can be known from Table 1 that by adjusting the individual content of short-chain alcohols (methanol), co-solvent (n-hexane) and water in the transesterification reaction solution, the method of the present invention uses dried algal flour as raw material to prepare the biomass. Diesel, the yield of which is above 90%, and even more than 96%, shows the high yield of the process of the invention.

Table 2 is a method for adjusting the transesterification reaction solution by using the wet algae having a water content of 70% to 90% as a raw material and using the immobilized lipolytic enzyme as a catalyst for the transesterification reaction by the above method of the present invention. The yield of biodiesel obtained after the content of methanol. The oil content of the wet algae body was 63.2 wt% (calculated as the weight of the wet algae body when dried).

In the reaction conditions listed in Table 2, the methanol content is the methanol addition amount (mL) per gram of wet algae body, and the content of n-hexane and immobilized lipolytic enzyme per gram of wet algae is fixed at 0.79 mL and 0.12. g, and the wet algae system is subjected to ultrasonic vibration as a method of breaking algae, and the reaction temperature/reaction rotation speed/reaction time are respectively 40 ° C, 600 rpm / 48 hours.

It can be known from Table 2 that the method of the present invention uses the wet algae as a raw material to prepare biodiesel, and the yield thereof is as high as 94% or more. It is obvious that the method of the present invention directly uses wet algae as a raw material and has excellent quality of raw materials. Diesel yield.

Table 3 adjusts the transesterification reaction solution by using the wet algae having a water content of 86% to 91% as a raw material and using the immobilized lipolytic enzyme as a catalyst for the transesterification reaction by the above method of the present invention. The yield of biodiesel obtained after the individual contents of the catalyst (immobilized lipolytic enzyme), n-hexane and methanol. Here, the "oil content" in Table 3 is obtained by converting the weight of the fat contained in the wet algae body when it is dried.

In the reaction conditions listed in Table 3, the content of catalyst, n-hexane and methanol is the individual addition amount per gram of wet algae body, and the wet algae system uses ultrasonic vibration as a method of algae breaking, and the reaction temperature / Reaction speed / reaction time were 40 ° C, 600 rpm / 48 hours, respectively.

It can be seen from Table 3 that, by the method of the present invention, even if the oil content of the algae as a raw material changes, even the algae having a low oil content (for example, the oil content is 13.5%), by adjusting the catalyst The content of n-hexane and methanol can still make the yield of biodiesel more than 90%, and will not be affected by the oil content of algae.

Table 4 uses the dry algae powder and the wet algae body having a water content of 80% as the raw material, and the modified alkaline cerium oxide as a catalyst for the transesterification reaction, through the above-mentioned The method comprises the following steps: adjusting the yield of the biodiesel obtained after adjusting the individual contents of the catalyst, n-hexane and methanol in the transesterification reaction solution. The oil content of the dry algae powder and the wet algae body is 45.6 wt% (the oil content of the wet algae body is obtained by converting the weight of the wet algae body).

In the reaction conditions listed in Table 4, the added amount of water, catalyst, n-hexane and methanol is the individual addition amount per gram of dry algae powder or wet algae body, and the algae-breaking method is applied with microwave. The reaction temperature/reaction rotation speed/reaction time were respectively 45 ° C, 600 rpm, and 3 hours.

It can be known from Table 4 that, when the catalyst is changed to an alkaline catalyst by the method of the present invention, whether the raw material of the algae is dry algae powder or wet algae body, by adjusting the catalyst and the positive After the content of alkane and methanol, the yield of biodiesel is up to 96%.

It can be seen from the above examples that the technique of the present invention omits the algae oil extraction step and directly performs the transesterification reaction with the oil-containing algae body, thereby saving the extraction step in addition to the complete utilization of the algae oil in the algae body. The cost of each cost. In addition, the present technology can also use wet algae as a raw material, thereby saving the steps of pre-drying treatment of algae, and further reducing the cost.

It can also be seen from the above embodiments that the present invention provides a mixture containing a raw diesel oil, the mixture comprising a mixture of broken algae obtained by destroying an algal body, wherein the algae-breaking mixture is esterified as a transesterification. The reactant of the reaction, which is obtained by the transesterification reaction, and the mixture can be used as a raw material for further purifying the biodiesel contained therein.

Summary As described above, the present invention provides a method for preparing biodiesel, which first provides biomass containing one of the oils, then destroys the biomass to obtain a crude mixture, and directly transesterifies the crude mixture as a reactant. The reaction is carried out to form biodiesel.

Furthermore, the present invention also provides a device for preparing biodiesel, the device comprising a first unit and a second unit, wherein the first unit is connected to the second unit, and the first unit is used to break The algal mixture is mixed with a catalyst, an alcohol and a cosolvent to form the biodiesel, and the algae mixture is supplied to the first unit by the second unit, and the second unit is a algae breaking device ( For example, a microwave device or an ultrasonic oscillating device, the algae-breaking mixture is obtained by destroying an algal body selected from a mixture of a dry algae powder and a liquid, a wet algae body or a combination thereof.

