CN112321423A - Synthesis process of tributyrin - Google Patents
Synthesis process of tributyrin Download PDFInfo
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- CN112321423A CN112321423A CN202011443089.0A CN202011443089A CN112321423A CN 112321423 A CN112321423 A CN 112321423A CN 202011443089 A CN202011443089 A CN 202011443089A CN 112321423 A CN112321423 A CN 112321423A
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- UYXTWWCETRIEDR-UHFFFAOYSA-N Tributyrin Chemical compound CCCC(=O)OCC(OC(=O)CCC)COC(=O)CCC UYXTWWCETRIEDR-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000003786 synthesis reaction Methods 0.000 title claims description 18
- 230000015572 biosynthetic process Effects 0.000 title claims description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims abstract description 54
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- 238000005886 esterification reaction Methods 0.000 claims abstract description 40
- 238000001914 filtration Methods 0.000 claims abstract description 34
- 239000007787 solid Substances 0.000 claims abstract description 28
- 230000002378 acidificating effect Effects 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 230000032050 esterification Effects 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 8
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910003082 TiO2-SiO2 Inorganic materials 0.000 claims abstract description 7
- 239000005909 Kieselgur Substances 0.000 claims abstract description 6
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 11
- 230000005587 bubbling Effects 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 238000005292 vacuum distillation Methods 0.000 claims description 6
- 238000004042 decolorization Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 210000003298 dental enamel Anatomy 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 239000010865 sewage Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 3
- 238000011085 pressure filtration Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000001704 evaporation Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000003223 protective agent Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 210000001035 gastrointestinal tract Anatomy 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000000968 intestinal effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 235000019737 Animal fat Nutrition 0.000 description 1
- 108090000371 Esterases Proteins 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 102000015728 Mucins Human genes 0.000 description 1
- 108010063954 Mucins Proteins 0.000 description 1
- 102000000591 Tight Junction Proteins Human genes 0.000 description 1
- 108010002321 Tight Junction Proteins Proteins 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 235000013310 margarine Nutrition 0.000 description 1
- 239000003264 margarine Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 210000001578 tight junction Anatomy 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a process for synthesizing tributyrin, which comprises the following steps: adding butyric acid, glycerol and a solid super acidic catalyst into a reaction kettle for heating esterification reaction, and simultaneously evaporating water generated in the reaction; step (2), distilling off excessive butyric acid in the reaction solution; step (3), filtering and recovering the solid super acidic catalyst; and (4) carrying out activated carbon decoloration treatment on the filtered crude tributyrin. The method is simple in operation and adopts SO4 2‑/SnO2Diatomaceous earth, SO4 2‑/MoO3‑TiO2‑SiO2、SO4 2‑/ZrO2‑NiO、SO4 2‑/ZrO2‑Sm2O3‑SiO2Any one of the two is used as a catalyst, the catalytic activity is high, the cost is low, the post-treatment operation method is simple, and the esterification rate can be kept high after repeated utilization, so that the method is suitable for industrial large-scale production.
Description
Technical Field
The invention belongs to the technical field of fine chemical synthesis, and particularly relates to a process for synthesizing tributyrin.
Background
The tributyrin naturally exists in animal fat, vegetable oil, dairy products and the like, is a product obtained by heating and esterifying glycerol and butyric acid, and has wide application. The method is mainly used for preparing spices such as cream, margarine and the like in the industrial field; in the field of biotechnology, the lipase is often used as a substrate for screening and characterizing esterase; can also be used as feed additive. Research reports that tributyrin can smoothly pass through the gastrointestinal tract and is slowly decomposed into butyric acid, and then reaches the rear end of the intestinal tract to exert corresponding physiological effects. The tributyrin can promote intestinal villus growth, enhance digestion of nutrient substances, maintain intestinal flora balance, enhance tight junction, promote secretion of mucin, improve immunity, and further improve animal productivity.
Currently, the main synthetic routes of tributyrin are: glycerol and butyric acid are used as raw materials, and toxic organic solvents (carbon tetrachloride, toluene, benzene and the like) are used as water-carrying agents under the catalysis of strong acid (p-toluenesulfonic acid, sulfuric acid, phosphoric acid and the like). The method generates more waste acid, seriously corrodes equipment, is not easy to control the process and is inconvenient to process and operate after reaction. Patent CN105801413A discloses a method for obtaining tributyrin by rectification and reduced pressure distillation using glycerol and butyric acid as raw materials, a solid super acidic catalyst, nitrogen as a protective agent and a water-carrying agent. However, the method described above uses SO42-/ZrO2-TiO2、SO42-/Fe2O3-TiO2、S2O8 2-/ZrO2-SiO2、SO4 2-/Fe2O3、SO4 2-/TiO2、SO4 2-/ZrO2As a solid super acidic catalyst, the solid super acidic catalyst has problems in use, such as poor stability and easy deactivation, and the esterification rate is reduced to 80% after the catalyst is used for 5 times. Therefore, a more complete synthesis process of tributyrin is urgently needed to be developed.
