CN104326911A - Method for preparing polyol from waste grease and application thereof - Google Patents
Method for preparing polyol from waste grease and application thereof Download PDFInfo
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- CN104326911A CN104326911A CN201410468577.5A CN201410468577A CN104326911A CN 104326911 A CN104326911 A CN 104326911A CN 201410468577 A CN201410468577 A CN 201410468577A CN 104326911 A CN104326911 A CN 104326911A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
- C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/10—Ester interchange
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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
- C08G2101/00—Manufacture of cellular products
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a method for preparing polyol from waste grease, comprising the following steps: a solid acid catalyst which has large hydrophobic surface and has both a sulfonic group and a carboxylic group is adopted to catalyze esterification and transesterification between waste grease and methanol so as to convert waste grease to fatty acid methyl ester and a by-product glycerin; saturated fatty acid ester in fatty acid methyl ester is separated; under the catalysis of a dual acid site solid acid and in cooperation of the dual acid site, 30% hydrogen peroxide is directly catalyzed for epoxidation of fatty acid methyl ester, an intermediate product is not separated, and the by-product glycerin is added for ring opening of alkoxylation after direct heating-up; and finally, filtration is carried out to recycle the catalyst, and reduced pressure distillation is carried out to remove water so as to obtain biological oil-based polyol. According to the method, waste grease is used as a raw material, thus turning waste into wealth. The polyol product obtained has good biodegradability; the preparation process is green; emission of three industrial wastes is low; product structure and hydroxyl value can be adjusted; the range of application is wide; and the level of effect on the environment is low.
Description
Technical field
The present invention relates to method and application that a kind of waste grease prepares polyvalent alcohol, belong to organic chemical synthesis technical field.
Background technology
Polyurethane material excellent performance, of many uses, China has become the market that urethane is with fastest developing speed in the world, and research and development of products, production, application etc. obtain marked improvement.In all kinds of polyurethane product, the purposes of polyurethane foam is the widest, and have huge development space in the field such as building energy conservation, solar water heater, imitative wooden furniture, piping insulation, embedding, the market requirement is vigorous.Conventional urethane polyvalent alcohol is generally the polyoxyalkylene hydrocarbon polyols of high functionality, high hydroxyl value (lower molecular weight), i.e. " polyether glycol ".Polyether glycol is normally by small molecule alcohol or the amine initiator of high functionality, under catalyst action, prepare with ring-opening polymerizations such as propylene oxide (PO), oxyethane (EO), synthesis material mostly derives from oil, the net importation amount of the oil of China in 2012 is up to 2.84 hundred million tons, along with the quickening of the paces that improve and build a well-off society in an all-round way of Economic development, social life, external oil interdependency improves constantly, and oil supply is become safely do not allow the problem of avoiding.In addition, the comparatively difficult degradation in its natural state of petroleum base hard polyurethane foam product, becomes white pollution source.Therefore, the important directions that green reproducible polyol masses just becomes current polyvalent alcohol industry development is found.The fatty acid triglyceride structure of bio oil has good hydrophobicity, and the polyurethane material of preparation has good physical and chemical performance, especially in hydrolytic resistance and thermostability.The environmental influence research of the biomass polyalcohol that American National Standard and technological associations (MST) complete recently shows, compared with petroleum-based polyols, the consumption of vegetable oil polyol overall energy reduces by 23%, nonrenewable resources consumption reduces by 61%, reduce 36% to airborne release greenhouse gases, obviously can alleviate the problems such as Global warming, smog formation, ecological degeneration.Mount Huang etc. (CN200710037248.5) are prepared vegetable oil polyol to alcoholysis method and have been carried out systematic study, select vegetables oil and Epoxy oil mixture respectively, with aliphatic amide and fatty alcohol for alcoholysis agent, under basic catalyst existence, prepare vegetable oil polyol.Benecke H P(CPI-Polyurethanes 2009 Technical Conference, 2009,5/10-7/10) vegetable oil polyol is prepared by ozone oxidation mode, under an acidic catalyst effect, by ozone oxidation vegetables oil, animal tallow, then, with small molecular alcohol, esterification is carried out to the carboxylic acid of fatty acid derived, thus obtain vegetable oil polyol.Petrovic Z etc. (US6433121) disclose a kind of vegetables oil that adopts and prepare the method for vegetable oil polyol by hydroxylation after first epoxidation.First joined in vegetables oil by peroxy acid and form epoxidized vegetable oil, epoxidation transformation efficiency is 91% ~ 94%, then adopts water or small molecular alcohol to form vegetable oil-based polyols under fluoroboric acid katalysis.Guo A etc. (Journal of Applied Polymer Science, 2000,77,467-473) adopt epoxy soybean oil to be raw material, carry out hydroxylation prepared soybean oil base polyol by methyl alcohol.Yao Zhihong etc. (CN 200610041380.9) select epoxy rapeseed oil under catalyst action and contain the nucleophilic reagent generation epoxy ring-opening reaction of reactive hydrogen, generate the tri-glyceride of hydroxyl, then add polyvalent alcohol or hydramine carries out alcoholysis reaction, prepare functionality and the high vegetable oil polyol product of hydroxyl value.Within 2011, China's edible oil aggregate consumption reaches 2,765 ten thousand tons, and wherein the degree of self-sufficiency only has 38.1%, and grain and oil safety has become the problem that China needs to pay close attention at present, therefore, edible oil is directly used in large-scale commercial production unrealistic.On the other hand, the waste cooking oil that a large amount of edible oil consumption produces is troubling problem always, and the pernicious sewer oil event that food and beverage waste oil and grease flows into dining table again occurred once in national multiple city.Waste cooking oil is seriously polluted, and oily(waste)water often causes blowdown pipe network to block, and brings difficulty to environmental sanitation work; If waste oil directly flows to rivers can worsen water body, totally unfavorable to environmental ecology.Therefore, these waste greases are effectively utilized just to seem particularly important.In order to overcome the above problems, the present invention considers to adopt waste grease raw material, to have the solid acid catalyst having sulfonic group and carboxylic acid group concurrently of large hydrophobic surface, catalysis waste grease carries out esterification respectively, epoxidation series connection alkoxide ring opening synthesis biopolyol, avoid the pollution of waste grease, reduce raw materials cost, achieve and turn waste into wealth, simultaneously in reaction process with solid tart flavour catalyzer, avoid the loaded down with trivial details aftertreatment of homogeneous catalyst, reaction terminates rear catalyst and carries out filtered and recycled, and carry out recirculation use, enormously simplify technical process, reduce the discharge of three industrial wastes.
