CN115582112A - Composite catalyst and application thereof in esterification reaction or ester exchange reaction - Google Patents
Composite catalyst and application thereof in esterification reaction or ester exchange reaction Download PDFInfo
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- CN115582112A CN115582112A CN202211279716.0A CN202211279716A CN115582112A CN 115582112 A CN115582112 A CN 115582112A CN 202211279716 A CN202211279716 A CN 202211279716A CN 115582112 A CN115582112 A CN 115582112A
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- antioxidant
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 43
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 30
- 125000004185 ester group Chemical group 0.000 title abstract 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 37
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 35
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 34
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical group [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003513 alkali Substances 0.000 claims abstract description 25
- 239000000376 reactant Substances 0.000 claims abstract description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 238000005809 transesterification reaction Methods 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 230000032050 esterification Effects 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 17
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- 230000007935 neutral effect Effects 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 31
- 239000000047 product Substances 0.000 description 31
- 150000002148 esters Chemical group 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000003756 stirring Methods 0.000 description 15
- FQMNUIZEFUVPNU-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co] FQMNUIZEFUVPNU-UHFFFAOYSA-N 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 8
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 6
- 239000001119 stannous chloride Substances 0.000 description 6
- 235000011150 stannous chloride Nutrition 0.000 description 6
- 235000021355 Stearic acid Nutrition 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 5
- 239000008117 stearic acid Substances 0.000 description 5
- 239000004359 castor oil Substances 0.000 description 4
- 235000019438 castor oil Nutrition 0.000 description 4
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 4
- 235000013773 glyceryl triacetate Nutrition 0.000 description 4
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 4
- 229960002622 triacetin Drugs 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004597 plastic additive Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- -1 stannous oxide) Chemical class 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000001087 glyceryl triacetate Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 1
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
-
- 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
-
- 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
- C11C3/02—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with glycerol
-
- 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
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of chemical industry, and particularly relates to a composite catalyst and application thereof in esterification reaction or ester exchange reaction. The invention provides a composite catalyst, which comprises an alkali catalyst and an antioxidant, wherein the antioxidant is sodium phosphite and/or sodium hypophosphite. The composite catalyst is prepared by compounding the alkali catalyst and the antioxidant, wherein the antioxidant is sodium phosphite and/or sodium hypophosphite, the sodium phosphite and the sodium hypophosphite belong to salts, are neutral and cannot react with each other after being mixed with the alkali catalyst, and the composite catalyst has good oxidation resistance in a catalytic esterification reaction or an ester exchange reaction, and can prevent the alkali catalyst from oxidizing reactants at a higher temperature so as to solve the problem of deepening the color of materials. And the prices of the sodium phosphite and the sodium hypophosphite are obviously lower than those of the stannous catalysts, so that the production cost can be reduced.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a composite catalyst and application thereof in esterification reaction or ester exchange reaction.
Background
The esterification catalyst is usually acid (such as phosphoric acid and sulfuric acid), alkali (such as sodium hydroxide and sodium carbonate), metal oxide (such as stannous oxide), and salt (such as stannous chloride). The acid has strong oxidizability and corrosivity, the alkali catalyst is selected more, compared with the acid, the corrosivity of the alkali to equipment is relatively small, and the acid catalyst and the alkali catalyst can both cause the color and luster of the material to be deepened in the esterification reaction of the fatty acid and the organic alcohol. In order to ensure that the color of reaction materials is not deepened, at present, stannous oxides and salts (such as stannous chloride and stannous oxide) are mostly used as catalysts for esterification reaction, the catalysts can not cause material oxidative discoloration in high-temperature reaction (below 250 ℃), but have the limitation that the catalysts can only be used for esterification reaction of acid and alcohol, and can not be used for ester exchange reaction and ester alcohol exchange reaction, and the greatly increased price of metal tin causes the production cost to rise straightly, and enterprises can not bear the cost, so that a catalyst which can not only reduce the production cost of esterification products, but also can control the color of the esterification reaction materials and the ester exchange reaction materials from deepening is urgently needed to be found.
Disclosure of Invention
The invention aims to provide a composite catalyst and application thereof in esterification reaction or ester exchange reaction aiming at the existing problems. The composite catalyst of the invention compounds alkali and antioxidant, which not only greatly reduces the cost of esterification products, but also can control the color of materials of esterification reaction and ester exchange reaction not to deepen.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a composite catalyst, which comprises an alkali catalyst and an antioxidant, wherein the antioxidant is sodium phosphite and/or sodium hypophosphite.