Disclosure of Invention
The invention aims to provide a process for synthesizing tributyrin, which aims to solve the technical problems of inconvenient treatment operation, poor catalyst stability and low catalyst recycling rate of the existing process for synthesizing tributyrin after reaction.
The synthesis process comprises the following steps:
step (1): opening a feed inlet of a reaction kettle, adding butyric acid, glycerol and a solid super acidic catalyst into the reaction kettle, starting a stirring device of the reaction kettle after the feeding is finished, introducing nitrogen into the reaction kettle, heating the reaction kettle for esterification reaction, simultaneously opening a steam valve of the reaction kettle, opening circulating water of a condenser, performing heating distillation operation, maintaining the temperature in the reaction kettle within the range of 100-105 ℃, collecting a first-stage fraction while performing esterification reaction until no fraction is evaporated out, and finishing the esterification reaction; the solid super acidic catalyst is SO4 2-/SnO2Diatomaceous earth, SO4 2-/MoO3-TiO2-SiO2、SO4 2-/ZrO2- NiO、SO4 2-/ ZrO2- Sm2O3-SiO2Any one of the above;
step (2): after the first-stage fraction is collected, heating and heating the reaction kettle continuously, keeping the temperature in the reaction kettle within the range of 120-135 ℃, stopping introducing nitrogen into the reaction kettle, collecting the second-stage fraction by adopting a vacuum distillation method until no fraction is evaporated, stopping heating and vacuumizing, weighing the obtained second-stage fraction, and barreling for later use for cyclic utilization in the next esterification reaction;
and (3): naturally cooling the residual materials in the reaction kettle to room temperature, then carrying out filtration operation, continuously recycling the solid super acidic catalyst obtained by filtration, and further purifying the crude tributyrin obtained by filtration;
and (4): and (4) adding activated carbon into the crude tributyrin obtained in the step (3) to carry out decoloring treatment, and after the decoloring treatment is finished, carrying out circulating filtration by using a felt filter with the pore size of 1200 meshes, wherein the pressure of the circulating filtration is 0.25MPa, and after the filtration is finished, obtaining colorless oily liquid tributyrin.
Preferably, the molar ratio of butyric acid to glycerol in step (1) is (3-5): 1, the mass ratio of the solid super acidic catalyst to the glycerol is 1-5%.
Preferably, the reaction time in step (1) is 3 to 5 hours and the degree of vacuum in step (2) is 0.05 to 0.1 MPa.
Preferably, the first stage fraction in the step (1) is water containing a small amount of butyric acid, the second stage fraction in the step (2) is butyric acid, a small amount of sodium hydroxide solution is added into the first stage fraction for neutralization treatment, and then the first stage fraction can be directly discharged into a sewage treatment station for treatment, and the second stage fraction is collected for later use.
Preferably, the solid super acidic catalyst obtained by filtering in the step (3) can be reused for more than 10 times, and the esterification rate is still more than 95% after the solid super acidic catalyst is reused for 10 times.
Preferably, the filtration mode in the step (3) is suction filtration or pressure filtration.
Preferably, in the step (4), nitrogen is introduced into the crude tributyrin for bubbling when the activated carbon decolorization treatment is performed.
Preferably, the reaction kettle is an enamel reaction kettle with a distillation device.