Summary of the invention
The object of the present invention is to provide a kind of eco-friendly, reproducible waste grease prepares green synthesis method and the application of polyvalent alcohol, the inventive method take waste grease as raw material, achieve and turn waste into wealth, gained polyol product biological degradability is good, and preparation process is green, three industrial wastes discharge is little, product structure and hydroxyl value adjustable, applied range, the feature that the level that affects of environment is low.
For achieving the above object, technical scheme of the present invention is:
A kind of waste grease prepares the method for polyvalent alcohol, comprise the steps: to adopt the solid acid catalyst having sulfonic group and carboxylic acid group concurrently with large hydrophobic surface, catalysis waste grease and methyl alcohol carry out esterification and transesterification reaction, waste grease are converted into fatty acid methyl ester and by-product glycerol; Then lower the temperature, the mode of the polyunsaturated fatty acid ester in fatty acid methyl ester by crystallization is separated, improve the content of double bond in fatty acid methyl ester; Then continue under bisgallic acid central solid acid catalysis, utilize the collaborative of bisgallic acid center, fatty acid methyl ester is carried out epoxidation by the hydrogen peroxide of direct catalysis 30%, and intermediate product, without separation, after directly heating up, adds by-product glycerol and carries out alkoxide open loop; Last filtering recovering catalyst, namely obtains bio oil polylol after underpressure distillation dewaters.By selecting different glyceride stocks, temperature of reaction, reaction times etc. to control level of response, Molecular regulator structure, hydroxyl value distribution etc., obtain the biopolyol product in applicable different application field.
Described step is specially:
1) there is the solid acid preparation having sulfonic group and carboxylic acid group concurrently of large hydrophobic surface
By unsaturated carboxylic acid, be dissolved in organic solvent containing the sulfonic acid of unsaturated double-bond and Vinylstyrene, solution solubility is 20 ~ 65%, mixed solvent hot copolymerization 2 ~ 10 h is carried out under the initiation of Diisopropyl azodicarboxylate initiator, initiator amount is 0.1% ~ 1% of reactant total mass, and solvent thermal polymerization temperature, at 80 ~ 180 DEG C, cools, filter, namely washing and drying obtains has the solid acid catalyst that large hydrophobic surface has sulfonic group and carboxylic acid group concurrently;
2) preprocessing process of waste grease
After waste grease being heated to 60 DEG C, carry out core filtration, the removing impurity such as earth, swill, washing composition wherein, then the mode of decompression 110 DEG C distillation is adopted, except the moisture in degrease, finally, add acidic white earth and carry out adsorption bleaching, obtain the waste grease after process;
3) esterification reaction of organic acid process
Waste grease pretreated for step 1) and methyl alcohol are uniformly mixed, control the mass ratio 1:0.2 ~ 1:1.1 of waste grease and methyl alcohol, add step 2) solid acid catalyst having sulfonic group and carboxylic acid group concurrently with large hydrophobic surface prepared, catalyst levels is 0.5% ~ 3% of reactant total mass, carry out heated and stirred 5 ~ 21 h at 60 ~ 80 DEG C after, filtering recovering catalyst, catalyzer can directly be reused, distillation removing excessive methanol, carry out layering, upper strata is fatty acid methyl ester, and lower floor is that glycerin by-products is collected respectively;
4) saturated fatty acid methyl ester sepn process.
Fatty acid methyl ester step 3) prepared cools to-5 ~ 15 DEG C, after carrying out standing 2 ~ 14h, filters, and separate solid saturated fatty acid methyl ester obtains the fatty acid methyl ester of high double bond content;
5) epoxidation series connection alkoxide open loop
Fatty acid methyl ester after step 4) being separated and the solid acid catalyst of recovery mix, catalyst levels is 0.5% ~ 2% of reactant total mass, heated and stirred is carried out at 50 ~ 80 DEG C, drip the hydrogen peroxide of 30%, the mass ratio of hydrogen peroxide and fatty acid methyl ester is 1:0.2 ~ 1:1, during dropping, control temperature is lower than 80 DEG C, after dripping off, continue to react 0.5 ~ 8h at such a temperature, complete epoxidation, then, temperature is risen to 80 ~ 100 DEG C, add by-product glycerin as alkoxide reagent, be 1:0.1 ~ 1:0.5 with the mass ratio of fatty acid methyl ester, continue reaction 0.5 ~ 4h, stopped reaction, filtered and recycled solid acid catalyst, carry out namely obtaining biopolyol product after distillation dewaters.