Preferably, the mass ratio of the antioxidant to the alkali catalyst is 1:3-4.
Preferably, the mass ratio of the antioxidant to the base catalyst is 1:3.
Preferably, the base catalyst comprises one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
Preferably, when the antioxidant is sodium phosphite and sodium hypophosphite, the mass ratio of the sodium phosphite to the sodium hypophosphite is 0.3-0.7.
Preferably, the mass ratio of sodium phosphite to sodium hypophosphite is 1:1.
The invention also provides the application of the composite catalyst in the technical scheme in esterification reaction or ester exchange reaction.
Preferably, the addition amount of the composite catalyst is 0.4 to 0.5% of the total mass of the reactants.
Preferably, the transesterification reaction comprises a transesterification reaction or an ester-alcohol exchange reaction.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a composite catalyst, which comprises an alkali catalyst and an antioxidant, wherein the antioxidant is sodium phosphite and/or sodium hypophosphite.
The composite catalyst of the invention compounds the alkali catalyst and the antioxidant, the antioxidant is sodium phosphite and/or sodium hypophosphite, the sodium phosphite and the sodium hypophosphite belong to salts, the salts are neutral, the sodium phosphite and the sodium hypophosphite cannot react with each other after being mixed with the alkali catalyst, the oxidation resistance is good in the catalytic esterification reaction or the ester exchange reaction, the alkali catalyst can be prevented from oxidizing reactants at a higher temperature, and the problem of deepening the color of the material is caused. And the price of the sodium phosphite and the sodium hypophosphite is obviously lower than that of the stannous catalyst, so that the production cost can be reduced.
Meanwhile, compared with stannous catalysts, the composite catalyst has wider application range and can be used in esterification reaction of acid and alcohol, ester and ester exchange reaction of ester and alcohol.
Furthermore, the composite catalyst of the invention is convenient to remove, and when the temperature is below 120 ℃ in the absence of water, sodium phosphite and sodium hypophosphite can exist in the materials in the form of crystalline solids, and can be removed by filtration. In the esterification reaction of the plastic additive product, the existence of sodium phosphite and sodium hypophosphite rather plays a good role in the thermal stability of plastic processing, and the sodium phosphite and the sodium hypophosphite can not be removed after being used, so that the processing performance of the plastic additive can be improved.
The invention also provides the application of the composite catalyst in the technical scheme in esterification reaction or ester exchange reaction, wherein the addition amount of the composite catalyst is 0.4-0.5% of the total mass of reactants, the composite catalyst is less in use amount, and the catalytic effect is good.
Detailed Description
The invention provides a composite catalyst, which comprises an alkali catalyst and an antioxidant, wherein the antioxidant is sodium phosphite and/or sodium hypophosphite.
In the present invention, unless otherwise specified, all the raw materials used are commercially available in the art.
In the present invention, the base catalyst is preferably an inorganic base catalyst, which preferably includes one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, more preferably sodium hydroxide.
In the invention, when the antioxidant is preferably sodium phosphite or sodium hypophosphite, the antioxidant is preferably sodium hypophosphite which can better prevent the color of the reacted materials from being darkened.
In the present invention, when the antioxidant is preferably a mixture of sodium phosphite and sodium hypophosphite, the mass ratio of the sodium phosphite to the sodium hypophosphite is preferably 0.3 to 0.7, and more preferably 1:1.
In the present invention, the mass ratio of the antioxidant to the alkali catalyst is preferably 1:3 to 4, and more preferably 1:3.
In the invention, the antioxidant (sodium phosphite and sodium hypophosphite) belongs to salts, is neutral, does not react with the alkali catalyst after being mixed, and can better play the catalytic action of the alkali catalyst and the antioxidant action of the antioxidant after being compounded, thereby preventing the alkali catalyst from oxidizing reactants at a higher temperature. However, when BHA, BHT, TBHQ, PG, methyl polysiloxane and the like are used as the antioxidant, they are expensive due to a large amount of the antioxidant added, and they are also ineffective when used in combination with an alkali catalyst.
The preparation method of the composite catalyst has no special requirements, the alkali catalyst and the antioxidant are uniformly mixed, and the preparation method is simple.