The invention has the beneficial effects that: the process route is mature, the safety risk is small, the post-treatment operation is simple, and the solid super acidic catalyst is adopted, so that compared with the prior art in which strong acidic catalysts such as p-toluenesulfonic acid, sulfuric acid and phosphoric acid are adopted, the process can avoid a large amount of waste acid from the reaction solution, simplify the operation steps of the post-treatment of the reaction and reduce the corrosion to equipment; and with SO4 2-/SnO2Diatomaceous earth, SO4 2-/MoO3-TiO2-SiO2、SO4 2-/ZrO2- NiO、SO4 2-/ ZrO2-Sm2O3-SiO2As a catalyst, the catalyst has high catalytic activity, low cost and simple post-treatment operation method, can still keep higher esterification rate after being repeatedly utilized for many times, meets the requirement of green sustainable development, and is suitable for industrial large-scale production.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
The invention provides a process for synthesizing tributyrin, which comprises the following steps:
step (1): opening a feed inlet of the reaction kettle, adding butyric acid, glycerol and a solid super acidic catalyst into the reaction kettle, starting a stirring device of the reaction kettle after the feeding is finished, introducing nitrogen into the reaction kettle, heating the reaction kettle to perform an esterification reaction, simultaneously opening a steam valve of the reaction kettle, opening circulating water of a condenser, performing heating distillation operation, maintaining the temperature in the reaction kettle within the range of 100-105 ℃, and collecting a first-stage fraction while performing the esterification reaction. On the one hand, the nitrogen serves as a water-carrying agent to accelerate the evaporation of water in the reaction liquid, so that the reaction is favorably carried out rightwards, the efficiency of the esterification reaction is improved, and on the other hand, the nitrogen can serve as a bubbling agent and a protective agent to ensure that the reaction atmosphere is in an inert environment, and the raw materials can be fully mixed to further promote the esterification reaction. Until no fraction is distilled, the esterification reaction is finished. The solid super acidic catalyst is SO4 2-/SnO2Diatomaceous earth, SO4 2-/MoO3-TiO2-SiO2、SO4 2-/ZrO2-NiO、SO4 2-/ZrO2- Sm2O3-SiO2Any one of them. Wherein, SO4 2-/SnO2-diatomaceous earth is SnCl4·5 H2The catalyst has the advantages of both the advantages of the solid acid catalyst of the multi-element oxide type and the sulfuric acid acidification modified natural clay solid acid, and has the advantages of high catalytic activity, low cost, simple preparation method and cyclic recycling. And after each solid super acidic catalyst is repeatedly used for 10 times, the esterification rate is still more than 95 percent.
Step (2): and after the first-stage fraction is collected, continuing heating and heating the reaction kettle, keeping the temperature in the reaction kettle within the range of 120-135 ℃, stopping introducing nitrogen into the reaction kettle, collecting the second-stage fraction by adopting a vacuum distillation method until no fraction is evaporated, stopping heating and vacuumizing, weighing the obtained second-stage fraction, and barreling for later use for recycling in the next esterification reaction. The vacuum distillation mode is adopted, the boiling point of butyric acid is reduced, the distillation efficiency is improved, the decomposition of the product in a high-temperature environment for a long time can be avoided, and the product quality is improved.
And (3): and naturally cooling the residual materials in the reaction kettle to room temperature, then carrying out filtration operation, continuously recycling the solid super acidic catalyst obtained by filtration, and further purifying the crude tributyrin obtained by filtration. The product and the catalyst can be separated through simple filtering operation, alkali washing, water washing and drying processes are not needed, no wastewater and waste solids are generated, and the requirements of green sustainable development are met.
And (4): and (4) adding activated carbon into the crude tributyrin obtained in the step (3) to carry out decoloring treatment, and after the decoloring treatment is finished, carrying out circulating filtration by using a felt filter with the pore size of 1200 meshes, wherein the pressure of the circulating filtration is 0.25MPa, and after the filtration is finished, obtaining colorless oily liquid tributyrin. The crude tributyrin is further purified, impurities and pigments contained in the crude tributyrin are removed, the bad smell of the product is improved, the acid value index of the product is qualified, and the quality of the product is improved.
Preferably, the molar ratio of butyric acid to glycerol in step (1) is (3-5): 1, the mass ratio of the solid super acidic catalyst to the glycerol is 1-5%.
Preferably, the reaction time in step (1) is 3 to 5 hours and the degree of vacuum in step (2) is 0.05 to 0.1 MPa.
Preferably, the first stage fraction in the step (1) is water containing a small amount of butyric acid, the second stage fraction in the step (2) is butyric acid, a small amount of sodium hydroxide solution is added into the first stage fraction for neutralization treatment, and then the first stage fraction can be directly discharged into a sewage treatment station for treatment, and the second stage fraction is collected for later use.
Preferably, the solid super acidic catalyst obtained by filtering in the step (3) can be reused for more than 10 times, and the esterification rate is still more than 95% after the solid super acidic catalyst is reused for 10 times.
Preferably, the filtration mode in the step (3) is suction filtration or pressure filtration.
Preferably, in the step (4), nitrogen is introduced into the crude tributyrin for bubbling when the activated carbon decolorization treatment is performed.
Preferably, the reaction kettle is an enamel reaction kettle with a distillation device.