Described have the preparation method that large hydrophobic surface has the solid acid catalyst of sulfonic acid and carboxylic acid group concurrently and be: by unsaturated carboxylic acid, be dissolved in organic solvent containing the sulfonic acid of unsaturated double-bond and Vinylstyrene, wherein unsaturated carboxylic acid, unsaturated sulfonic acid and Vinylstyrene mass ratio be (0.05 ~ 0.2): (0.01 ~ 0.3): 1, mixed solvent hot copolymerization 2 ~ 10 h is carried out under the initiation of Diisopropyl azodicarboxylate initiator, polymerization temperature is at 80 ~ 180 DEG C, cooling, filter, namely washing and drying obtains has the solid acid catalyst that large hydrophobic surface has sulfonic group and carboxylic acid group concurrently, wherein said unsaturated carboxylic acid adopts the one in vinylformic acid, butenoic acid, toxilic acid, fumaric acid, pentenoic acid, the described sulfonic acid containing unsaturated double-bond adopts the one in styrene sulfonic acid, vinyl sulfonic acid, propene sulfonic acid, hydroxy ethyl sulphonate, described organic solvent adopts the one in ethyl acetate, propyl carbinol, tetrahydrofuran (THF), Virahol, acetone.
The animal-plant oil not allowing to eat that described waste grease adopts food and drink, food-processing unit and family to produce, animal slaughtering segmentation and leather processing repair the grease of the offal treatment refinement of cutting, the grease produced in the food oils refining course of processing, the one in the expired grease produced in Oil processing or grease storage process.The animal-plant oil not allowing to eat that described food and drink, food-processing unit and family produce adopts the one in swill oil, frying abendoned oil, sewer oil and smoke exhaust ventilator condensate oil; Described animal slaughtering segmentation and leather processing repair the one that grease that the offal treatment of cutting refines adopts useless butter, useless sheep oil, useless lard, gives up in chicken fat; The grease produced in the described food oils refining course of processing adopts the one in acidification oil, carclazyte oil, deodorization distilled oil; The expired grease produced in described Oil processing or grease storage process adopts expired rapeseed oil, expired soybean oil, the one in plant produced heat conduction abendoned oil.
The application of polyvalent alcohol prepared by a kind of method utilizing described waste grease to prepare polyvalent alcohol, described waste grease is prepared polyvalent alcohol and is had molecular structure and all adjustable feature of hydroxyl value, various polyurethane coating, urethane foam, sizing agent, rapid prototyping material, fibre reinforced composites, surfactant field can be widely used in, as the green replacer of conventional polyether polyols or polyester polyol.
The invention has the beneficial effects as follows: (1) is raw material with waste grease, reduces raw materials cost, avoids the pollution problem of waste grease, achieves and turn waste into wealth.(2) biological degradability of the biopolyol of gained is good, can fast degradation at nature, avoids white pollution.(4) employing has the esterification having the solid acid catalysis waste grease of sulfonic group and carboxylic acid group concurrently, the epoxidation series connection alkoxide ring opening process of large hydrophobic surface, simplify technical process, avoid the loaded down with trivial details aftertreatment of homogeneous acid catalyst, reduce the three waste discharge of industry.(5) the biopolyol molecular structure of gained and hydroxyl value all adjustable, can according to material choice and feed ratio Molecular regulator structure and hydroxyl value.(6) of many uses, alternative conventional petroleum polylol, for fields such as polyurethane foam, sizing agent, polyurethane coating, tensio-active agents.
Embodiment
embodiment 1
A kind of waste grease of the present embodiment prepares the method for polyvalent alcohol, comprises the steps:
1st step has the solid acid preparation having sulfonic group and carboxylic acid group concurrently of large hydrophobic surface
By vinylformic acid, styrene sulfonic acid and Vinylstyrene are dissolved in ethyl acetate, solution solubility is 35%, wherein unsaturated carboxylic acid, unsaturated sulfonic acid and Vinylstyrene mass ratio be 0.1:0.3:1, under the initiation of Diisopropyl azodicarboxylate initiator, carry out mixed solvent hot copolymerization 5 h, initiator amount is 0.3% of reactant total mass, solvent thermal polymerization temperature is at 100 DEG C, cooling, filter, namely washing and drying obtains has the solid acid catalyst that large hydrophobic surface has sulfonic group and carboxylic acid group concurrently.
The preprocessing process of the 2nd step waste grease
After swill oil being heated to 60 DEG C, carry out core filtration, the removing impurity such as earth, swill, washing composition wherein, then, the mode of decompression 110 DEG C distillation is adopted, except the moisture in degrease, finally, add acidic white earth and carry out adsorption bleaching, obtain the swill oil after process.
3rd ground beetle esterification reaction process
Pretreated swill oil and methyl alcohol are uniformly mixed, control the mass ratio 1:0.3 of swill oil and methyl alcohol, add the solid acid catalyst having sulfonic group and carboxylic acid group concurrently with large hydrophobic surface, catalyst levels is 1% of reactant total mass, carry out heated and stirred 12 h at 70 DEG C after, filtering recovering catalyst, catalyzer can directly be reused, distillation removing excessive methanol, carry out layering, upper strata is fatty acid methyl ester, yield 98%, and lower floor is that glycerin by-products is collected respectively;
4th step saturated fatty acid methyl ester sepn process.
Fatty acid methyl ester is cooled to 2 DEG C, after carrying out standing 5h, filter, separate solid saturated fatty acid methyl ester, obtain the fatty acid methyl ester of high double bond content.
5th step epoxidation series connection alkoxide open loop
The solid acid catalyst of the fatty acid methyl ester after separation and recovery is mixed, catalyst levels is 1% of reactant total mass, heated and stirred is carried out at 70 DEG C, drip the hydrogen peroxide of 30%, the mass ratio of hydrogen peroxide and fatty acid methyl ester is 1:0.5, during dropping, control temperature is lower than 80 DEG C, after dripping off, continue to react 4h at such a temperature, then, temperature is risen to 90 DEG C, add by-product glycerin as alkoxide reagent, be 1:0.3 with the mass ratio of fatty acid methyl ester, continue reaction 2h, stopped reaction, filtered and recycled solid acid catalyst, carry out namely obtaining swill oil polylol product after distillation dewaters, hydroxyl value is 338mgKOH/g.
