CN111909788A

CN111909788A - Preparation method of zinc oxide waste edible oil coagulant

Info

Publication number: CN111909788A
Application number: CN202010617649.3A
Authority: CN
Inventors: 刘艺
Original assignee: Anhui Jinhua Zinc Oxide Co ltd
Current assignee: Anhui Jinhua Zinc Oxide Co ltd
Priority date: 2020-07-01
Filing date: 2020-07-01
Publication date: 2020-11-10
Anticipated expiration: 2040-07-01
Also published as: CN111909788B

Abstract

The invention belongs to the field of high polymer materials, and particularly relates to a preparation method of a zinc oxide waste edible oil coagulant, which has a simple production process and wide raw material sources, wherein zinc oxide gel is synthesized by hydrothermal method and is subjected to graft polymerization modification, the zinc oxide waste edible oil coagulant is prepared by wax crystal load consisting of Chinese insect wax, beeswax and poly (12-hydroxystearic acid) stearate, the coagulant has a good coagulation effect, is more suitable for oil, has a high coagulation speed, can realize rapid coagulation of waste edible oil by dual functions of chemistry and physics, the coagulation point of the oil is increased by adding the coagulant, the fog point of the oil is improved, the coagulant is nontoxic, odorless, green and environment-friendly, and has a certain antibacterial and fresh-keeping effect, and the occurrence of oil deterioration is slowed down in the coagulation process and the coagulation and transportation process, so that catering and catering are easier to treat, Food processing factory, family kitchen etc. are discarded edible oil in large quantities.

Description

Preparation method of zinc oxide waste edible oil coagulant

Technical Field

The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of a zinc oxide waste edible oil coagulant.

Background

The waste edible oil coagulator is a frequently used article for housewives abroad. When the factors of detail and environmental pollution are emphasized, the chicken, the fried steak and the croquette are fried at home, redundant oil after the food is fried cannot be directly poured into a sewer of a water pool, the pipeline is blocked due to long time, and peculiar smell is emitted. In order to prevent the generation of peculiar smell, people usually prefer a clean and tidy home environment, and properly process the waste edible oil to ensure good hygienic habit. Generally, waste oil is poured into a bowl, then a coagulant is added, all the oil is coagulated into blocks in about 20 minutes, and then the blocks are wrapped by newspaper and placed in a plastic bag to be thrown away conveniently and clean a pot without polluting the environment when fixed garbage is thrown away. When the sewer is not irradiated by sunlight, is dark and moist, has bacteria breeding, smells and rich contents all the year round, the sewer is not only filled with grease and detergent discharged from a kitchen, but also contains washing powder, laundry detergent and cloth fibers discharged from a washing machine, bath foam, hair conditioner and a large amount of hair discharged from a bathroom, and the situation that untreated sewage ruminates back from the sewer before reaching a sewage treatment facility is occasionally seen in life. This condition is known as sewer flooding. People who have experienced sewer spills in person often have some psychological shadow left because the process is particularly nausea. When the sewer overflows, the sewage permeates bacteria in the sewer into underground water to pollute the ecological environment, so that human suffers from gastrointestinal diseases. Spills in lakes and the ocean can cause death of fish, plankton and other aquatic life, and even cause dangers to large marine mammals such as lions and seals. Humans also have varying degrees of adverse effects after eating animals contaminated with sewage. Therefore, some countries can close the beach of the region in time after sewage overflows, limit swimming and forbid eating aquatic products. According to the statistics of the Environmental Protection Agency (EPA), 23000-75000 sewer overflow events occur in the whole United states every year. Canada, italy, france, and also have plagued many years with public health problems that have been associated with the prevention of sewer spills. Most sewer overflows are caused by blockage, and almost half of the blockage is waste food oil. In China, the oil content is large in diet, the population base number, the diet structure, the diameter of a sewer drain pipe and other comprehensive factors are considered, and particularly the problem to be solved is to properly process waste edible oil such as chafing dish, fried food and the like. The drainage pipeline of a common residential building is often blocked due to fat accumulation, so that the rapid development of the drainage dredging industry is caused, and various drainage trails can be seen in streets and alleys. But clearance is basically palliative and not radical. The special grease coagulant can discard the coagulated oil as combustible garbage. Some dishes need a large amount of oil for cooking, the oil is not suitable for being repeatedly used, and the oil can be specially recycled as a renewable resource in some countries and is used for a recycled diesel engine of a diesel engine. And can be used as industrial raw materials such as soap, coating, paint and the like, fertilizers, feeds and the like. A maleate polymer. Chinese patent CN2019107625139 discloses a maleate polymer, a waste edible oil coagulant and a preparation method thereof, but the maleate polymer has no lubrication effect and has odor, and a special viscosity reducer including the maleate polymer enters colloid molecules through the molecules thereof with strong hydrogen bond forming capability and strong penetration and dispersion capability, so as to disperse the internal structure of the colloid molecules, thereby reducing the viscosity of oil, but the self is not beneficial to the coagulation of waste edible oil, the use effect is not good, and along with the gradual implementation of the garbage classification policy in China, the classification of living garbage is carried out by' recyclables, harmful garbage and kitchen garbage (including kitchen garbage, household kitchen garbage and other kitchen garbage), the use amount of waste oil is large, the problems are more, and the renewable garbage with high recycling value is needed, so technical personnel in the art need to develop a preparation method of a zinc oxide waste edible oil coagulant, the method and the device meet the existing use requirements and performance requirements, improve the resource utilization efficiency and reduce the burden of domestic garbage terminal disposal.

