CN110951067A - Method for preparing polyether polyol by using high-acid-value waste oil - Google Patents
Method for preparing polyether polyol by using high-acid-value waste oil Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2615—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen the other compounds containing carboxylic acid, ester or anhydride groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2648—Alkali metals or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2696—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the process or apparatus used
Abstract
The invention discloses a method for preparing polyether polyol by using high-acid-value waste grease, and belongs to the technical field of polyether polyol preparation. The method comprises the following steps: carrying out esterification deacidification reaction on the waste oil and the polyhydric alcohol under a Lewis acid catalyst, cooling and filtering a reactant after deacidification is finished to obtain a reaction precursor, and recovering the Lewis acid catalyst for recycling; and adding a catalyst into the reaction precursor, continuously introducing propylene oxide to carry out polymerization reaction, and removing water and small molecules after the reaction is finished to obtain the crude product of the waste grease polyether polyol. The preparation method disclosed by the invention can well reduce foaming, has a good catalytic effect, greatly improves the yield of the polyether polyol, has low production cost, high efficiency and stable product, can change waste into valuable, and is energy-saving and environment-friendly.
Description
Technical Field
The invention relates to the technical field of polyether polyol preparation, in particular to a method for preparing polyether polyol by using high-acid-value waste grease.
Background
Waste oil refers to inedible animal and vegetable oil produced in the production process, and the sources of the waste oil are mainly food processing industry and catering industry. The raw materials can be divided into three categories: (1) frying waste oil; (2) the inferior oil and the swill oil are separated by the oil-water separator; (3) putrefactive animal fat and oil. The amount of waste edible oil produced in China is about 625 ten thousand tons every year, and the amount of waste oil is huge. During the process of frying food by using grease, the moisture in the food is greatly lost, so that the moisture content in the grease is increased, the grease is hydrolyzed under the high-temperature condition to generate free fatty acid, and the acid value of the obtained waste grease is high. In addition, the waste oil is easy to be rancid during storage at normal temperature, which is another reason for the excessive acid value of the waste oil. Due to the unreasonable source and extraction process of the waste grease, the waste grease can cause great harm to human bodies after flowing into the dining table again. Therefore, the polyether polyol prepared by using the waste oil with high acid value has good social and economic benefits.
At present, polyether polyol is mainly prepared from petroleum nonrenewable resources and low molecular alcohols, and the production process is complex and can not meet the actual demand of polyether polyol in the market. The polyether polyol prepared by utilizing renewable resources such as waste oil and the like can well relieve the shortage of petroleum and can also recycle the waste oil and the like. For example, chinese patent CN200710021804 reports a method for preparing polyether from waste grease, i.e. polyether is prepared from waste grease and small molecular alcohol under the action of catalyst such as KOH. However, in the case of a feedstock oil with an excessively high acid value, the catalyst KOH or the like reacts preferentially with free fatty acids in the oil to form soaps, which causes severe foaming and seriously affects the catalytic effect of the catalyst and the yield of polyether. Chinese patent CN104974340A discloses a method for preparing polyether by using acid-base two-step catalysis, namely, firstly using sulfuric acid or p-toluenesulfonic acid for catalytic esterification, and then using a base catalyst for catalytic polymerization to prepare polyether polyol. However, the method needs a large amount of water to wash the acid catalyst after esterification, so that the water resource loss is large, and the treatment of waste acid water can further increase the production cost, which is also a threat to the environment. In addition, the esterification process of the method needs 8-12h, and has the disadvantages of long synthesis period and high energy consumption.
Therefore, it is necessary to develop a new method for preparing polyether polyol by using waste gas oil and fat, which can reduce foaming, has good catalytic effect and improves polyether yield.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the method for preparing the polyether polyol by using the waste oil with the high acid value, which has the advantages of low production cost, high efficiency, stable product, energy conservation and environmental protection.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a method for preparing polyether polyol by using high-acid-value waste grease comprises the following steps:
s1, carrying out esterification and deacidification reaction on the waste oil and the polyhydric alcohol under a Lewis acid catalyst, placing nitrogen for 3 times, and carrying out esterification and deacidification for 1.5-3 h under the conditions that the reaction temperature is 100-180 ℃ and the vacuum degree is-0.08-0.098 MPa;
s2, cooling the reactant after the deacidification is finished to 70-80 ℃, performing suction filtration to obtain a reaction precursor, and recovering and recycling the Lewis acid catalyst;
and S3, adding a catalyst into the reaction precursor filtered in the step S2, continuously introducing propylene oxide to perform polymerization reaction at the reaction temperature of 110-140 ℃ and under the pressure of less than 0.35MPa, continuing to react for 1h until the final pressure is lowest and is not changed any more, and removing water and small molecules to obtain the crude product of the waste grease polyether polyol.
