TW201538715A - Method for reusing waste cooking vegetable oil and its application on polyvinylchloride plastisol - Google Patents

Abstract

This invention provides a method for reusing a waste cooking vegetable oil comprising the steps of providing a mixture containing an organic acid, a peroxide, and a waste containing a waste vegetable oil and at least one chemical material selected from the group consisting of a monoglyceride-based compound, a diglyceride-based compound, and a fatty acid-based compound; making said mixture formed an epoxidized product, containing an epoxidized vegetable oil and at least one an epoxidized material selected from the group consisting of an epoxidized monoglyceride-based compound, an epoxidized diglyceride-based compound and an epoxidized fatty acid-based compound, by an epoxidation, wherein a temperature range and a reaction time of said epoxidation are from 40 DEG C. to 70 DEG C. and from 2 hour to 6 hours.

Description

Method for recycling waste edible vegetable oil and application thereof to polychlorinated Vinyl plastisol

The present invention relates to a method for recycling waste edible vegetable oil, and more particularly to a method for recycling waste edible vegetable oil comprising an epoxidation reaction step.

Polyvinyl chloride is widely manufactured due to its low cost and simple manufacturing process, and is used in various products such as food packaging bags, cling film or children's toys. Polyvinyl chloride is a hard polymer because it contains chlorine. In order to make it widely used, plasticizers are generally added to it to have better softness. The plasticizer to be added may be a phthalate, a trimellitate or an epoxidized vegetable oil.

Although phthalates can give PVC products better softness, when the phthalate plasticizer is oozing out of polyvinyl chloride products, it will endanger human health if it enters the human body. . In addition, the raw material of the phthalate is petroleum, and petroleum is a non-renewable energy source. Faced with the exhaustion of the dilemma. The epoxidized vegetable oil is a plasticizer which is harmless to the human body, and is obtained by extracting the vegetable oil from the plant and epoxidizing it. Therefore, the epoxidized vegetable oil has become a plasticizer which is currently attracting attention.

In addition to the extraction of fresh vegetable oil from plants as a starting material for epoxidized vegetable oils, the use of discarded edible vegetable oils has increased with the improvement of quality of life, which has caused a negative impact on the environment and the sewage sewer system. Therefore, if the edible edible vegetable oil can be used after being treated and the application value of the discarded edible vegetable oil can be improved, it is a subject that can be further broken by those skilled in the technical field.

Accordingly, a first object of the present invention is to provide a method of recycling edible vegetable oil.

The method for recycling waste edible vegetable oil of the present invention comprises the steps of: providing a mixture comprising an organic acid, a peroxide and a waste, wherein the waste comprises waste edible vegetable oil and at least one chemical group consisting of the following: a substance: a monoglyceride compound, a diglyceride compound, and a fatty acid compound; subjecting the mixture to an epoxidation reaction to form an epoxidized product, wherein the epoxidized product comprises an epoxidized vegetable oil and at least one of the following The epoxy group constituting the group: an epoxy monoglyceride compound, an epoxy bisglyceride compound, and an epoxy fatty acid compound; wherein the epoxidation reaction has an operating temperature range of 40 ° C to 70 ° C, and Operating time ranges from 2 hours to 6 hours.

The effect of the invention is to enhance the application value of waste edible vegetable oil by epoxidizing the waste edible vegetable oil. .

Preferably, the total amount of double bonds in the waste is in the range of 2 moles or more based on the total amount of the waste.

Preferably, the waste edible vegetable oil comprises a triglyceride vegetable oil.

Preferably, the organic acid is used in an amount ranging from 0.1 mole to 5 moles, based on 1 mole of double bond in the waste. Preferably, the peroxide is used in an amount ranging from 0.5 moles to 10 moles, based on 1 mole of double bond in the waste.

The organic acid may be an organic acid which can form a peroxyacid compound as an epoxidizing agent. The organic acid may be used singly or in combination, and the organic acid is, for example, but not limited to, acetic acid or formic acid or the like.

The peroxide may be a peroxide which can form a peroxyacid compound as an epoxidizing agent. The peroxide may be used singly or in combination, and the peroxide is, for example but not limited to, sodium peroxide, potassium peroxide, calcium peroxide, magnesium peroxide, zinc peroxide, potassium persulfate, or cerium peroxide.

Preferably, the mixture further comprises a catalyst. The catalyst may be used singly or in combination, and the catalyst is, for example but not limited to, an acidic catalyst or the like. The acidic catalyst is, for example but not limited to, sulfuric acid, nitric acid, phosphoric acid, aluminum sulfate, chlorosulfonic acid, tartaric acid, zeolite, cerium aluminum oxide, diatomaceous earth or kaolin.

Preferably, the epoxy content of the epoxidized product ranges from 80% or more.

