CN107930660B - A kind of catalyst and its method for preparing epoxidized linseed oil - Google Patents
A kind of catalyst and its method for preparing epoxidized linseed oil Download PDFInfo
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- CN107930660B CN107930660B CN201711187968.XA CN201711187968A CN107930660B CN 107930660 B CN107930660 B CN 107930660B CN 201711187968 A CN201711187968 A CN 201711187968A CN 107930660 B CN107930660 B CN 107930660B
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- linseed oil
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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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
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/06—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the liquid phase
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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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- Catalysts (AREA)
Abstract
A kind of catalyst and its method for preparing epoxidized linseed oil, belong to technical field of organic synthesis, wherein catalyst is made via following steps: a) being roasted, ground to kaolin；B) take grinding after kaolin mixed with calcirm-fluoride, cobalt oxide and zinc oxide, mixed system with the rate of 15~25 DEG C/min be warming up to 750~760 DEG C of 3~6 h of heat preservation to get.The composite catalyst raw material is extensive, low in cost, and preparation process is simple, facilitates recycling after use, has great promotional value.Utilize the method for the catalyst preparation epoxidized linseed oil, comprising the following steps: 1) mix linseed oil, solvent, catalyst；2) reaction gas and 1.1~1.2 atmospheric pressure of maintenance system pressure are passed through, 2~4h are stirred to react at 70~85 DEG C, separating-purifying is up to product epoxidized linseed oil.This method reaction process is simple direct, green safe, obtains the epoxide number of product up to 10 or more.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of kaolin composite catalyst and utilize the catalysis
The method that agent prepares epoxidized linseed oil.
Background technique
With the rapid development of modern plastics industry and textile and dyeing industry, the dosage of plasticizer is dramatically increased.City at present
More common plasticizer is phthalate on field, and phthalic ester plasticizer can be to empty gas and water and soil
It is polluted to food, and degradation speed is extremely slow in the environment, thus becomes the global environmental contaminants being concerned.Epoxy
Class plasticizer is a kind of novel non-toxic plasticizer of successful exploitation recently, it refers to organic with epoxy group in molecular structure
Compound has many advantages, such as that nontoxic, heat-resisting and light resistance is good compared with traditional adjacent benzene class plasticizer；Not only polyvinyl chloride is risen
Plasticization, and the hydrogen chloride of the degradation releasing because of light and heat can be absorbed rapidly, unstable hydroxy chloride is reduced for alkene
The continuous decomposition of igelite is blocked in the formation of propyl conjugated double bond, therefore it plays stabilizer again.Meanwhile it
It can be combined with polyesters plasticizer, have apparent synergistic effect to the migration for reducing polyester, moreover it is possible to stablize with organic metal salt
Agent uses simultaneously and generates synergistic effect, reduces the dosage of organic metal salt.
As a kind of high-quality plants oil, itself has 3 carbon-carbon double bonds, the ring of high epoxy value can be made linseed oil
Oxygen compound is that current other plant oil is incomparable.Existing synthesizing epoxy linseed oil mainly uses hydrogen peroxide as epoxy
Reagent (such as CN201610706491, CN201610706488, CN200710180042, CN201610706722,
CN201610707033, CN201610730746), the seriously polluted defect of equipment, production process is easily corroded, it is simultaneously synthesizing
Epoxidized vegetable oil stability is lower, can not efficient long duration of action therefore find that a kind of efficient, synthetic method is simple and ring
The method of guarantor is necessary.
Summary of the invention
The purpose of the present invention is intended to provide a kind of kaolin composite catalyst, provides and utilizes the catalyst preparation epoxy flax
The method of oil is then another goal of the invention of the invention.
Based on above-mentioned purpose, this invention takes following technical solutions: a kind of catalyst, which is characterized in that the catalysis
Agent is made via following steps: a) being roasted, is ground to kaolin；B) kaolin and calcirm-fluoride, cobalt oxide after taking grinding
With zinc oxide mix, mixed system with the rate of 15~25 DEG C/min be warming up to 750~760 DEG C of 3~6 h of heat preservation to get.Metal
Oxide mixed with kaolin after through high temperature sintering, different sintering temperatures have different reforming structures, and heating rate is too fast at this time,
It is easy to cause in sintering process that each component Structural assignments are excessively chaotic, the final structure for being unfavorable for catalyst is reformed, and is formed opposite
Unified arrangement (realization that the structure is conducive to best catalytic effect)；Heating rate is excessively slow, imitates to the catalysis of catalyst
Fruit is not improved, elapsed time.3~6 h are kept the temperature, reconstruction optimization is conducive to improve catalytic efficiency.At 750~760 DEG C
It is sintered, advantageously forms to form the structure with preferable catalytic activity；Sintering temperature is low, then metallic compound cannot be regular
Ground loads on kaolin, and the active interface of formation is not abundant enough, reduces catalytic efficiency；Higher than this temperature, each metal oxide
Preferably support structures in kaolin can be broken, and part of the metal oxide part is caused to be enriched with, and be unfavorable for optimizing interface
Formation, reduce catalytic efficiency.