The present embodiment has following features: (1) the present embodiment is raw material with waste grease, reduces raw materials cost, avoids the pollution problem of waste grease, achieves and turn waste into wealth.(2) biological degradability of the biopolyol of gained is good, can fast degradation at nature, avoids white pollution.(4) employing has the esterification having the solid acid catalysis waste grease of sulfonic group and carboxylic acid group concurrently, the epoxidation series connection alkoxide ring opening process of large hydrophobic surface, simplify technical process, avoid the loaded down with trivial details aftertreatment of homogeneous acid catalyst, reduce the three waste discharge of industry.(5) the biopolyol molecular structure of gained and hydroxyl value all adjustable, can according to material choice and feed ratio Molecular regulator structure and hydroxyl value.(6) of many uses, alternative conventional petroleum polylol, for fields such as polyurethane foam, sizing agent, polyurethane coating, tensio-active agents.
embodiment 2
A kind of waste grease of the present embodiment prepares the method for polyvalent alcohol, comprises the steps:
1st step has the solid acid preparation having sulfonic group and carboxylic acid group concurrently of large hydrophobic surface
By toxilic acid, vinyl sulfonic acid and Vinylstyrene are dissolved in propyl carbinol, solution solubility is 40%, wherein unsaturated carboxylic acid, unsaturated sulfonic acid and Vinylstyrene mass ratio be 0.12:0.2:1, under the initiation of Diisopropyl azodicarboxylate initiator, carry out the hot copolymerization 8h of mixed solvent, initiator amount is 0.5% of reactant total mass, solvent thermal polymerization temperature is at 120 DEG C, cooling, filter, namely washing and drying obtains has the solid acid catalyst that large hydrophobic surface has sulfonic group and carboxylic acid group concurrently.
The preprocessing process of the 2nd step waste grease
After frying abendoned oil is heated to 60 DEG C, carry out core filtration, the removing impurity such as earth, swill, washing composition wherein, then, the mode of decompression 110 DEG C distillation is adopted, except the moisture in degrease, finally, add acidic white earth and carry out adsorption bleaching, obtain the frying abendoned oil after process.
3rd ground beetle esterification reaction process
Pretreated frying abendoned oil and methyl alcohol are uniformly mixed, control the mass ratio 1:0.35 of frying abendoned oil and methyl alcohol, add the solid acid catalyst having sulfonic group and carboxylic acid group concurrently with large hydrophobic surface, catalyst levels is 1.5% of reactant total mass, carry out heated and stirred 12 h at 65 DEG C after, filtering recovering catalyst, catalyzer can directly be reused, distillation removing excessive methanol, carry out layering, upper strata is fatty acid methyl ester, yield 97%, and lower floor is that glycerin by-products is collected respectively;
4th step saturated fatty acid methyl ester sepn process.
Fatty acid methyl ester is cooled to 3 DEG C, after carrying out standing 10h, filter, separate solid saturated fatty acid methyl ester, obtain the fatty acid methyl ester of high double bond content.
5th step epoxidation series connection alkoxide open loop
The solid acid catalyst of the fatty acid methyl ester after separation and recovery is mixed, catalyst levels is 1.5% of reactant total mass, heated and stirred is carried out at 70 DEG C, drip the hydrogen peroxide of 30%, the mass ratio of hydrogen peroxide and fatty acid methyl ester is 1:0.4, during dropping, control temperature is lower than 80 DEG C, after dripping off, continue to react 3h at such a temperature, complete epoxidation, then, temperature is risen to 90 DEG C, add by-product glycerin as alkoxide reagent, be 1:0.2 with the mass ratio of fatty acid methyl ester, continue reaction 3h, stopped reaction, filtered and recycled solid acid catalyst, carry out after distillation dewaters, namely obtaining frying abendoned oil polylol product, hydroxyl value is 293mgKOH/g.
The present embodiment has following features: (1) the present embodiment is raw material with waste grease, reduces raw materials cost, avoids the pollution problem of waste grease, achieves and turn waste into wealth.(2) biological degradability of the biopolyol of gained is good, can fast degradation at nature, avoids white pollution.(4) employing has the esterification having the solid acid catalysis waste grease of sulfonic group and carboxylic acid group concurrently, the epoxidation series connection alkoxide ring opening process of large hydrophobic surface, simplify technical process, avoid the loaded down with trivial details aftertreatment of homogeneous acid catalyst, reduce the three waste discharge of industry.(5) the biopolyol molecular structure of gained and hydroxyl value all adjustable, can according to material choice and feed ratio Molecular regulator structure and hydroxyl value.(6) of many uses, alternative conventional petroleum polylol, for fields such as polyurethane foam, sizing agent, polyurethane coating, tensio-active agents.
embodiment 3
A kind of waste grease of the present embodiment prepares the method for polyvalent alcohol, comprises the steps:
1st step has the solid acid preparation having sulfonic group and carboxylic acid group concurrently of large hydrophobic surface
By butenoic acid, propene sulfonic acid and Vinylstyrene are dissolved in Virahol, solution solubility is 40%, wherein unsaturated carboxylic acid, unsaturated sulfonic acid and Vinylstyrene mass ratio be 0.13:0.25:1, under the initiation of Diisopropyl azodicarboxylate initiator, carry out mixed solvent hot copolymerization 5 h, initiator amount is 0.6% of reactant total mass, solvent thermal polymerization temperature is at 120 DEG C, cooling, filter, namely washing and drying obtains has the solid acid catalyst that large hydrophobic surface has sulfonic group and carboxylic acid group concurrently.
The preprocessing process of the 2nd step waste grease
After sewer oil being heated to 60 DEG C, carry out core filtration, the removing impurity such as earth, swill, washing composition wherein, then, the mode of decompression 110 DEG C distillation is adopted, except the moisture in degrease, finally, add acidic white earth and carry out adsorption bleaching, obtain the sewer oil after process.