Example 1
Synthesis process of tributyrin
The synthesis process comprises the following steps: step (1): opening a feed inlet of a reaction kettle which is an enamel reaction kettle with a distillation device, and adding butyric acid (288 g 3.27 mol), glycerol (100 g 1.09 mol) and SO4 2-/SnO2Adding diatomite (1 g) into the reaction kettle, starting a stirring device of the reaction kettle after the addition is finished, introducing nitrogen into the reaction kettle, and heating the reaction kettle to perform esterification reaction. On the one hand, the nitrogen serves as a water-carrying agent to accelerate the evaporation of water in the reaction liquid, so that the reaction is favorably carried out rightwards, the efficiency of the esterification reaction is improved, and on the other hand, the nitrogen can serve as a bubbling agent and a protective agent to ensure that the reaction atmosphere is in an inert environment, and the raw materials can be fully mixed to further promote the esterification reaction. And simultaneously opening a steam valve of the reaction kettle, opening circulating water of the condenser, carrying out heating distillation operation, maintaining the temperature in the reaction kettle within the range of 100-105 ℃, collecting the first-stage fraction while carrying out esterification reaction until no fraction is evaporated, finishing the esterification reaction, and reacting for 3-5 hours. The first stage fraction is water containing a small amount of butyric acid, and a small amount of sodium hydroxide solution is added into the first stage fraction for neutralization treatment, and then the neutralized first stage fraction can be directly discharged into a sewage treatment station for treatment.
Step (2): and after the first-stage fraction is collected, continuing heating and heating the reaction kettle, maintaining the temperature in the reaction kettle within the range of 120-135 ℃, stopping introducing nitrogen into the reaction kettle, collecting the second-stage fraction by adopting a vacuum distillation method until no fraction is evaporated, stopping heating and vacuumizing, wherein the vacuum degree is 0.05-0.1MPa, weighing the obtained second-stage fraction, barreling for later use for cyclic utilization in the next esterification reaction, and the second-stage fraction is butyric acid. The vacuum distillation mode is adopted, the boiling point of butyric acid is reduced, the distillation efficiency is improved, the decomposition of the product in a high-temperature environment for a long time can be avoided, and the product quality is improved.
And (3): naturally cooling the residual materials in the reaction kettle to room temperature, and then carrying out filtration operation, wherein the filtration mode is suction filtration or filter pressing, the solid super acidic catalyst obtained by filtration can be continuously recycled, and the crude tributyrin obtained by filtration is further purified. The product and the catalyst can be separated through simple filtering operation, alkali washing, water washing and drying processes are not needed, no wastewater and waste solids are generated, and the requirements of green sustainable development are met.
And (4): and (4) adding activated carbon into the crude tributyrin obtained in the step (3) for decolorization, introducing nitrogen into the crude tributyrin for bubbling, performing circulating filtration by using a felt filter with the aperture of 1200 meshes after the decolorization is finished, wherein the pressure of the circulating filtration is 0.25MPa, and obtaining colorless oily liquid tributyrin after the filtration is finished. The crude tributyrin is further purified, impurities and pigments contained in the crude tributyrin are removed, the bad smell of the product is improved, the acid value index of the product is qualified, and the quality of the product is improved. 336g of colorless oily tributyrin final product (purity 96%, esterification rate 98%) is finally obtained. SO recovered in the step (3)4 2-/SnO2After the diatomite is recycled for 10 times, the esterification rate is still 95.5 percent.
Example 2
Synthesis process of tributyrin
Butyric acid (384 g 4.36 mol), glycerol (100 g 1.09 mol) and SO4 2-/MoO3- TiO2-SiO2(2g) The obtained mixture was put into a reaction vessel and the process was the same as in example 1, whereby 333g (purity: 97%, esterification rate: 98.2%) of a colorless oily tributyrin was obtained. SO recovered in the step (3)4 2-/MoO3- TiO2-SiO2After the compound is repeatedly used for 10 times, the esterification rate is still 96 percent.
Example 3
Synthesis process of tributyrin
Butyric acid (479.6 g 5.45 mol), glycerol (100 g 1.09 mol) and SO4 2-/ZrO2NiO (3 g) is added into the reaction kettle, the process is the same as that of example 1, and 330.6g of colorless oily tributyrin final product (purity 98%, esterification rate 98.5%) is finally obtained. SO recovered in the step (3)4 2-/ZrO2After the-NiO is repeatedly used for 10 times, the esterification rate is still 97.2 percent.
Example 4
Synthesis process of tributyrin
Butyric acid (431.6 g 4.9 mol), glycerol (100 g 1.09 mol) and SO4 2-/ZrO2- Sm2O3-SiO2(4g) The mixture is added into a reaction kettle, the technological process is the same as that of example 1, and 329g of colorless oily tributyrin final product (the purity is 97%, and the esterification rate is 97%) is finally prepared. SO recovered in the step (3)4 2-/ZrO2- Sm2O3-SiO2After the compound is repeatedly used for 10 times, the esterification rate is still 96.1 percent.