Preferably, the method for recycling waste edible vegetable oil of the present invention Also included is a pretreatment step of the waste prior to forming the mixture, wherein the pretreatment step comprises at least one processing step consisting of a filtration treatment, a washing treatment, a de-floating treatment, and a decolorization treatment.

This pretreatment step allows the reaction to be easily controlled and the reaction process to be more stable, followed by obtaining an epoxidized product of high quality.

In order to make the epoxidation product have high quality to avoid affecting the effect of subsequent use and to have a higher proportion of ester compounds (such as waste edible vegetable oil) in the waste, preferably, the filtration treatment step is to use a filter or a filter. The mesh removes heterogeneous impurities from the waste. The heterogeneous impurity refers to a substance which is a non-ester compound and which has a different phase from the ester compound and is present in the waste.

In order to make the epoxidation product have high quality to avoid affecting the effect of subsequent use and to have a higher proportion of ester compounds (such as waste edible vegetable oil) in the waste, preferably, the washing treatment step is to use an organic solvent or The water is washed away to the homogeneous impurities in the waste. The homogeneous impurity refers to a non-ester compound and has the same phase as the ester compound and is present in the waste, and the substance is, for example, an impurity dissolved in the outside during heating or a derivative produced during heating.

Preferably, the step of removing the float is to scrape the foam and solid fat on the surface of the waste. In order to make the epoxidation product have high quality to avoid affecting the effect of subsequent use, preferably, the de-floating treatment step must be carried out in an environment relatively lower than room temperature to make the solid matter or foam-forming substance in the waste (such as saturation) Fatty acid) precipitates.

Because the color of the waste is mostly dark yellow or brown, or due to heating In the process, the pigment dissolved in the outside causes the color to become dark, so that the subsequent application is considered. Preferably, the decoloring treatment step is to lighten the color of the waste by using activated carbon or oil filter powder (for example, synthetic magnesium ruthenate).

In order to make the epoxidation product have high quality to avoid affecting the effect of subsequent use, preferably, the method for recycling the discarded edible vegetable oil of the present invention further comprises a post-treatment step performed after the epoxidation reaction, wherein the post-treatment step comprises And treatment, water washing treatment, deodorization treatment, filtration treatment and water removal treatment.

Preferably, the neutralization treatment step is to neutralize the acidic substance with a basic substance to bring the pH to 7.0.

Preferably, the water washing treatment step is to remove impurities or unreacted components in the mixture by washing with water.

Preferably, the deodorizing treatment step is an adsorption treatment using activated carbon or oil filter powder (for example, synthetic magnesium niobate).

Preferably, the filtering treatment step is to remove heterogeneous impurities using a filter or a sieve.

Preferably, the water removal treatment step is to remove water by distillation.

The epoxidation product of the present invention is obtained by an epoxidation reaction comprising a mixture of an organic acid, a peroxide and a waste, wherein the waste comprises waste edible vegetable oil and at least one chemical group consisting of the following groups; : monoglyceride compounds, diglyceride compounds, and fatty acid compounds.

The organic acid, organic acid, peroxide, waste and epoxy The reaction is as described above, so it will not be described again.

A second object of the present invention is to provide a polyvinyl chloride plastomer having better mechanical properties and low mobility.

The polyvinyl chloride plastisol of the present invention comprises: 100 parts by weight of polyvinyl chloride; and 40 parts by weight to 70 parts by weight of a bioplasticizer; the bioplasticizer comprising an ester compound and as described in claim 1 An epoxidized product obtained by a method for recycling waste edible vegetable oil, and the ester compound is selected from the group consisting of a citrate compound, a sebacate compound, a succinate compound, and a fatty acid glyceride compound. Or a combination thereof; wherein the ester compound is used in an amount ranging from 50% by weight to 90% by weight based on 100% by weight of the total amount of the raw plasticizer.

Preferably, the epoxy content of the epoxidized product ranges from 80% or more.

Preferably, the citrate compound is prepared by an esterification reaction comprising a mixture of citric acid and an alcohol compound. Preferably, the alcohol compound is selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, hexanol, or a combination thereof. Preferably, the citrate compound is selected from the group consisting of acetyl tributyl citrate (ATBC), acetyl triethyl citrate (ATEC), and citric acid. Acetyl trihexyl citrate (ATHC), or a combination of these.

The sebacate compound is, for example but not limited to, dibutyl sebacate or dioctyl sebacate. The succinate compound is, for example but not limited to, dibutyl succinate or diethylhexyl succinate.

The fatty acid glyceride compound is, for example but not limited to, acetyl glycerol monolaurate or glycerol monostearate.