In a preferred embodiment of the present invention, the mass ratio of the polyol to the waste oil and fat in step S1 is 1:1 to 5, and the amount of the Lewis acid catalyst added is 0.1% to 1% of the mass of the waste oil and fat.
In a preferred embodiment of the present invention, the acid value of the waste oil or fat in the step S1 is 40 to 160 mgKOH/g.
In a preferred embodiment of the present invention, the waste oil and fat in step S1 is one or a mixture of any two or more of rapeseed acidified oil, peanut acidified oil, palmitic acidified oil, soybean acidified oil, coconut acidified oil and ricinoleic acid oil.
In a preferred embodiment of the present invention, the polyol in step S1 is one or a mixture of two or more selected from ethylene glycol, propylene glycol, glycerol, diethylene glycol, triethylene glycol, 1, 4-butanediol, pentaerythritol, and sorbitol.
As a preferred embodiment of the present invention, the Lewis acid catalyst in the step S1 is selected from AlCl3、 ZnCl2、ZnO、TiCl4、Zn(AC)2、SnCl4One or a mixture of any two or more of them.
In a preferred embodiment of the present invention, the mass ratio of the reaction precursor to propylene oxide in step S3 is 1:0.5 to 1.5.
In a preferred embodiment of the present invention, the catalyst is added in step S3 in an amount of 2 to 3.5 parts per thousand by mass based on the mass of the reaction precursor.
In a preferred embodiment of the present invention, the catalyst in step S3 is selected from one or a mixture of two or more of potassium methoxide, sodium methoxide, potassium hydroxide, and sodium hydroxide.
Compared with the prior art, the invention has the beneficial effects that:
according to the method, the high-acid-value waste oil is preferentially subjected to esterification and deacidification in the polyether preparation process, so that the soap generated by the direct reaction of the subsequently added alkaline catalyst and free fatty acid in the waste oil is effectively avoided, the foaming is effectively reduced, and the yield of polyether polyol is greatly improved; meanwhile, the Lewis acid catalyst added in the esterification deacidification process can be recycled, so that the production cost is further saved. On the other hand, the method for preparing the polyether polyol by using the waste oil acidified after food processing can effectively avoid the great harm to human bodies caused by the waste oil flowing into dining tables again, not only can improve the urban ecological environment and reduce the waste oil treatment expenditure, but also can change waste into valuable and increase the financial income, and the obtained polyether polyol can replace part of petroleum-based polyol and reduce the burden brought by the traditional fossil energy to a certain extent. In conclusion, the preparation method disclosed by the invention can well reduce foaming, has a good catalytic effect, greatly improves the yield of polyether polyol, has the advantages of low production cost, high efficiency and stable product, can change waste into valuable, and is energy-saving and environment-friendly.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
A method for preparing polyether polyol by using high-acid-value waste grease comprises the following steps:
s1, carrying out esterification and deacidification reaction on the waste oil and the polyhydric alcohol under a Lewis acid catalyst, placing nitrogen for 3 times, and carrying out esterification and deacidification for 1.5-3 h under the conditions that the reaction temperature is 100-180 ℃ and the vacuum degree is-0.08-0.098 MPa; wherein the acid value of the waste oil is 40-160 mgKOH/g; the mass ratio of the polyhydric alcohol to the waste oil is 1: 1-5, and the addition amount of the Lewis acid catalyst is 0.1-1% of the mass of the waste oil;
s2, cooling the reactant after the deacidification is finished to 70-80 ℃, performing suction filtration to obtain a reaction precursor, and recovering and recycling the Lewis acid catalyst;
s3, adding a catalyst into the reaction precursor filtered in the step S2, continuously introducing propylene oxide according to the mass ratio of the reaction precursor to the propylene oxide of 1: 0.5-1.5 at the reaction temperature of 110-140 ℃ and under the pressure of 0.35MPa for polymerization reaction, continuing to react for 1 hour after the final pressure is lowest and is not changed, and removing moisture and small molecules to obtain the crude product of the waste oil polyether polyol.