Disclosure of Invention

Aiming at the problems, the invention aims to provide a preparation method of a zinc oxide waste edible oil coagulant.

The invention is realized by the following technical scheme:

a preparation method of a zinc oxide waste edible oil coagulant comprises the following steps: (1) adding 18-20 parts of glycerol into 8-10 parts of 10-15% by mass of zinc acetate solution, transferring the mixture to a hydrothermal reaction kettle, adding 25-30 parts of 8-10% by mass of zinc nitrate solution and 2-4 parts of ion exchange resin 717, placing the mixture in the hydrothermal reaction kettle, slowly adding 1-2 parts of polyacrylic acid as a template agent, uniformly stirring, adding 2-4 parts of propylene epoxide as a gel promoter, performing hydrothermal stirring reaction at 90-95 ℃ for 1-3 hours, and filtering to obtain a nano zinc oxide gel; (2) preparing graft modified nano zinc oxide gel: adding 18-20 parts of the nano zinc oxide gel obtained in the step (1) into 20-30 parts of water, carrying out ultrasonic treatment for 18-20 min, transferring the nano zinc oxide gel into another reaction kettle, adding 2-4 parts of dimethyl diallyl ammonium chloride and 0.01-0.05 initiator into the reaction kettle at the temperature of 75-80 ℃ in a water bath and the stirring speed of 300-350 rpm, reacting for 10-15 min, adding 2-4 parts of allyl glycidyl ether and 1-2 parts of cross-linking agent, reacting for 10-15 min, adding 0.8-1 part of allyl glycidyl ether, carrying out heat preservation stirring reaction for 2-4 h, cooling to room temperature, adjusting the pH value of the system to be 6.8-7.0 by using 1.0 wt% hydrochloric acid, transferring the system into a shaping mold for gelling, preparing wet gel, washing with deionized water, and carrying out vacuum freeze drying treatment to obtain graft modified zinc oxide gel; (3) putting insect white wax, beeswax and poly (12-hydroxystearic acid) stearate into a dipping tank according to the weight ratio of 1-2: 2-3: 3-4, completely melting the mixture into wax crystal liquid at 75-80 ℃, then placing a beaker into a vacuum oven at 75-80 ℃, adding the grafted modified zinc oxide gel prepared in the step (2) into the dipping tank, dipping the mixture by adopting a vacuum dipping method, sealing a tank cover, vacuumizing, controlling the negative pressure in the tank to be 0.07-0.08 MPa, controlling the vacuumizing time to be 10-15 min, releasing pressure, filtering, taking out the grafted modified zinc oxide gel dipped in the wax crystal liquid, cooling for 12-24 h at 30-35 ℃, and grinding by using a ball mill until the powder is 500-800 meshes to obtain the edible zinc oxide waste oil coagulant.