The weight ratio of kaolin and calcirm-fluoride, cobalt oxide, zinc oxide is 1:(0.015~0.023): (0.026~
0.033): (0.009~0.016).Under this ratio, kaolinic porous structure can preferably distribute supported catalyst, make
Reaction gas and linseed oil are obtained under interface interaction, it is easier to oxidation occur, form epoxy construction.
In the step a), kaolin is warming up to 350~355 DEG C with the rate of 2~5 DEG C/min, roasts 5~7 h.Roasting
Burning kaolin can be allowed to activate, and heating rate is excessively slow when roasting, time-consuming too long, influence production efficiency；It heats up too fast, is easy to lead
Kaolin hardness and Density inhomogeneity are caused, load effect is influenced, and is unfavorable for grinding in next step.It is experimentally confirmed that being warming up to 350-
355 DEG C of roasting a period of times, load effect are good；Continue to improve maturing temperature, load effect difference is little, wastes energy consumption.
In the step a), kaolin is ground to 400~600 mesh.The kaoline loaded rate of fineness structure that is high, and being formed
Stablize, excellent catalytic effect.
Utilize the method for the catalyst preparation epoxidized linseed oil, comprising the following steps:
1) linseed oil, solvent, catalyst are mixed；
2) reaction gas and 1.1~1.2 atmospheric pressure of maintenance system pressure are passed through, are stirred to react 2~4h at 70~85 DEG C,
Separating-purifying is up to product epoxidized linseed oil；
In step 1), the solvent is the mixture of water and organic solvent；
In step 2, the reaction gas is air, oxygen or ozone.
In step 1), the linseed oil, solvent, catalyst three weight ratio 1:(30~45): (0.02~0.05).
In step 1), the organic solvent be one or both of petroleum ether, dioxane, n-hexane, hexamethylene with
Upper mixture；Weight ratio 1:(7.5~9 of water and the organic solvent).A small amount of water is added, in order to adjust mixed solvent
Interfacial tension, increase response area when being passed through reaction gas, that is, adjust the size of reaction bubble
The concrete operations of separating-purifying are as follows: add water to filter, gained filtrate adds organic solvent extraction, takes organic phase to be evaporated off molten
Agent.After reaction, linseed oil and epoxidized linseed oil Polarity comparision are strong, and kaolin, which meets, is partially dissolved in reactant in catalyst
In system, adds water filtering to be on the one hand to remove the impurity insoluble in water-oil phase, be on the other hand equivalent to " extraction ", remove and produce
Polar substances in object.
The organic solvent used is extracted as ether.
In separating-purifying, the additional amount of water is 1~1.5 times of solvent gross weight in step 1).
Compared with prior art, the present invention has following technical effect that
1) composite catalyst provided by the invention, raw material is extensive, low in cost, and preparation process is simple, facilitates back after use
It receives, there is great promotional value.
2) the present invention make by oneself kaolin composite catalyst under the action of, linseed oil is reacted with oxidizing gas, gas with
The form of free radical directly opens the double bond structure of linseed oil, forms three-membered ring structures, realizes epoxidation, not only reaction process
Simply, directly；And epoxide number is higher, epoxide number is up to 10 or more；
3) method of the invention is avoided using oxidizing gas such as air, oxygen as reaction gas using hydrogen peroxide, acid etc.
Epoxy agent not only reduces equipment corrosion, reduces cost of equipment maintenance, operate it is also safer, and when using air, cost
Lower, operation is also more convenient.
Specific embodiment
Combined with specific embodiments below, the invention will be further described.
Embodiment 1
A kind of catalyst is made via following steps:
A) it takes kaolin to be warming up to 350 DEG C with the rate of 2 DEG C/min, roasts 5 h, be then ground to 400 mesh；
B) kaolin after taking grinding is with calcirm-fluoride, cobalt oxide and zinc oxide according to the weight of 1:0.015:0.026:0.009
Amount is warming up to 750 DEG C of 3 h of heat preservation with the rate of 15 DEG C/min than mixing, mixed system to get catalyst A.