The polyvinyl plastisol further comprises a thermal stabilizer. The thermal stabilizer comprises at least one compound consisting of a calcium stabilizer, a zinc stabilizer, an anthraquinone stabilizer, an organotin stabilizer, a lead stabilizer, a cadmium stabilizer, and a lanthanide stabilizer. Agent. The heat stabilizer is used in an amount ranging from 0.1 part by weight to 5 parts by weight based on 100 parts by weight of the total amount of the polyvinyl chloride. The thermal stabilizer inhibits the problem of thermal cracking of the polyvinyl chloride during subsequent processing. The use amount of the thermal stabilizer is less than 0.1 parts by weight, which may cause the subsequent processing to be difficult to operate and is limited, and the use amount of the thermal stabilizer is more than 5 parts by weight, which may result in the mechanical properties of the subsequently formed polyvinyl chloride soft rubber. good. The calcium-based stabilizer is, for example but not limited to, calcium stearate. The zinc-based stabilizer is, for example but not limited to, zinc stearate.

The method for preparing the polyvinyl chloride plastisol is not particularly limited as long as the polyvinyl chloride and the bioplasticizer and the heat stabilizer can be uniformly mixed.

The invention is further described in the following examples, but it should be understood that these examples are for illustrative purposes only and are not to be construed as limiting.

<Example 1>

Disposal of waste [source: raw soy salad oil (produced by the company), after the high temperature use by food merchants or vendors, and self-recycling after disposal] The filtrate is obtained by filtration, and then washed with water to obtain the upper layer solution, after which After cooling to below room temperature, the solid is precipitated, and then subjected to a flotation treatment by filtration. After obtaining the filtrate, adding activated carbon for decolorization treatment, and then performing filtration treatment to remove activated carbon, thereby obtaining a pale yellow treated waste. . Mixing 1 mole of treated waste (double molar content of 2 moles / 1 mole of treated waste), 1 mole of acetic acid, 3 moles of hydrogen peroxide, and 0.1 mole of sulfuric acid to form a mixture. Then, the epoxidation reaction was carried out at 60 ° C for 1 hour to obtain a crude epoxidized product, followed by neutralization treatment by adding 1 mol of sodium hydroxide, followed by decolorization and deodorization treatment by activated carbon, followed by filtration treatment. The filtrate was taken, and then pure water was added for washing treatment and allowed to stand. Then, the supernatant liquid was obtained, and finally, the water removal treatment was carried out by a distillation apparatus to obtain an epoxidized product.

<Examples 2 to 6>

Examples 2 to 6 were prepared in the same manner as in Example 1 except that the reaction time was changed as shown in Table 1.

<Application Example 1>

100 parts by weight of polyvinyl chloride, with 60 parts by weight of a bioplasticizer comprising 90% by weight of ATBC and 10% by weight of the epoxidized product of Example 1, and 0.15 parts by weight of zinc stearate with 0.15 parts by weight of hard The calcium citrate is mixed, stirred and mixed with a glass rod, and then gelled, and then stirred by a mechanical motor at 500 rpm for 2 minutes to obtain a polyvinyl chloride plastisol, and then further placed in a vacuum oven, and The vacuum of the vacuum oven was controlled at 0.1 torr, and the polyvinyl chloride plastisol was allowed to stand for 15 minutes to remove bubbles dissolved therein. After that, it is placed in a heat treatment apparatus (brand: Timing Machinery; model: CM-50) for heat treatment for 10 minutes, and the temperature of the heat treatment apparatus is controlled at 170 ° C, and the pressure is controlled at 75 kg / cm ² Get a PVC soft gel.

<Application Example 2 and Comparative Application Example 1>

Application Example 2 The polyvinyl chloride plastisol and the polyvinyl chloride soft gel were prepared in the same manner as in Application Example 1, except that the epoxidized vegetable oil and its use amount were changed as shown in Table 2.

<test item>

Mechanical properties: The polyvinyl chloride soft gels of Application Examples 1 to 2 and Comparative Application Example 1 were respectively tested by a micro load universal material testing machine (label: Shimadzu; model: AG-IS), and the stretching rate was controlled at 10 mm/ Min, and recorded the maximum stress, elongation at break and elastic modulus, three times in total and the average value.

Mobility; polystyrene standard sheet: A low-density polystyrene was placed in a mold having a thickness of 1 mm, and hot-pressed at 140 ° C, and then cut into a size of 1 cm × 1 cm and weighed (W1).

Test piece to be tested: Application Example 1 and Comparative Application Example 1 of polyvinyl chloride soft rubber They are cut into sizes of 1 cm × 1 cm and weighed separately (W2).

To facilitate the description of the measurement process, the following is described in Application Example 1, and the remaining samples to be tested are measured in accordance with this method.