Further, the initiator in the step (2) is one of azodiisopropyl imidazoline hydrochloride, potassium persulfate and azodiisobutyl amidine hydrochloride.

Further, the cross-linking agent in the step (2) is formed by mixing 0.05-0.4 part of bis (dioctyloxy pyrophosphate) ethylene titanate, 0.01-0.02 part of 4- (N-maleimide methyl) cyclohexane-1-carboxylic sulfonic acid group succinimide ester sodium salt and 0.1-0.2 part of N, N-methylene bisacrylamide.

Further, the ball mill in the step (3) is one of a conical ball mill, an ultra-fine laminated ball mill, a ceramic ball mill and a lattice type ball mill.

The waste edible oil is natural animal oil or vegetable oil, such as olive oil, cocoa butter, coconut oil, beef tallow, almond oil, wheat germ oil, rice germ oil, safflower oil, soybean oil, tea seed oil, camellia oil, corn oil, jojoba oil, lard, mutton fat, rapeseed oil, avocado oil, linseed oil, walnut oil, perilla oil, palm oil, sunflower seed oil, safflower oil, sesame oil, cottonseed oil, rice bran oil, peanut oil.

The invention has the beneficial effects that:

the invention prepares zinc oxide gel through hydrothermal reaction, thereby influencing the action of the waste edible oil on a motion interface, and the zinc oxide is nontoxic and harmless, does not influence the further application of the waste used oil in the fields of feed, fertilizer, soap and the like, and can promote the formation, growth and precipitation of wax crystals in the oil of the waste edible oil through the interaction of the zinc oxide and insect wax through further graft polymerization modification and wax crystal liquid loading, macroscopically reduce the room temperature fluidity of the waste edible oil, solidify the waste edible oil, analyze and promote the improvement of fog point of the oil by the insect wax, beeswax and poly (12-hydroxystearic acid) stearate loaded by the zinc oxide, and induce the wax crystal to develop as crystal nuclei to increase and accumulate the wax crystals in the oil product, thereby forming a body-shaped structure and achieving the solidification effect. The graft polymerization modified zinc oxide realizes grafting through a cross-linking agent and an initiator in the process of initiating polymerization, a high molecular chain and a porous microstructure are adsorbed on precipitated wax crystals to distort crystal forms, the surface characteristics of the wax crystals are changed, the growth of the wax crystals is promoted to form a body-shaped structure, the wax crystals are precipitated together, the side chain of the long high molecular chain is eutectic with the wax, a polar group promotes the wax crystals to grow further, and the graft modified zinc oxide coagulant has certain surface activity, so that the solubility of insect white wax in edible oil can be reduced, and the wax precipitation amount is increased. The fluidity of the used oil is reduced, and because the addition of the coagulant precipitates flaky and needle-shaped wax crystals at low temperature, under the conditions that the edible oil mist point is increased and the freezing point is increased, the waste oil is mutually combined to form a body-shaped structure, and important impurities such as colloid, starch slag and the like in the waste oil are adsorbed around the waste oil or wrapped in the body-shaped structure to form a wax paste-shaped substance, so that the fluidity of the used oil is reduced, and the macroscopic solidification effect of the waste edible oil is caused. The invention promotes the solidification and simultaneously performs the synergistic action with the antibacterial property of the zinc oxide by modification methods such as graft polymerization and the like, so that the zinc oxide has a certain antibacterial and fresh-keeping effect.

Compared with the prior art, the invention has the following advantages:

the production process is simple, the raw material source is wide, zinc oxide gel is synthesized by hydrothermal method and graft polymerization modification is carried out, and the zinc oxide waste edible oil coagulator is prepared by wax crystal loading consisting of Chinese wax, beeswax and poly (12-hydroxystearic acid) stearate, the coagulant has good coagulation effect, is suitable for more oils, has high coagulation speed, realizes the rapid coagulation of the waste edible oil through the dual functions of chemistry and physics, the coagulating agent is added to ensure that the freezing point of the grease is increased and the fog point is improved, the coagulating agent is non-toxic, odorless and environment-friendly, and the grafted dimethyl diallyl ammonium chloride and the zinc oxide have the effects of certain antibiosis and freshness preservation on the coagulated waste edible oil, in the solidification process and the solidification and transportation process, the oil deterioration is slowed down, and a large amount of waste edible oil in catering, food processing factories, family kitchens and the like is easier to treat.