In the above method, the waste oil in step S1 is one or a mixture of two or more of rapeseed acidified oil, peanut acidified oil, palmitic acidified oil, soybean acidified oil, coconut acidified oil, and ricinoleic acid oil; the polyalcohol is one or mixture of more than two of ethylene glycol, propylene glycol, glycerol, diethylene glycol, triethylene glycol, 1, 4-butanediol, pentaerythritol and sorbitol; the Lewis acid catalyst is selected from AlCl3、ZnCl2、 ZnO、TiCl4、Zn(AC)2、SnCl4One or a mixture of any two or more of them. The catalyst in step S3 is selected from one or a mixture of any two or more of potassium methoxide, sodium methoxide, potassium hydroxide, sodium hydroxide, etc., and the addition amount of the catalyst is 2 to 3.5 per mill of the mass of the reaction precursor.
Example 1:
a method for preparing polyether polyol by using high-acid-value waste grease comprises the following steps:
S1、mixing ethylene glycol, soybean acidified oil, AlCl3According to the mass ratio of ethylene glycol to soybean acidified oil to AlCl3Putting the mixture into a four-neck flask at a ratio of 250:500:0.5, adding nitrogen for 3 times, heating, and esterifying and deacidifying for 2 hours at the temperature of 120-130 ℃ and the vacuum degree of-0.08-0.098 MPa;
s2, after the deacidification is finished, cooling the reactant to 70-80 ℃, and performing suction filtration to obtain a reaction precursor;
s3, putting the reaction precursor into a reaction kettle, adding a KOH catalyst with the mass of 3.0 thousandth of that of the reaction precursor, placing nitrogen for 3 times, heating to 110-115 ℃, continuously introducing propylene oxide into the reaction precursor according to the mass ratio of 500:500 of propylene oxide to carry out polymerization reaction, controlling the pressure to be below 0.35MPa, after the propylene oxide is introduced, keeping the temperature of 110-120 ℃ for reaction until the pressure is the lowest and does not change any more, continuing the reaction for 1 hour, and finally removing water and small molecules to obtain the crude product of the waste grease polyether polyol.
The product indexes of the polyether polyol prepared by the embodiment are as follows: appearance: a light yellow transparent liquid; hydroxyl value: 265 mgKOH/g; moisture content: 0.08 percent; viscosity (25 ℃): 1370 mpa.s; the product yield is as follows: 89.6 percent.
Example 2:
a method for preparing polyether polyol by using high-acid-value waste grease comprises the following steps:
s1, mixing triethylene glycol, ricinoleic acid oil and ZnCl2Triethylene glycol according to the mass ratio: ricinoleic acid oil: ZnCl2Putting 200:500:0.5 into a four-neck flask, adding nitrogen for 3 times, heating, and esterifying and deacidifying for 2.5h at the temperature of 120-130 ℃ and the vacuum degree of-0.08-0.098 MPa;
s2, after the deacidification is finished, cooling the reactant to 70-80 ℃, and performing suction filtration to obtain a reaction precursor;
s3, putting the reaction precursor into a reaction kettle, adding a potassium methoxide catalyst with the mass being 2 per thousand of that of the reaction precursor, placing nitrogen for 3 times, heating, keeping the reaction precursor, namely propylene oxide, 500:750 in mass ratio to carry out polymerization reaction when the temperature is increased to 110-115 ℃, keeping the temperature of 115-120 ℃ after the propylene oxide is introduced until the pressure is the lowest and does not change any more, continuing the reaction for 1 hour, and finally removing water and small molecules to obtain the crude product of the waste grease polyether polyol.
The product indexes of the polyether polyol prepared by the embodiment are as follows: appearance: a light yellow transparent liquid; hydroxyl value: 207 mgKOH/g; moisture content: 0.1 percent; viscosity (25 ℃): 1540 mpa.s; the product yield is as follows: 85.5 percent.