In particular, the present invention will be more clearly described by the following examples.

A method for preparing a biodiesel comprising: providing an algal body; destroying the algae to obtain a mixture of algae; and mixing the algae mixture with a catalyst, an alcohol, and a cosolvent to The biodiesel is formed.

2. The method of embodiment 1, wherein the algal body is selected from the group consisting of a mixture of dry algae powder and a liquid, a wet algae body, or a combination thereof.

3. The method of embodiment 1, wherein the catalyst is selected from the group consisting of a transesterification esterase, an acid catalyst, an alkaline catalyst, or a combination thereof in any ratio.

4. The method of embodiment 1, wherein the alcohol is a short chain alcohol selected from the group consisting of methanol, monoethanol, monopropanol, monobutanol, monopentanol or any thereof. In a proportional combination, the cosolvent is selected from the group consisting of monohexane, monoacetone, monochloroform, mono petroleum ether or a combination thereof in any ratio.

5. A device for preparing biodiesel comprising a first unit for mixing a mixture of algae and a catalyst, an alcohol and a cosolvent to form the biodiesel.

6. The device of embodiment 5, further comprising a second unit for providing the algae-breaking mixture to the first unit, wherein the second unit is a microwave device or an ultrasonic oscillating device, the broken The algal mixture is obtained by destroying an algal body selected from the group consisting of a mixture of dry algae powder and a liquid, a wet algae body or a combination thereof.

A method for preparing a biodiesel comprising: providing a mixture of a broken algae; and performing a transesterification reaction using the algae mixture as a reactant to form the biodiesel.

8. A mixture comprising a primary diesel fuel comprising: a mixture of a broken algae obtained by destroying an algal body, wherein the algae-breaking mixture is a reactant of a transesterification reaction, the biodiesel is permeated This transesterification reaction is obtained.

9. A method of producing a biomass diesel, comprising: providing a biomass, wherein the biomass comprises at least one oil; obtaining a crude mixture of the biomass; and performing a transesterification reaction using the crude mixture as a reactant To form the biodiesel.

10. The method of embodiment 9, wherein the biomass is an alga.

It is to be understood that the present invention has been described in detail by the above-described embodiments, and may be modified by those skilled in the art without departing from the scope of the appended claims. .

11, 12, 13, 14, 15, 16 and 17 ‧ ‧ steps

Figure 1 is a flow chart of a method for producing biodiesel according to the present invention.

Claims (7)

A method for preparing a biomass diesel comprising: providing an algal body; destroying the algae to form a mixture of algae; and mixing the algae mixture directly with a catalyst, an alcohol, and a cosolvent to form The biodiesel, wherein the catalyst is selected from the group consisting of a transesterification enzyme, an acid catalyst, an alkaline catalyst or any combination thereof, and the alcohol is a short-chain alcohol, and the short-chain alcohol is selected. The cosolvent is selected from the group consisting of monohexane, monoacetone, monochloroform, mono petroleum ether or any combination thereof in a combination of methanol, monoethanol, monopropanol, monobutanol, monopentanol or any ratio thereof. The method of claim 1, wherein the algal body is selected from the group consisting of a mixture of dry algae powder and a liquid, a wet algae body, or a combination thereof. A device for preparing biodiesel comprising: a first unit for mixing a mixture of algae and a catalyst, an alcohol and a cosolvent to form the biodiesel, wherein the catalyst is selected from the group consisting of Promoting transesterification enzyme, an acidic catalyst, an alkaline catalyst or any combination thereof, the alcohol is a short-chain alcohol selected from the group consisting of methanol, monoethanol, monopropanol, and Butanol, monopentanol or a combination thereof in any ratio selected from the group consisting of monohexane, monoacetone, monochloroform, mono petroleum ether or a combination thereof in any ratio. The device of claim 3, further comprising: a second unit for providing the algae-breaking mixture to the first unit, wherein the second unit is a microwave device or an ultrasonic oscillating device, The algae-breaking mixture is obtained by destroying an algal body selected from the group consisting of a mixture of dry algae powder and a liquid, a wet algae body or a combination thereof. A method for preparing a biomass diesel comprising: providing a mixture of a broken algae; and performing a transesterification reaction using the algae mixture as a reactant to form the biodiesel. A mixture comprising a primary diesel fuel comprising: a mixture of a broken algae formed directly by destroying an algal body, wherein the algae-breaking mixture is a reactant of a transesterification reaction, the biodiesel is passed through the It is obtained by transesterification. A method for preparing a biomass diesel, comprising: providing a biomass, wherein the algae comprises at least one oil; destroying the algae to form a crude mixture of the algae; and reacting the crude mixture The product is subjected to a transesterification reaction to form the biodiesel.