Detailed Description

The invention is illustrated by the following specific examples, which are not intended to be limiting.

Example 1

A preparation method of a zinc oxide waste edible oil coagulant comprises the following steps: (1) adding 20 parts of glycerol into 5 parts of 15 mass percent zinc acetate solution, transferring the solution to a hydrothermal reaction kettle, adding 30 parts of 10 mass percent zinc nitrate solution and 4 parts of ion exchange resin 717, placing the mixture in the hydrothermal reaction kettle, slowly adding 2 parts of template agent polyacrylic acid, stirring uniformly, adding 4 parts of gel accelerator propylene oxide, carrying out hydrothermal stirring reaction at 95 ℃ for 3 hours, and filtering to obtain nano zinc oxide gel; (2) preparing graft modified nano zinc oxide gel: adding 18 parts of the nano zinc oxide gel obtained in the step (1) into 30 parts of water, carrying out ultrasonic treatment for 20min, transferring the nano zinc oxide gel into another reaction kettle, adding 4 parts of dimethyldiallylammonium chloride and 0.05 initiator azodiisopropyl imidazoline hydrochloride into the reaction kettle at the water bath temperature of 80 ℃ and the stirring speed of 350rpm, reacting for 15min, adding 4 parts of allyl glycidyl ether and 2 parts of cross-linking agent, reacting for 15min, adding 1 part of allyl glycidyl ether, carrying out heat preservation stirring reaction for 4h, cooling to room temperature, adjusting the pH value of the system to be 7.0 by hydrochloric acid with the weight fraction of 1.0%, transferring the obtained solution into a shaping mold for gelation, preparing wet gel, washing by using deionized water, and carrying out vacuum freeze drying treatment to obtain graft modified zinc oxide gel; (3) putting insect white wax, beeswax and poly (12-hydroxystearic acid) stearate into an impregnation tank according to the weight ratio of 1:2:3, completely melting the mixture into wax crystal liquid at 80 ℃, then placing a beaker into a vacuum oven at 80 ℃, adding the grafted modified zinc oxide gel prepared in the step (2) into the impregnation tank, impregnating by adopting a vacuum impregnation method, sealing a tank cover, vacuumizing, controlling the negative pressure in the tank to be 0.08MPa, vacuumizing for 15min, decompressing, filtering, taking out the grafted modified zinc oxide gel impregnated with the wax crystal liquid, cooling for 24h at 35 ℃, grinding by using a cone ball mill until the powder is 800 meshes to obtain the waste zinc oxide edible oil coagulant, wherein the cross-linking agent in the step (2) is 0.4 part of bis (dioctyloxypyrophosphate) ethylene titanate, 0.02 part of 4- (N-maleimidomethyl) cyclohexane-1-carboxylic acid sulfo succinimide ester sodium salt, and the like, 0.2 portion of N, N-methylene bisacrylamide.