The invention also provides the application of the composite catalyst in the technical scheme in esterification reaction or ester exchange reaction.
In the present invention, the amount of the composite catalyst added is preferably 0.4 to 0.5%, more preferably 0.5%, of the total mass of the reactants.
The temperature and time of the esterification reaction or transesterification reaction are not particularly limited in the present invention, and may be those well known to those skilled in the art.
In the present invention, the transesterification reaction preferably includes a transesterification reaction or an ester-alcohol exchange reaction.
In the invention, the esterification product mainly refers to a product obtained by esterification reaction of acid and alcohol, or ester exchange reaction of ester and ester, and the acid value index of the product is required to be less than 2 or 3. The higher the acid value, the incomplete reaction is indicated, and the lower the acid value, the more complete reaction is indicated. After the composite catalyst disclosed by the invention is used, the acid value of the product meets the requirement and is lower, which shows that the composite catalyst disclosed by the invention has a good catalytic effect.
In order to further illustrate the present invention, the composite catalyst of the present invention and its application in esterification or transesterification are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The reactants are as follows: stearic acid and pentaerythritol.
The feeding proportion of reactants is as follows: 320 g of stearic acid, 80 g of pentaerythritol and 400 g of the total.
The feeding amount of the composite catalyst (the mass ratio of sodium hydroxide to sodium hypophosphite is 3:1): 2 g.
The operation is as follows: firstly putting reactants into a reaction bottle, then adding a composite catalyst, introducing nitrogen after closing, starting stirring, heating to 205 ℃ under stirring, reacting for 90 minutes, continuously heating to 235 ℃, reacting for 90 minutes, and reacting for 180 minutes to finish the reaction. Cooling to 100 ℃, closing nitrogen and stirring, and pouring the product into a clean porcelain dish.
And (3) determination: acid value of the product: 0.89KOHmg/g; cobalt iron color comparison: no. 3.
Comparative example 1
The difference between the comparative example and the example 1 is only the difference of the catalyst, the catalyst of the comparative example is changed into sodium hydroxide, and the feeding amount is as follows: 2 g.
And (3) determination: acid value of the product: 0.91KOHmg/g; cobalt iron color comparison: no. 5.
Comparative example 2
The difference between the comparative example and the example 1 is only the difference of the catalyst, the catalyst of the comparative example is changed into stannous chloride, and the feeding amount is as follows: 1.2 g.
And (3) determination: acid value of the product: 0.90KOHmg/g; cobalt iron color comparison: no. 3.
Example 2
The reactants are as follows: hydrogenated oil, pentaerythritol.
The feeding proportion of reactants is as follows: 350 g of hydrogenated oil and 50 g of pentaerythritol, and the total amount is 400 g.
The feeding amount of the composite catalyst (the mass ratio of sodium hydroxide to sodium hypophosphite to sodium phosphite is 3: 2 g.
The operation is as follows: firstly putting reactants into a reaction bottle, then adding a composite catalyst, introducing nitrogen after closing, starting stirring, heating to 195 ℃ under stirring, reacting for 60 minutes, continuously heating to 225 ℃, reacting for 120 minutes, and reacting for 180 minutes to finish the reaction. Cooling to 100 ℃, turning off nitrogen and stirring, and pouring the product into a clean porcelain plate.
And (3) determination: acid value of the product: 0.56KOHmg/g; cobalt iron color comparison: no. 3.
Comparative example 3
The difference between the comparative example and the example 2 is only the difference of the catalyst, the catalyst of the comparative example is sodium hydroxide, the feeding amount is: 2 g.
And (3) determination: acid value of the product: 0.61KOHmg/g; cobalt iron color comparison: no. 5.
Example 3
The reactants are as follows: refined soybean oil and glycerol.
The feeding proportion of reactants is as follows: 250 g of refined soybean oil and 50 g of glycerol, and the total weight is 400 g.
The material feeding amount of the composite catalyst (the mass ratio of sodium hydroxide to sodium hypophosphite is 3:1): 2 g.
The operation is as follows: firstly putting reactants into a reaction bottle, then adding a composite catalyst, introducing nitrogen after closing, starting stirring, heating to 190 ℃ under stirring, reacting for 90 minutes, continuously heating to 225 ℃, reacting for 90 minutes, and reacting for 180 minutes to finish the reaction. The temperature is reduced to 100 ℃, the nitrogen is closed and the stirring is carried out, and the product is poured into a clean glass beaker.