3rd ground beetle esterification reaction process
Pretreated sewer oil and methyl alcohol are uniformly mixed, control the mass ratio 1:0.4 of sewer oil and methyl alcohol, add the solid acid catalyst having sulfonic group and carboxylic acid group concurrently with large hydrophobic surface, catalyst levels is 1.2% of reactant total mass, carry out heated and stirred 17 h at 65 DEG C after, filtering recovering catalyst, catalyzer can directly be reused, distillation removing excessive methanol, carry out layering, upper strata is fatty acid methyl ester, and yield is 95%, and lower floor is that glycerin by-products is collected respectively;
4th step saturated fatty acid methyl ester sepn process.
Fatty acid methyl ester is cooled to 3 DEG C, after carrying out standing 10h, filter, separate solid saturated fatty acid methyl ester, obtain the fatty acid methyl ester of high double bond content.
5th step epoxidation series connection alkoxide open loop
The solid acid catalyst of the fatty acid methyl ester after separation and recovery is mixed, catalyst levels is 1% of reactant total mass, heated and stirred is carried out at 75 DEG C, drip the hydrogen peroxide of 30%, the mass ratio of hydrogen peroxide and fatty acid methyl ester is 1:0.6, during dropping, control temperature is lower than 80 DEG C, after dripping off, continue to react 5h at such a temperature, then, temperature is risen to 90 DEG C, add by-product glycerin as alkoxide reagent, be 1:0.3 with the mass ratio of fatty acid methyl ester, continue reaction 3h, stopped reaction, filtered and recycled solid acid catalyst, carry out namely obtaining sewer oil polylol product after distillation dewaters, hydroxyl value is 384mgKOH/g.
The present embodiment has following features: (1) the present embodiment is raw material with waste grease, reduces raw materials cost, avoids the pollution problem of waste grease, achieves and turn waste into wealth.(2) biological degradability of the biopolyol of gained is good, can fast degradation at nature, avoids white pollution.(4) employing has the esterification having the solid acid catalysis waste grease of sulfonic group and carboxylic acid group concurrently, the epoxidation series connection alkoxide ring opening process of large hydrophobic surface, simplify technical process, avoid the loaded down with trivial details aftertreatment of homogeneous acid catalyst, reduce the three waste discharge of industry.(5) the biopolyol molecular structure of gained and hydroxyl value all adjustable, can according to material choice and feed ratio Molecular regulator structure and hydroxyl value.(6) of many uses, alternative conventional petroleum polylol, for fields such as polyurethane foam, sizing agent, polyurethane coating, tensio-active agents.
embodiment 4
A kind of waste grease of the present embodiment prepares the method for polyvalent alcohol, comprises the steps:
1st step has the solid acid preparation having sulfonic group and carboxylic acid group concurrently of large hydrophobic surface
By toxilic acid, hydroxy ethyl sulphonate and Vinylstyrene are dissolved in propyl carbinol, solution solubility is 35%, wherein unsaturated carboxylic acid, unsaturated sulfonic acid and Vinylstyrene mass ratio be 0.12:0.22:1, mixed solvent hot copolymerization 8 h is carried out under the initiation of Diisopropyl azodicarboxylate initiator, initiator amount is 0.5% of reactant total mass, solvent thermal polymerization temperature is at 140 DEG C, cooling, filter, namely washing and drying obtains has the solid acid catalyst that large hydrophobic surface has sulfonic group and carboxylic acid group concurrently.
The preprocessing process of the 2nd step waste grease
After condensate oil being heated to 60 DEG C, carry out core filtration, the removing impurity such as earth, swill, washing composition wherein, then, the mode of decompression 110 DEG C distillation is adopted, except the moisture in degrease, finally, add acidic white earth and carry out adsorption bleaching, obtain the condensate oil after process.
3rd ground beetle esterification reaction process
Pretreated condensate oil and methyl alcohol are uniformly mixed, control the mass ratio 1:0.45 of bio oil and methyl alcohol, add the solid acid catalyst having sulfonic group and carboxylic acid group concurrently with large hydrophobic surface, catalyst levels is 1.5% of reactant total mass, carry out heated and stirred 14 h at 75 DEG C after, filtering recovering catalyst, catalyzer can directly be reused, distillation removing excessive methanol, carry out layering, upper strata is fatty acid methyl ester, yield 98%, and lower floor is that glycerin by-products is collected respectively;
4th step saturated fatty acid methyl ester sepn process.
Fatty acid methyl ester is cooled to 2 DEG C, after carrying out standing 7h, filter, separate solid saturated fatty acid methyl ester, obtain the fatty acid methyl ester of high double bond content.
5th step epoxidation series connection alkoxide open loop
The solid acid catalyst of the fatty acid methyl ester after separation and recovery is mixed, catalyst levels is 1.5% of reactant total mass, heated and stirred is carried out at 70 DEG C, drip the hydrogen peroxide of 30%, the mass ratio of hydrogen peroxide and fatty acid methyl ester is 1:0.5, during dropping, control temperature is lower than 80 DEG C, after dripping off, continue to react 5h at such a temperature, complete epoxidation, then, temperature is risen to 90 DEG C, add by-product glycerin as alkoxide reagent, be 1:0.45 with the mass ratio of fatty acid methyl ester, continue reaction 3h, stopped reaction, filtered and recycled solid acid catalyst, carry out namely obtaining condensate oil polylol product after distillation dewaters, hydroxyl value is 259mgKOH/g.