Example 2

A preparation method of a zinc oxide waste edible oil coagulant comprises the following steps: (1) adding 20 parts of glycerol into 8 parts of 15 mass percent zinc acetate solution, transferring the solution to a hydrothermal reaction kettle, adding 30 parts of 10 mass percent zinc nitrate solution and 4 parts of ion exchange resin 717, placing the mixture in the hydrothermal reaction kettle, slowly adding 2 parts of template agent polyacrylic acid, stirring uniformly, adding 2 parts of gel accelerator propylene oxide, carrying out hydrothermal stirring reaction at 90 ℃ for 1 hour, and filtering to obtain nano zinc oxide gel; (2) preparing graft modified nano zinc oxide gel: adding 20 parts of water into 20 parts of the nano zinc oxide gel obtained in the step (1), performing ultrasonic treatment for 18min, transferring the nano zinc oxide gel into another reaction kettle, adding 2 parts of dimethyldiallylammonium chloride and 0.05 initiator azodiisobutyramidine hydrochloride into the reaction kettle at the temperature of 75 ℃ in a water bath and the stirring speed of 300rpm, reacting for 10min, adding 4 parts of allyl glycidyl ether and 1 part of cross-linking agent, reacting for 10min, adding 0.8 part of allyl glycidyl ether, performing heat preservation stirring reaction for 2h, cooling to room temperature, adjusting the pH value of the system to be 6.8 by using hydrochloric acid with the weight fraction of 1.0%, transferring the mixture into a shaping mold for gelation to prepare wet gel, washing by using deionized water, and performing vacuum freeze drying treatment to obtain graft modified zinc oxide gel; (3) putting insect white wax, beeswax and poly (12-hydroxystearic acid) stearate into an impregnation tank according to the weight ratio of 2:3:4, completely melting the mixture into wax crystal liquid at 75 ℃, then putting a beaker into a vacuum oven at 80 ℃, putting the grafted modified zinc oxide gel prepared in the step (2) into the impregnation tank, impregnating by adopting a vacuum impregnation method, sealing a tank cover, vacuumizing, controlling the negative pressure in the tank to be 0.07MPa, vacuumizing for 10min, decompressing, filtering, taking out the grafted modified zinc oxide gel impregnated with the wax crystal liquid, cooling for 12h at 30 ℃, performing superfine lamination ball mill grinding until the powder is 800 meshes to obtain the waste edible oil coagulant of zinc oxide, wherein the cross-linking agent in the step (2) is 0.4 part of bis (dioctyloxypyrophosphate), ethylene titanate, 0.02 part of 4- (N-maleimidomethyl) cyclohexane-1-carboxylic acid sulfo succinimide ester sodium salt, and the like, 0.1 part of N, N-methylene bisacrylamide.

Comparative example 1

This comparative example 1 compares to example 1 in that poly (12-hydroxystearic acid) stearate was not used in step (3) except that the process steps were the same.

Comparative example 2

This comparative example 2 compares to example 2 in that no beeswax was used in step (3) except that the process steps were the same.

Comparative example 3

This comparative example 3 compares to example 2 in that in step (3) no impregnation with a mixture of insect wax and beeswax, poly (12-hydroxystearic acid) stearate was used, except that the process steps were the same.

Comparative example 4

This comparative example 4 compares with example 2, omitting step (2), except that the process steps are otherwise the same.

The results of the performance test of the edible oil coagulants of examples 1-2 and comparative examples 1-4 are shown in tables 1, 2 and 3:

table 1 results of comparing physical and chemical property tests of edible oil coagulants in examples and comparative examples 1-4

Item	Example 1	Example 2	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4
							Oil absorption g/100g	234	245	243	246	258	212
Boiling oil absorption mL/100g	218	226	224	225	237	191
							Setting time/min	10.5	11.3	12.1	13.2	14.3	12.8

Note: reference is made to Japanese general Standard JIS K5101-13-1-2004 pigment test method, which widely uses waste edible oil coagulants, section 13 oil absorption section 1, JIS K5101-13-2-2004 pigment test method, by refined flax oil method, section 13 oil absorption section 2, boiling flax oil method.

TABLE 2 comparison of the results of the test for the cloud point and freezing point elevation of the edible oil coagulants of examples and comparative examples 1-4

Note: in palm oil (palm oil of Johnson's seal with condensation point of 24 deg.C and fog point of 12 deg.C), rice bran oil (with condensation point of 19 deg.C, fog point of 17 deg.C, acid value of 5.6 mg KOH/g, peroxide value of 2.2 mmol/kg, saponification value of 184.9 mg KOH/g, and iodine value of 119.1 g I₂The edible oil coagulants of examples 1-2 and comparative examples 1-4, which are respectively added with the edible oil coagulants accounting for 4% of the oil content, are respectively added into 100g of self-squeezed rice bran oil and peanut oil (the first-grade peanut oil of Shandong Fukang with the condensation point of 3 ℃ and the fog point of 5 ℃), and the tests are carried out according to the edible oil condensation point and fog point test standards.