The method for preparing epoxidized linseed oil using catalyst A, comprising the following steps:
1) water and hexamethylene are mixed according to weight ratio 1:7.5, reaction dissolvent is made；Take 10 g linseed oil, 300 g reaction
Solvent, the mixing of 0.2 g catalyst；
2) 70 DEG C are warming up to, air maintenance system pressure is continually fed into 1.1 atmospheric pressure, is stirred to react 2h.Reaction knot
According to following operation separating-purifying after beam: 300g water is added, stirs, filtering, filtrate adds ether extraction, takes organic phase and is evaporated off
Solvent obtains product epoxidized linseed oil O1。
Embodiment 2
A kind of catalyst is made via following steps:
A) it takes kaolin to be warming up to 350 DEG C with the rate of 4 DEG C/min, roasts 6h, be then ground to 500 mesh；
B) kaolin after taking grinding is with calcirm-fluoride, cobalt oxide and zinc oxide according to the weight of 1:0.02:0.03:0.012
Than mixing, mixed system is warming up to 755 DEG C of 5 h of heat preservation with the rate of 20 DEG C/min to get catalyst B.
The method for preparing epoxidized linseed oil using catalyst B, comprising the following steps:
1) water and dioxane are mixed according to weight ratio 1:8, reaction dissolvent is made；Take 10 g linseed oil, 400 g reaction
Solvent, the mixing of 0.4 g catalyst；
2) 80 DEG C are warming up to, air maintenance system pressure is continually fed into 1.15 atmospheric pressure, is stirred to react 3h.Reaction knot
According to following operation separating-purifying after beam: 600g water is added, stirs, filtering, filtrate adds ether extraction, takes organic phase and is evaporated off
Solvent obtains product epoxidized linseed oil O1。
Embodiment 3
A kind of catalyst is made via following steps:
A) it takes kaolin to be warming up to 355 DEG C with the rate of 5 DEG C/min, roasts 7 h, be then ground to 600 mesh；
B) kaolin after taking grinding is with calcirm-fluoride, cobalt oxide and zinc oxide according to the weight of 1:0.023:0.033:0.016
Amount is warming up to 760 DEG C of 6 h of heat preservation with the rate of 25 DEG C/min than mixing, mixed system to get catalyst C.
The method for preparing epoxidized linseed oil using catalyst C, comprising the following steps:
1) water and petroleum ether are mixed according to weight ratio 1:9, reaction dissolvent is made；Take 10 g linseed oil, 450 g reaction molten
Agent, the mixing of 0.5 g catalyst；
2) 85 DEG C are warming up to, air maintenance system pressure is continually fed into 1.2 atmospheric pressure, is stirred to react 4h.Reaction knot
According to following operation separating-purifying after beam: 540g water is added, stirs, filtering, filtrate adds ether extraction, takes organic phase and is evaporated off
Solvent obtains product epoxidized linseed oil O1。
4 comparative test of embodiment
Technical effect of the invention compares test.
The method referring to as defined in " measurement of GB/T1677-2008 plasticizer epoxide number " measures epoxide number: with the present invention
Epoxidized linseed oil O1, O2 and O3 obtained by embodiment measure epoxide number as experiment sample；With documents CN201610706491,
CN201610706488, CN200710180042, CN201610706722, CN201610707033, CN201610730746 are each
Control sample is prepared from embodiment method, measures respectively maximum epoxide number.
The epoxide number test result of 1 present invention of table and reference substance
As can be seen from Table 1, compared with reference substance, the epoxide number of present invention gained epoxidized linseed oil is higher, and quality is more preferable.
Claims (8)
1. a kind of catalyst, which is characterized in that the catalyst is made via following steps:
A) kaolin roasted, ground；
B) kaolin after taking grinding is mixed with calcirm-fluoride, cobalt oxide and zinc oxide, and mixed system is with the speed of 15~25 DEG C/min
Rate be warming up to 750~760 DEG C of 3~6 h of heat preservation to get；
Wherein, the weight ratio of kaolin and calcirm-fluoride, cobalt oxide, zinc oxide is 1:(0.015~0.023): (0.026~
0.033): (0.009~0.016).
2. catalyst as described in claim 1, which is characterized in that in the step a), by kaolin with 2~5 DEG C/min's
Rate is warming up to 350~355 DEG C, roasts 5~7 h.