The present embodiment has following features: (1) the present embodiment is raw material with waste grease, reduces raw materials cost, avoids the pollution problem of waste grease, achieves and turn waste into wealth.(2) biological degradability of the biopolyol of gained is good, can fast degradation at nature, avoids white pollution.(4) employing has the esterification having the solid acid catalysis waste grease of sulfonic group and carboxylic acid group concurrently, the epoxidation series connection alkoxide ring opening process of large hydrophobic surface, simplify technical process, avoid the loaded down with trivial details aftertreatment of homogeneous acid catalyst, reduce the three waste discharge of industry.(5) the biopolyol molecular structure of gained and hydroxyl value all adjustable, can according to material choice and feed ratio Molecular regulator structure and hydroxyl value.(6) of many uses, alternative conventional petroleum polylol, for fields such as polyurethane foam, sizing agent, polyurethane coating, tensio-active agents.
embodiment 5
A kind of waste grease of the present embodiment prepares the method for polyvalent alcohol, comprises the steps:
1st step has the solid acid preparation having sulfonic group and carboxylic acid group concurrently of large hydrophobic surface
By unsaturated carboxylic acid as vinylformic acid, styrene sulfonic acid and Vinylstyrene are dissolved in acetone, solution solubility is 25%, wherein unsaturated carboxylic acid, unsaturated sulfonic acid and Vinylstyrene mass ratio be 0.2:0.2:1, the hot copolymerization 8h of mixed solvent is carried out under the initiation of Diisopropyl azodicarboxylate initiator, initiator amount is 0.8% of reactant total mass, solvent thermal polymerization temperature is at 160 DEG C, cooling, filter, namely washing and drying obtains has the solid acid catalyst that large hydrophobic surface has sulfonic group and carboxylic acid group concurrently.
The preprocessing process of the 2nd step waste grease
After useless sheep oil is heated to 60 DEG C, carry out core filtration, the removing impurity such as earth, swill, washing composition wherein, then, the mode of decompression 110 DEG C distillation is adopted, except the moisture in degrease, finally, add acidic white earth and carry out adsorption bleaching, obtain the useless sheep oil after process.
3rd ground beetle esterification reaction process
Pretreated useless sheep oil is uniformly mixed with methyl alcohol, control the mass ratio 1:0.45 of useless sheep oil and methyl alcohol, add the solid acid catalyst having sulfonic group and carboxylic acid group concurrently with large hydrophobic surface, catalyst levels is 1.5% of reactant total mass, carry out heated and stirred 12h at 70 DEG C after, filtering recovering catalyst, catalyzer can directly be reused, distillation removing excessive methanol, carry out layering, upper strata is fatty acid methyl ester, and yield is 97%, and lower floor is that glycerin by-products is collected respectively;
4th step saturated fatty acid methyl ester sepn process.
Fatty acid methyl ester is cooled to 0 DEG C, after carrying out standing 12h, filter, separate solid saturated fatty acid methyl ester, obtain the fatty acid methyl ester of high double bond content.
5th step epoxidation series connection alkoxide open loop
The solid acid catalyst of the fatty acid methyl ester after separation and recovery is mixed, catalyst levels is 1.5% of reactant total mass, heated and stirred is carried out at 70 DEG C, drip the hydrogen peroxide of 30%, the mass ratio of hydrogen peroxide and fatty acid methyl ester is 1:0.7, during dropping, control temperature is lower than 80 DEG C, after dripping off, continue to react 6h at such a temperature, then, temperature is risen to 90 DEG C, add by-product glycerin as alkoxide reagent, be 1:0.3 with the mass ratio of fatty acid methyl ester, continue reaction 3h, stopped reaction, filtered and recycled solid acid catalyst, carry out namely obtaining useless sheep based oil product after distillation dewaters, hydroxyl value is 412mgKOH/g.
The present embodiment has following features: (1) the present embodiment is raw material with waste grease, reduces raw materials cost, avoids the pollution problem of waste grease, achieves and turn waste into wealth.(2) biological degradability of the biopolyol of gained is good, can fast degradation at nature, avoids white pollution.(4) employing has the esterification having the solid acid catalysis waste grease of sulfonic group and carboxylic acid group concurrently, the epoxidation series connection alkoxide ring opening process of large hydrophobic surface, simplify technical process, avoid the loaded down with trivial details aftertreatment of homogeneous acid catalyst, reduce the three waste discharge of industry.(5) the biopolyol molecular structure of gained and hydroxyl value all adjustable, can according to material choice and feed ratio Molecular regulator structure and hydroxyl value.(6) of many uses, alternative conventional petroleum polylol, for fields such as polyurethane foam, sizing agent, polyurethane coating, tensio-active agents.
embodiment 6
A kind of waste grease of the present embodiment prepares the method for polyvalent alcohol, comprises the steps:
1st step has the solid acid preparation having sulfonic group and carboxylic acid group concurrently of large hydrophobic surface
Direct use embodiment 5 reclaims catalyzer.
The preprocessing process of the 2nd step waste grease
After carclazyte oil is heated to 60 DEG C, carry out core filtration, the removing impurity such as earth, swill, washing composition wherein, then, the mode of decompression 110 DEG C distillation is adopted, except the moisture in degrease, finally, add acidic white earth and carry out adsorption bleaching, obtain the oil of the carclazyte after process.
3rd ground beetle esterification reaction process
Pretreated carclazyte oil is uniformly mixed with methyl alcohol, control the mass ratio 1:0.3 of carclazyte oil and methyl alcohol, add the solid acid catalyst having sulfonic group and carboxylic acid group concurrently with large hydrophobic surface, catalyst levels is 1.5% of reactant total mass, carry out heated and stirred 13 h at 70 DEG C after, filtering recovering catalyst, catalyzer can directly be reused, distillation removing excessive methanol, carry out layering, upper strata is fatty acid methyl ester, yield 98%, and lower floor is that glycerin by-products is collected respectively;
4th step saturated fatty acid methyl ester sepn process.
Fatty acid methyl ester is cooled to 3 DEG C, after carrying out standing 12h, filter, separate solid saturated fatty acid methyl ester, obtain the fatty acid methyl ester of high double bond content.