Two sheets of the test piece of Application Example 1 were clamped to a polystyrene standard sheet to form a composite sheet, and the composite sheet was placed upright in an oven, and then a 200 g weight was placed on the top end of the composite sheet. Thereafter, the temperature of the oven was controlled at 50 ° C and the pressure was controlled at 19.6 kPa, and allowed to stand for five days. After five days, the composite sheet was taken out, and the weight (W3) of the sheet to be tested of Application Example 1 was weighed. The mobility calculation was performed by the following formula: mobility (%) = (W3-W2) × 100 / W2.

Conversion rate: the wastes of Examples 1 to 8 and the obtained epoxidized product were each measured by a nuclear magnetic resonance spectrometer, and the absorption peak area (A) of CH ₂ on the glycerol group in the triglyceride was calculated, and The normalisation factor (NF) is obtained by the formula (1). Next, calculate the absorption peak area (B) of the CH on the double bond, and calculate the number of double bonds (ND of LD) contained per 1 mole of triglyceride by the formula (2). ). The conversion rate can be obtained by taking the double-key molar number into the formula (3) for calculation.

NF=(A/4) Formula (1)

ND=(B-NF)/2NF (2)

Conversion rate (%) = [(ND _{waste -} ND _{epoxidation product} ) × 100 / ND _waste ] Formula (3)

Epoxy rate: The epoxidized products obtained in Examples 1 to 8 were measured by a nuclear magnetic resonance spectrometer, and the absorption of CH on the epoxy group was calculated. Peak area (C and D) and obtained by calculation of formula (4).

Epoxy rate (%) = [(C + D) / 2] × 100 / (NF _waste × ND _waste ) Formula (4)

In summary, the waste edible vegetable oil is reused after epoxidation to enhance the application value of discarded edible vegetable oil. Moreover, the use of the epoxidized product obtained by the epoxidation of the waste of the invention in the polyvinyl chloride soft rubber can make the polyvinyl chloride soft rubber have both low mobility and better mechanical properties, so it can be achieved. The object of the invention.

The above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made by the patent application scope and patent specification content of the present invention, All remain within the scope of the invention patent.

Claims (10)

A method for recycling edible vegetable oil, comprising the steps of: providing a mixture comprising an organic acid, a peroxide, and a waste, wherein the waste comprises waste edible vegetable oil and at least one chemical consisting of: a monoglyceride compound, a diglyceride compound, and a fatty acid compound; subjecting the mixture to an epoxidation reaction to form an epoxidized product, wherein the epoxidized product comprises an epoxidized vegetable oil and at least one group consisting of the following Group of epoxy materials: epoxy monoglycerides, epoxy glycerides and epoxide fatty acid compounds; wherein the epoxidation reaction temperature ranges from 40 ° C to 70 ° C, and the operation time The range is from 2 hours to 6 hours. The method for recycling waste edible vegetable oil according to claim 1, wherein the total amount of the waste is 1 mol, and the double bond content in the waste is in the range of 2 mol or more. The method for recycling waste edible vegetable oil according to claim 1, wherein the waste edible vegetable oil comprises triglyceride-based vegetable oil. The method for recycling waste edible vegetable oil according to claim 1, wherein the organic acid is used in an amount ranging from 0.1 mol to 5 mol, based on 1 mol of the double bond content in the waste. The method for recycling waste edible vegetable oil according to claim 1, wherein the peroxide is used in an amount ranging from 0.5 mol to 10 mol, based on 1 mol of the double bond content in the waste. a method for recycling waste edible vegetable oil according to claim 1, which The epoxy content of the epoxidized product ranges from 80% or more. The method for recycling waste edible vegetable oil according to claim 1, further comprising a pretreatment step of the waste before forming the mixture, wherein the pretreatment step comprises at least one treatment consisting of the following group Step: filtration treatment, washing treatment, de-floating treatment and decolorization treatment. The method for recycling waste edible vegetable oil according to claim 1, further comprising a post-treatment step performed after the epoxidation reaction, wherein the post-treatment step comprises a neutralization treatment, a water washing treatment, a deodorization treatment, a filtration treatment, and Remove water treatment. A polyvinyl chloride plastisol comprising: 100 parts by weight of polyvinyl chloride; and 40 parts by weight to 70 parts by weight of a bioplasticizer; the bioplasticizer comprising an ester compound and the composition described in claim 1 An epoxidized product obtained by a method of recycling edible vegetable oil, and the ester compound is selected from the group consisting of a citrate compound, a sebacate compound, a succinate compound, a fatty acid glyceride compound, or Such a combination; wherein the ester compound is used in an amount ranging from 50% by weight to 90% by weight based on 100% by weight of the total amount of the raw plasticizer. The polyvinyl plastisol according to claim 8, wherein the epoxidized product has an epoxy ratio in a range of 80% or more.