Example 3:
a method for preparing polyether polyol by using high-acid-value waste grease comprises the following steps:
s1, mixing glycerol, rapeseed acidified oil, palmitic acidified oil and TiCl4Glycerol according to the mass ratio: rapeseed acidified oil: palmitic acid oil: TiCl (titanium dioxide)4Putting 200:250:250:1.5 into a four-neck flask, adding nitrogen for 3 times, heating, and esterifying and deacidifying for 2.5h at the temperature of 120-130 ℃ and the vacuum degree of-0.08-0.098 MPa;
s2, after the deacidification is finished, cooling the reactant to 70-80 ℃, and performing suction filtration to obtain a reaction precursor;
s3, putting the reaction precursor into a reaction kettle, adding NaOH catalyst with the mass of 3.5 per thousand of that of the reaction precursor, placing nitrogen for 3 times, heating, keeping the reaction precursor, namely propylene oxide 500:400 in a mass ratio for polymerization reaction when the temperature is increased to 115-120 ℃, keeping the temperature of 120-125 ℃ after the propylene oxide is introduced, keeping the reaction for 1 hour after the pressure is not changed until the pressure is the lowest, and finally removing water and small molecules to obtain the crude product of the waste grease polyether polyol.
The product indexes of the polyether polyol prepared by the embodiment are as follows: appearance: a light yellow transparent liquid; hydroxyl value: 346 mgKOH/g; moisture content: 0.06 percent; viscosity (25 ℃): 930 mpa.s; the product yield is as follows: 90.1 percent.
Example 4:
a method for preparing polyether polyol by using high-acid-value waste grease comprises the following steps:
s1, mixing pentaerythritol, arachidic oil, coconut acid oil, Zn (AC)2Pentaerythritol in mass ratio: arachidic oil production: coconut acidified oil: zn (AC)2Putting 200:250:300:3.3 into a four-neck flask, putting nitrogen for 3 times, and then putting the flask into a nitrogen tankHeating, and esterifying and deacidifying for 2.5 hours at the temperature of 120-130 ℃ and the vacuum degree of-0.08-0.098 MPa;
s2, after the deacidification is finished, cooling the reactant to 70-80 ℃, and performing suction filtration to obtain a reaction precursor;
s3, putting the reaction precursor into a reaction kettle, adding a sodium methoxide catalyst with the mass of 2.5 per thousand of that of the reaction precursor, placing nitrogen for 3 times, heating, keeping the reaction precursor, namely propylene oxide 500:400 in a mass ratio for polymerization reaction when the temperature is increased to 115-120 ℃, keeping the temperature of 120-125 ℃ for reaction after the propylene oxide is introduced, keeping the reaction for 1 hour after the pressure is not changed until the pressure is the lowest, and finally removing water and small molecules to obtain the crude product of the waste grease polyether polyol.
The product indexes of the polyether polyol prepared by the embodiment are as follows: appearance: a light yellow transparent liquid; hydroxyl value: 367 mgKOH/g; moisture content: 0.09%; viscosity (25 ℃): 1030 mpa.s; the product yield is as follows: 86.7 percent.
Example 5:
a method for preparing polyether polyol by using high-acid-value waste grease comprises the following steps:
s1, mixing glycerol, pentaerythritol, arachidic oil, coconut acidified oil, SnCl4Glycerol is added according to the mass ratio: pentaerythritol: arachidic oil production: coconut acidified oil: SnCl4Putting 150:150:250:250:1.5 into a four-neck flask, adding nitrogen for 3 times, heating, and esterifying and deacidifying for 2.5h at the temperature of 120-130 ℃ and the vacuum degree of-0.08-0.098 MPa;
s2, after the deacidification is finished, cooling the reactant to 70-80 ℃, and performing suction filtration to obtain a reaction precursor;
s3, putting the reaction precursor into a reaction kettle, adding a potassium methoxide catalyst with the mass being 2 per thousand of that of the reaction precursor, placing nitrogen for 3 times, heating, keeping the reaction precursor, namely propylene oxide 500:400 in a mass ratio to carry out polymerization reaction when the temperature is raised to 115-120 ℃, keeping the temperature of 120-125 ℃ after the propylene oxide is introduced, reacting for 1 hour after the pressure is kept to be the lowest and is not changed, and finally removing water and small molecules to obtain the crude product of the waste grease polyether polyol.