5th step epoxidation series connection alkoxide open loop
The solid acid catalyst of the fatty acid methyl ester after separation and recovery is mixed, catalyst levels is 1.5% of reactant total mass, heated and stirred is carried out at 70 DEG C, drip the hydrogen peroxide of 30%, the mass ratio of hydrogen peroxide and fatty acid methyl ester is 1:0.5, during dropping, control temperature is lower than 80 DEG C, after dripping off, continue to react 5h at such a temperature, then, temperature is risen to 85 DEG C, add by-product glycerin as alkoxide reagent, be 1:0.4 with the mass ratio of fatty acid methyl ester, continue reaction 3h, stopped reaction, filtered and recycled solid acid catalyst, carry out namely obtaining carclazyte based oil product after distillation dewaters, hydroxyl value is 403mgKOH/g.
The present embodiment has following features: (1) the present embodiment is raw material with waste grease, reduces raw materials cost, avoids the pollution problem of waste grease, achieves and turn waste into wealth.(2) biological degradability of the biopolyol of gained is good, can fast degradation at nature, avoids white pollution.(4) employing has the esterification having the solid acid catalysis waste grease of sulfonic group and carboxylic acid group concurrently, the epoxidation series connection alkoxide ring opening process of large hydrophobic surface, simplify technical process, avoid the loaded down with trivial details aftertreatment of homogeneous acid catalyst, reduce the three waste discharge of industry.(5) the biopolyol molecular structure of gained and hydroxyl value all adjustable, can according to material choice and feed ratio Molecular regulator structure and hydroxyl value.(6) of many uses, alternative conventional petroleum polylol, for fields such as polyurethane foam, sizing agent, polyurethane coating, tensio-active agents.
embodiment 7
Apply in polyurethane coating
Agitator is being housed, thermometer, swill oil polylol in 100 parts of embodiments 1 is added by a certain percentage in the 250ml four-hole boiling flask of reflux condensing tube and nitrogen conduit, 20 parts of dimethylol propionic acids and 60 parts of isophorone diisocyanates, be warming up to 90 DEG C, reaction 4h, be cooled to 60 DEG C, then, add 20 parts of triethylamines, carry out salt-forming reaction 1h, add 30 parts of methyl acrylates and 0.5 part of Diisopropyl azodicarboxylate, stirring after 20 minutes is scattered in 500 parts of water, add amine chainextender again and react 2h at 60 DEG C, slowly be warming up to 70 DEG C, reaction 1h, obtain aqueous polyurethane coating.
embodiment 8
Apply in polyurethane foam
By sheep based oil useless in 110 parts of embodiments 5,0.57 part of dibutyl tin dilaurate catalyzer, 3 parts of silicone oil stablizers, 4 parts of whipping agents are placed in solvent and are pre-mixed, turn 10 minutes with 1000 ~ 1200 rpm, then, the polymethylene multi-phenenyl isocyanate of 60 parts is added with in upper container, be uniformly mixed about 30 seconds with hand-held high speed agitator 2500 ~ 3000 rpm, mixture at room temperature reacts to expand and forms foam.
embodiment 9
Apply in adhesive for polyurethane
The sewer oil polylol 90 parts of preparation in embodiment 3, join in four-hole boiling flask, be warmed up to 105 DEG C, vacuumize 4h, logical nitrogen concora crush, after bubbling is stable, stops vacuumizing, be cooled to about 70 DEG C, 0.4 part of dibutyl tin dilaurate catalyzer, adds tolylene diisocyanate 50 parts, isophorone diisocyanate 60 parts, have from warming phenomenon, be warmed up to 85 DEG C, be incubated at 85 DEG C of 2h, until reach one section of reaction end (titration of toluene Di-n-Butyl Amine method), add the toluene solvant of 200 parts, obtain adhesive for polyurethane.
Claims (6)
1. a waste grease prepares the method for polyvalent alcohol, it is characterized in that, comprise the steps: to adopt the solid acid catalyst having sulfonic group and carboxylic acid group concurrently with large hydrophobic surface, catalysis waste grease and methyl alcohol carry out esterification and transesterification reaction, waste grease are converted into fatty acid methyl ester and by-product glycerol; Then lower the temperature, the mode of the polyunsaturated fatty acid ester in fatty acid methyl ester by crystallization is separated, improve the content of double bond in fatty acid methyl ester; Then continue under bisgallic acid central solid acid catalysis, utilize the collaborative of bisgallic acid center, fatty acid methyl ester is carried out epoxidation by the hydrogen peroxide of direct catalysis 30%, and intermediate product, without separation, after directly heating up, adds by-product glycerol and carries out alkoxide open loop; Last filtering recovering catalyst, namely obtains bio oil polylol after underpressure distillation dewaters.
2. a kind of waste grease according to claim 1 prepares the method for polyvalent alcohol, it is characterized in that, described step is specially:
1) there is the solid acid preparation having sulfonic group and carboxylic acid group concurrently of large hydrophobic surface
By unsaturated carboxylic acid, be dissolved in organic solvent containing the sulfonic acid of unsaturated double-bond and Vinylstyrene, solution solubility is 20 ~ 65%, mixed solvent hot copolymerization 2 ~ 10 h is carried out under the initiation of Diisopropyl azodicarboxylate initiator, initiator amount is 0.1% ~ 1% of reactant total mass, and solvent thermal polymerization temperature, at 80 ~ 180 DEG C, cools, filter, namely washing and drying obtains has the solid acid catalyst that large hydrophobic surface has sulfonic group and carboxylic acid group concurrently;
2) preprocessing process of waste grease
After waste grease being heated to 60 DEG C, carry out core filtration, the removing impurity such as earth, swill, washing composition wherein, then the mode of decompression 110 DEG C distillation is adopted, except the moisture in degrease, finally, add acidic white earth and carry out adsorption bleaching, obtain the waste grease after process;
3) esterification reaction of organic acid process
Waste grease pretreated for step 1) and methyl alcohol are uniformly mixed, control the mass ratio 1:0.2 ~ 1:1.1 of waste grease and methyl alcohol, add step 2) solid acid catalyst having sulfonic group and carboxylic acid group concurrently with large hydrophobic surface prepared, catalyst levels is 0.5% ~ 3% of reactant total mass, carry out heated and stirred 5 ~ 21 h at 60 ~ 80 DEG C after, filtering recovering catalyst, catalyzer can directly be reused, distillation removing excessive methanol, carry out layering, upper strata is fatty acid methyl ester, and lower floor is that glycerin by-products is collected respectively;
4) saturated fatty acid methyl ester sepn process.