Example 5
Synthesis process of tributyrin
Butyric acid (335.7 g 3.81 mol), glycerol (100 g 1.09 mol) and SO4 2-/ZrO2NiO (5 g) is added into the reaction kettle, the process is the same as that of example 1, and 339.4g (purity 95%, esterification rate 98%) of a colorless oily tributyrin final product is finally obtained. SO recovered in the step (3)4 2-/ZrO2After the NiO is repeatedly used for 10 times, the esterification rate is still 96.8 percent.
In conclusion, by adopting the preparation process and the catalyst, the esterification rate is still above 95% after the catalyst is repeatedly used for 10 times, the catalytic activity is high, the cost is low, the post-treatment operation method is simple, the higher esterification rate can be still maintained after the catalyst is repeatedly used for multiple times, the requirement of green sustainable development is met, and the preparation process and the catalyst are suitable for industrial large-scale production.
What has been described above are merely some embodiments of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the inventive concept thereof, and these changes and modifications can be made without departing from the spirit and scope of the invention.
Claims (8)
1. A process for synthesizing tributyrin is characterized in that: the method comprises the following steps:
step (1): opening a feed inlet of a reaction kettle, adding butyric acid, glycerol and a solid super acidic catalyst into the reaction kettle, starting a stirring device of the reaction kettle after the feeding is finished, introducing nitrogen into the reaction kettle, heating the reaction kettle for esterification reaction, simultaneously opening a steam valve of the reaction kettle, opening circulating water of a condenser, performing heating distillation operation, maintaining the temperature in the reaction kettle within the range of 100-105 ℃, collecting a first-stage fraction while performing esterification reaction until no fraction is evaporated out, and finishing the esterification reaction; the solid super acidic catalyst is SO4 2-/SnO2Diatomaceous earth, SO4 2-/MoO3-TiO2-SiO2、SO4 2-/ZrO2- NiO、SO4 2-/ ZrO2- Sm2O3-SiO2Any one of the above;
step (2): after the first-stage fraction is collected, heating and heating the reaction kettle continuously, keeping the temperature in the reaction kettle within the range of 120-135 ℃, stopping introducing nitrogen into the reaction kettle, collecting the second-stage fraction by adopting a vacuum distillation method until no fraction is evaporated, stopping heating and vacuumizing, weighing the obtained second-stage fraction, and barreling for later use for cyclic utilization in the next esterification reaction;
and (3): naturally cooling the residual materials in the reaction kettle to room temperature, then carrying out filtration operation, continuously recycling the solid super acidic catalyst obtained by filtration, and further purifying the crude tributyrin obtained by filtration;
and (4): and (4) adding activated carbon into the crude tributyrin obtained in the step (3) to carry out decoloring treatment, and after the decoloring treatment is finished, carrying out circulating filtration by using a felt filter with the pore size of 1200 meshes, wherein the pressure of the circulating filtration is 0.25MPa, and after the filtration is finished, obtaining colorless oily liquid tributyrin.
2. A process for the synthesis of tributyrin according to claim 1, characterized in that: the molar ratio of butyric acid to glycerol in the step (1) is (3-5): 1, the mass ratio of the solid super acidic catalyst to the glycerol is 1-5%.
3. A process for the synthesis of tributyrin according to claim 2, characterized in that: the reaction time in the step (1) is 3-5 hours, and the vacuum degree in the step (2) is 0.05-0.1 MPa.
4. A process for the synthesis of tributyrin according to claim 2, characterized in that: the first-stage fraction in the step (1) is water containing a small amount of butyric acid, the second-stage fraction in the step (2) is butyric acid, a small amount of sodium hydroxide solution is added into the first-stage fraction for neutralization treatment, and then the first-stage fraction can be directly discharged into a sewage treatment station for treatment, and the second-stage fraction is collected for later use.
5. A process for the synthesis of tributyrin according to claim 2, characterized in that: the solid super acidic catalyst obtained by filtering in the step (3) can be reused for more than 10 times, and the esterification rate is still more than 95% after the solid super acidic catalyst is reused for 10 times.
6. A process for the synthesis of tributyrin according to claim 2, characterized in that: the filtering mode in the step (3) is suction filtration or pressure filtration.
7. A process for the synthesis of tributyrin according to claim 2, characterized in that: and (4) introducing nitrogen into the crude tributyrin for bubbling when activated carbon decolorization treatment is carried out in the step (4).
8. A process for the synthesis of tributyrin according to any one of claims 1 to 7, characterized in that: the reaction kettle is an enamel reaction kettle with a distillation device.
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