The product indexes of the polyether polyol prepared by the embodiment are as follows: appearance: a light yellow transparent liquid; hydroxyl value: 405 mgKOH/g; moisture content: 0.05 percent; viscosity (25 ℃): 1250 mpa.s; the product yield is as follows: 86.9 percent.
Comparative example 1:
a method of preparing a fatty acid polyether polyol, comprising the steps of:
150g of waste grease, 9g of catalyst potassium methoxide and 120g of glycerol are put into a reaction kettle, nitrogen is placed for 3 times, and then the temperature is raised. When the temperature reaches 140 ℃, 200g of ethylene oxide and 200g of propylene oxide are equivalently and circularly introduced, and the reaction is carried out for 60min under the conditions of 130 ℃ and 0.6MP after the epoxy is introduced each time until the reaction is finished after the epoxy is introduced. The reaction was stopped and evacuated. Vacuum-pumping at 120 deg.C/10 mmHg for 40min to obtain crude product of fatty acid polyether polyol.
The product indexes of the polyether polyol prepared by the comparative example are as follows: appearance: a light yellow transparent liquid; hydroxyl value: 437 mgKOH/g; moisture content: 0.08 percent; viscosity (25 ℃): 1850 mpa.s; the product yield is as follows: 73.1 percent.
Comparative example 2:
a method of preparing a fatty acid polyether polyol, comprising the steps of:
150g of waste grease, 1g of catalyst KOH and 60g of triethylene glycol are put into a reaction kettle, nitrogen is placed for 3 times, and then the temperature is raised. When the temperature is 150 ℃, introducing 110g of ethylene oxide and 110g of propylene oxide in an equivalent circulation manner, reacting for 30min at the temperature of 130 ℃ and at the temperature of 0.3MP after finishing each time of introducing the epoxy, and ending the reaction after finishing introducing the epoxy. The reaction was stopped and evacuated. And (3) vacuumizing under the condition of 100 ℃/10mmHg for 30min to obtain a crude product of the fatty acid polyether polyol.
The product indexes of the polyether polyol prepared by the comparative example are as follows: appearance: a light yellow transparent liquid; hydroxyl value: 401 mgKOH/g; moisture content: 0.10 percent; viscosity (25 ℃): 1210 mpa.s; the product yield is as follows: 75.3 percent.
Comparative example 3:
a method of preparing a fatty acid polyether polyol, comprising the steps of:
350g of waste grease, 6g of potassium glycerol as a catalyst and 120g of trimethylolpropane are put into a reaction kettle, nitrogen is placed for 3 times, and then the temperature is raised. When the temperature reaches 140 ℃, 410g of ethylene oxide and 410g of propylene oxide are introduced in an equivalent circulation manner, and after each time of epoxy introduction, the reaction is carried out for 40min under the conditions of 140 ℃ and 0.8MP until the reaction is finished after the epoxy introduction. The reaction was stopped and evacuated. And (3) vacuumizing under the condition of 110 ℃/10mmHg for 30min to obtain a crude product of the fatty acid polyether polyol.
The product indexes of the polyether polyol prepared by the comparative example are as follows: appearance: a light yellow transparent liquid; hydroxyl value: 410 mgKOH/g; moisture content: 0.04 percent; viscosity (25 ℃): 950 mpa.s; the product yield is as follows: 74.7 percent.
From the data of examples 1-5 and comparative examples 1-3, it can be found that the method not only can synthesize polyether polyol products with indexes similar to those of the comparative examples, but also has the polyether polyol yield which is about 15% higher than that of the comparative examples. This is because the alkaline catalyst added in the comparative example reacts preferentially with the free fatty acid in the waste oil to form soap, which causes an increase in by-products and severe foaming, resulting in a decrease in product yield. On the other hand, the consumption of the base catalyst can cause the deterioration of the catalytic effect, thereby affecting the polymerization process with the epoxide. Therefore, the method effectively avoids the direct reaction of the subsequently added alkaline catalyst and the free fatty acid in the waste oil to generate the soap, thereby effectively reducing the foaming and greatly improving the yield of the polyether polyol; meanwhile, the Lewis acid catalyst added in the esterification deacidification process can be recycled, so that waste acid water is not generated, and the production cost is further saved; compared with the prior art, the synthesis period is greatly shortened, the production efficiency is high, and the energy consumption is low.