3. fatty acid methyl ester prepared by step 3) is cooled to-5 ~ 15 DEG C, after carrying out standing 2 ~ 14h, filter, separate solid saturated fatty acid methyl ester, obtain the fatty acid methyl ester of high double bond content;
5) epoxidation series connection alkoxide open loop
Fatty acid methyl ester after step 4) being separated and the solid acid catalyst of recovery mix, catalyst levels is 0.5% ~ 2% of reactant total mass, heated and stirred is carried out at 50 ~ 80 DEG C, drip the hydrogen peroxide of 30%, the mass ratio of hydrogen peroxide and fatty acid methyl ester is 1:0.2 ~ 1:1, during dropping, control temperature is lower than 80 DEG C, after dripping off, continue to react 0.5 ~ 8h at such a temperature, complete epoxidation, then, temperature is risen to 80 ~ 100 DEG C, add by-product glycerin as alkoxide reagent, be 1:0.1 ~ 1:0.5 with the mass ratio of fatty acid methyl ester, continue reaction 0.5 ~ 4h, stopped reaction, filtered and recycled solid acid catalyst, carry out namely obtaining biopolyol product after distillation dewaters.
4. a kind of waste grease according to claim 1 and 2 prepares the method for polyvalent alcohol, it is characterized in that, described have the preparation method that large hydrophobic surface has the solid acid catalyst of sulfonic acid and carboxylic acid group concurrently and be: by unsaturated carboxylic acid, be dissolved in organic solvent containing the sulfonic acid of unsaturated double-bond and Vinylstyrene, wherein unsaturated carboxylic acid, unsaturated sulfonic acid and Vinylstyrene mass ratio be (0.05 ~ 0.2): (0.01 ~ 0.3): 1, mixed solvent hot copolymerization 2 ~ 10 h is carried out under the initiation of Diisopropyl azodicarboxylate initiator, polymerization temperature is at 80 ~ 180 DEG C, cooling, filter, namely washing and drying obtains has the solid acid catalyst that large hydrophobic surface has sulfonic group and carboxylic acid group concurrently, wherein said unsaturated carboxylic acid adopts the one in vinylformic acid, butenoic acid, toxilic acid, fumaric acid, pentenoic acid, the described sulfonic acid containing unsaturated double-bond adopts the one in styrene sulfonic acid, vinyl sulfonic acid, propene sulfonic acid, hydroxy ethyl sulphonate, described organic solvent adopts the one in ethyl acetate, propyl carbinol, tetrahydrofuran (THF), Virahol, acetone.
5. a kind of waste grease according to claim 1 and 2 prepares the method for polyvalent alcohol, it is characterized in that: the animal-plant oil not allowing to eat that described waste grease adopts food and drink, food-processing unit and family to produce, animal slaughtering segmentation and leather processing repair the grease of the offal treatment refinement of cutting, the grease produced in the food oils refining course of processing, the one in the expired grease produced in Oil processing or grease storage process; The animal-plant oil not allowing to eat that described food and drink, food-processing unit and family produce adopts the one in swill oil, frying abendoned oil, sewer oil and smoke exhaust ventilator condensate oil; Described animal slaughtering segmentation and leather processing repair the one that grease that the offal treatment of cutting refines adopts useless butter, useless sheep oil, useless lard, gives up in chicken fat; The grease produced in the described food oils refining course of processing adopts the one in acidification oil, carclazyte oil, deodorization distilled oil; The expired grease produced in described Oil processing or grease storage process adopts expired rapeseed oil, expired soybean oil, the one in plant produced heat conduction abendoned oil.
6. the application of polyvalent alcohol prepared of the method utilizing the waste grease described in claim 1 to prepare polyvalent alcohol, it is characterized in that: waste grease as claimed in claim 1 is prepared polyvalent alcohol and had molecular structure and all adjustable feature of hydroxyl value, various polyurethane coating, urethane foam, sizing agent, rapid prototyping material, fibre reinforced composites, surfactant field can be widely used in, as the green replacer of conventional polyether polyols or polyester polyol.
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| CN105567758A (en) * | 2016-01-12 | 2016-05-11 | 华南理工大学 | Method for preparing epoxy fatty acid methyl ester |
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| CN106520381A (en) * | 2016-11-11 | 2017-03-22 | 云南磷化集团有限公司 | Decoloration and deodorization method for drainage oil fatty acid |
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| CN110092882A (en) * | 2019-05-31 | 2019-08-06 | 山东理工大学 | Method based on waste paint slag preparation flame retarded polyurethane-foam material |
| CN110092882B (en) * | 2019-05-31 | 2021-06-22 | 山东理工大学 | Method for preparing flame-retardant polyurethane foam material based on waste paint residues |
| CN116396455A (en) * | 2023-05-26 | 2023-07-07 | 广州艾科新材料股份有限公司 | Method for preparing polyol and polyurethane from reclaimed oil |
| CN116396455B (en) * | 2023-05-26 | 2023-08-11 | 广州艾科新材料股份有限公司 | Method for preparing polyol and polyurethane from reclaimed oil |
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