Table 3 comparative results of the no-flow setting time test of edible oil coagulants in examples and comparative examples 1-4

Item	Example 1	Example 2	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4
							Non-flowing and solidifying time/min of rice bran oil at 30 DEG C	12.1	13.2	13.4	15.1	16.4	16.5
Non-flowing palm coagulation time/min at 30 DEG C	10.5	11.3	12.1	13.2	14.3	12.8

Note: in palm oil (palm oil of Johnson's seal with condensation point of 24 deg.C and fog point of 12 deg.C), rice bran oil (with condensation point of 19 deg.C, fog point of 17 deg.C, acid value of 5.6 mg KOH/g, peroxide value of 2.2 mmol/kg, saponification value of 184.9 mg KOH/g, and iodine value of 119.1 g I₂100g of self-squeezed rice bran oil), the edible oil coagulants of examples 1-2 and comparative examples 1-4, in which the edible oil coagulants accounting for 3% of the respective oil contents were added, respectively, were tested.

Claims

1. A preparation method of a zinc oxide waste edible oil coagulant is characterized by comprising the following steps: (1) adding 18-20 parts of glycerol into 8-10 parts of 10-15% by mass of zinc acetate solution, transferring the mixture to a hydrothermal reaction kettle, adding 25-30 parts of 8-10% by mass of zinc nitrate solution and 2-4 parts of ion exchange resin 717, placing the mixture in the hydrothermal reaction kettle, slowly adding 1-2 parts of polyacrylic acid as a template agent, uniformly stirring, adding 2-4 parts of propylene epoxide as a gel promoter, performing hydrothermal stirring reaction at 90-95 ℃ for 1-3 hours, and filtering to obtain a nano zinc oxide gel; (2) preparing graft modified nano zinc oxide gel: adding 18-20 parts of the nano zinc oxide gel obtained in the step (1) into 20-30 parts of water, carrying out ultrasonic treatment for 18-20 min, transferring the nano zinc oxide gel into another reaction kettle, adding 2-4 parts of dimethyl diallyl ammonium chloride and 0.01-0.05 initiator into the reaction kettle at the temperature of 75-80 ℃ in a water bath and the stirring speed of 300-350 rpm, reacting for 10-15 min, adding 2-4 parts of allyl glycidyl ether and 1-2 parts of cross-linking agent, reacting for 10-15 min, adding 0.8-1 part of allyl glycidyl ether, carrying out heat preservation stirring reaction for 2-4 h, cooling to room temperature, adjusting the pH value of the system to be 6.8-7.0 by using 1.0 wt% hydrochloric acid, transferring the system into a shaping mold for gelling, preparing wet gel, washing with deionized water, and carrying out vacuum freeze drying treatment to obtain graft modified zinc oxide gel; (3) putting insect white wax, beeswax and poly (12-hydroxystearic acid) stearate into a dipping tank according to the weight ratio of 1-2: 2-3: 3-4, completely melting the mixture into wax crystal liquid at 75-80 ℃, then placing a beaker into a vacuum oven at 75-80 ℃, adding the grafted modified zinc oxide gel prepared in the step (2) into the dipping tank, dipping the mixture by adopting a vacuum dipping method, sealing a tank cover, vacuumizing, controlling the negative pressure in the tank to be 0.07-0.08 MPa, controlling the vacuumizing time to be 10-15 min, releasing pressure, filtering, taking out the grafted modified zinc oxide gel dipped in the wax crystal liquid, cooling for 12-24 h at 30-35 ℃, and grinding by using a ball mill until the powder is 500-800 meshes to obtain the edible zinc oxide waste oil coagulant.

2. The method for preparing the coagulant for waste zinc oxide edible oil and fat according to claim 1, wherein the initiator in the step (2) is one of azodiisopropyl imidazoline hydrochloride, potassium persulfate and azodiisobutyl amidine hydrochloride.

3. The method for preparing the coagulant for waste zinc oxide edible oil and fat according to claim 1, wherein the cross-linking agent in the step (2) is a mixture of 0.05 to 0.4 part of bis (dioctyloxypyrophosphate) ethylene titanate, 0.01 to 0.02 part of sodium 4- (N-maleimidomethyl) cyclohexane-1-carboxysulfosuccinimide ester, and 0.1 to 0.2 part of N, N-methylenebisacrylamide.

4. The method for preparing the coagulant of waste edible zinc oxide oil and fat according to claim 1, wherein the ball mill in the step (3) is one of a conical ball mill, an ultra-fine laminated ball mill, a ceramic ball mill or a lattice ball mill.