3. catalyst as claimed in claim 2, which is characterized in that in the step a), kaolin is ground to 400~600 mesh.
4. utilizing the method for catalyst preparation epoxidized linseed oil described in claim 1, which comprises the following steps:
1) linseed oil, solvent, catalyst are mixed；The linseed oil, solvent, catalyst three weight ratio 1:(30~45):
(0.02~0.05)；
2) reaction gas and 1.1~1.2 atmospheric pressure of maintenance system pressure are passed through, 2~4h is stirred to react at 70~85 DEG C, are separated
It purifies up to product epoxidized linseed oil；
In step 1), the solvent is the mixture of water and organic solvent；
In step 2, the reaction gas is air, oxygen or ozone.
5. the method for preparing epoxidized linseed oil as claimed in claim 4, which is characterized in that in step 1), the organic solvent is
One or more mixtures of petroleum ether, dioxane, n-hexane, hexamethylene；The weight of water and the organic solvent
Than 1:(7.5~9).
6. preparing the method for epoxidized linseed oil as described in claim 4 or 5, which is characterized in that the concrete operations of separating-purifying are as follows:
Water is added to filter, gained filtrate adds organic solvent extraction, takes organic phase that solvent is evaporated off.
7. the method for preparing epoxidized linseed oil as claimed in claim 6, which is characterized in that extract the organic solvent used as second
Ether.
8. the method for preparing epoxidized linseed oil as claimed in claim 7, which is characterized in that in separating-purifying, the additional amount of water is
1~1.5 times of solvent gross weight in step 1).
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3340213A (en) * | 1964-05-19 | 1967-09-05 | Union Carbide Corp | Coating compositions from monoepoxy alcohols |
| CA807184A (en) * | 1969-02-25 | Halcon International | Epoxidation process | |
| CA2821469A1 (en) * | 2012-07-27 | 2014-01-27 | Xerox Corporation | Chemical binding of renewable oils to polyester emulsion |
| CN105153074A (en) * | 2015-10-01 | 2015-12-16 | 常州市奥普泰科光电有限公司 | Method for preparing epoxy flax oil plasticizers |
| CN106221244A (en) * | 2016-08-23 | 2016-12-14 | 成都米特瑞新材料科技有限公司 | A kind of epoxidized linseed oil and citric acid composite elasticizer |
| CN106244336A (en) * | 2016-08-26 | 2016-12-21 | 南通海珥玛科技股份有限公司 | A kind of preparation method of high epoxy value epoxidized linseed oil |
| CN106316989A (en) * | 2016-08-23 | 2017-01-11 | 成都米特瑞新材料科技有限公司 | Preparation technique of improved epoxy flaxseed oil plasticizer |
| CN106398236A (en) * | 2016-08-23 | 2017-02-15 | 成都米特瑞新材料科技有限公司 | Process for compounding epoxy linseed oil and citric acid to obtain plasticizer |
-
2017
- 2017-11-24 CN CN201711187968.XA patent/CN107930660B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA807184A (en) * | 1969-02-25 | Halcon International | Epoxidation process | |
| US3340213A (en) * | 1964-05-19 | 1967-09-05 | Union Carbide Corp | Coating compositions from monoepoxy alcohols |
| CA2821469A1 (en) * | 2012-07-27 | 2014-01-27 | Xerox Corporation | Chemical binding of renewable oils to polyester emulsion |
| CN105153074A (en) * | 2015-10-01 | 2015-12-16 | 常州市奥普泰科光电有限公司 | Method for preparing epoxy flax oil plasticizers |
| CN106221244A (en) * | 2016-08-23 | 2016-12-14 | 成都米特瑞新材料科技有限公司 | A kind of epoxidized linseed oil and citric acid composite elasticizer |
| CN106316989A (en) * | 2016-08-23 | 2017-01-11 | 成都米特瑞新材料科技有限公司 | Preparation technique of improved epoxy flaxseed oil plasticizer |
| CN106398236A (en) * | 2016-08-23 | 2017-02-15 | 成都米特瑞新材料科技有限公司 | Process for compounding epoxy linseed oil and citric acid to obtain plasticizer |
| CN106244336A (en) * | 2016-08-26 | 2016-12-21 | 南通海珥玛科技股份有限公司 | A kind of preparation method of high epoxy value epoxidized linseed oil |
Non-Patent Citations (1)
| Title |
|---|
| "臭氧用于油脂环氧化";姚东阳;《化学工程与装备》;20170131(第1期);第57-59页 |
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