In conclusion, the preparation method disclosed by the invention can well inhibit foaming, has a good catalytic effect, remarkably improves the yield of the polyether polyol, and has the advantages of low production cost, high efficiency, stable product, energy conservation, environmental friendliness and the like, and can change waste into valuable.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (9)
1. A method for preparing polyether polyol by using high-acid-value waste grease is characterized by comprising the following steps: the method comprises the following steps:
s1, carrying out esterification and deacidification reaction on the waste oil and the polyhydric alcohol under a Lewis acid catalyst, placing nitrogen for 3 times, and carrying out esterification and deacidification for 1.5-3 h under the conditions that the reaction temperature is 100-180 ℃ and the vacuum degree is-0.08-0.098 MPa;
s2, cooling the reactant after the deacidification is finished to 70-80 ℃, performing suction filtration to obtain a reaction precursor, and recovering and recycling the Lewis acid catalyst;
and S3, adding a catalyst into the reaction precursor filtered in the step S2, continuously introducing propylene oxide to perform polymerization reaction at the reaction temperature of 110-140 ℃ and under the pressure of less than 0.35MPa, continuing to react for 1h until the final pressure is lowest and is not changed any more, and removing water and small molecules to obtain the crude product of the waste grease polyether polyol.
2. The method for preparing polyether polyol by using waste oil with high acid value as claimed in claim 1, wherein: the mass ratio of the polyhydric alcohol to the waste oil in the step S1 is 1: 1-5, and the addition amount of the Lewis acid catalyst is 0.1% -1% of the mass of the waste oil.
3. The method for preparing polyether polyol by using high acid value waste grease according to claim 1 or 2, wherein: the acid value of the waste oil in the step S1 is 40-160 mgKOH/g.
4. The method for preparing polyether polyol by using high acid value waste grease as claimed in claim 3, wherein the method comprises the following steps: the waste oil in step S1 is one or a mixture of any two or more of rapeseed acidified oil, peanut acidified oil, palmitic acid oil, soybean acidified oil, coconut acidified oil and ricinoleic acid oil.
5. The method for preparing polyether polyol by using high acid value waste grease according to claim 1 or 2, wherein: the polyol in step S1 is selected from one or a mixture of any two or more of ethylene glycol, propylene glycol, glycerol, diethylene glycol, triethylene glycol, 1, 4-butanediol, pentaerythritol, and sorbitol.
6. The method for preparing polyether polyol by using high acid value waste grease according to claim 1 or 2, wherein: the Lewis acid catalyst in the step S1 is selected from AlCl3、ZnCl2、ZnO、TiCl4、Zn(AC)2、SnCl4One or a mixture of any two or more of them.
7. The method for preparing polyether polyol by using high acid value waste grease according to claim 1 or 2, wherein: the mass ratio of the reaction precursor to the propylene oxide in the step S3 is 1: 0.5-1.5.
8. The method for preparing polyether polyol by using high acid value waste grease according to claim 1 or 2, wherein: the adding amount of the catalyst in the step S3 is 2-3.5 per mill of the mass of the reaction precursor.
9. The method for preparing polyether polyol by using waste oil with high acid value as claimed in claim 8, wherein: the catalyst in step S3 is selected from one or a mixture of two or more of potassium methoxide, sodium methoxide, potassium hydroxide, sodium hydroxide, and the like.
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| CN114409888A (en) * | 2022-02-28 | 2022-04-29 | 浙江皇马科技股份有限公司 | Method for preparing high molecular weight polyether polyol by using waste oil |
| CN116651506A (en) * | 2023-03-27 | 2023-08-29 | 中国石油大学(华东) | Oil-soluble molybdenum-based catalyst, and preparation method and application thereof |
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| CN116651506A (en) * | 2023-03-27 | 2023-08-29 | 中国石油大学(华东) | Oil-soluble molybdenum-based catalyst, and preparation method and application thereof |
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