And (3) determination: acid value of the product: 0.58KOH mg/g; cobalt iron color comparison: no. 3.
Removal of antioxidant sodium hypophosphite: the product in the glass beaker was filtered through a 120 mesh stainless steel mesh to remove the antioxidant and obtain a clear liquid.
Comparative example 4
The difference between the comparative example and the example 3 is only the difference of the catalyst, the catalyst of the comparative example is changed into sodium hydroxide, and the feeding amount is as follows: 2 g.
And (3) determination: acid value of the product: 0.62KOHmg/g; cobalt iron color comparison: no. 6.
The color comparison of the cobalt-iron colorimeter is to illustrate the light and the dark of the color of a sample by using a color number, and standard solution prepared by using standard cobalt-iron colorimetric solution is numbered according to the light and the dark of the standard solution: no. 1-15, no. 1 is the lightest color, and No. 15 is the darkest color (i.e. small color number, light color, large color number, dark color). Generally, the color ratio of esterification reaction is in the range of No. 1 to No. 10, and most of liquid materials before reaction are in the color of No. 2 to No. 4. Table 1 shows the results of examples 1 to 3 and comparative examples 1 to 4, in which, for example, in comparative example 4, the color of the material before the reaction was No. 3 and was lighter, and after the reaction at a high temperature, the reaction product was oxidized to change to No. 6, which increased the color number, indicating that the color was darker.
TABLE 1 summary of the results of examples 1 to 3 and comparative examples 1 to 4
As can be seen from the data of example 1 and comparative example 2, when the composite catalyst of the present invention and stannous chloride are used respectively, the reactants are not discolored before and after the reaction, that is, the reactants are not oxidized, and the color of the esterified product prepared by using the composite catalyst of the present invention is substantially the same as that of the product using stannous chloride as the catalyst. The acid value of the product, namely example 1, is slightly lower than that of the product, namely comparative example 2, which shows that the composite catalyst can achieve the effect equivalent to or slightly better than that of stannous chloride serving as the catalyst. And the price of the tin catalyst is high, and the complexing agent provided by the invention is used, so that the production cost can be obviously reduced.
Example 4
Preparing cold-resistant lubricating oil
The reactants are as follows: refined castor oil and glycerol triacetate.
The feeding proportion of reactants is as follows: 320 g of refined castor oil and 80 g of glycerol triacetate, and the total weight is 400 g.
The feeding amount of the composite catalyst (the mass ratio of sodium hydroxide, sodium phosphite and sodium hypophosphite is 4: 2 g.
The operation is as follows: firstly putting reactants into a reaction bottle, then adding a composite catalyst, introducing nitrogen after closing, starting stirring, heating to 190 ℃ under stirring, reacting for 120 minutes, continuously heating to 215 ℃, reacting for 120 minutes, and reacting for 240 minutes to finish the reaction. The temperature is reduced to 100 ℃, the nitrogen is closed and the stirring is carried out, and the product is poured into a clean glass beaker.
And (3) determination: acid value of the product: 0.25KOHmg/g; cobalt iron color comparison: no. 2.
Removal of antioxidant sodium phosphite and sodium hypophosphite: the antioxidant can be removed by filtering through a 120-mesh stainless steel net to obtain a transparent liquid.
Example 5
The difference between the present embodiment and embodiment 4 is only that the mass ratio of sodium phosphite to sodium hypophosphite in the composite catalyst is different, and the mass ratio of sodium hydroxide, sodium phosphite and sodium hypophosphite in the composite catalyst of the present embodiment is 4.3.
And (3) determination: acid value of the product: 0.25KOHmg/g; cobalt iron color comparison: no. 2.
Comparative example 5
The difference between the comparative example and the example 4 is only the difference of the catalyst, the catalyst of the comparative example is changed into sodium hydroxide, the feeding amount is as follows: 2 g.
And (3) determination: acid value of the product: 0.45KOHmg/g; cobalt iron color comparison: no. 6.
The refined castor oil is viscous liquid oil with a freezing point of-10 ℃, and after ester exchange reaction with glycerol triacetate, liquid lubricating oil with reduced viscosity and a freezing point below-25 ℃ is generated. The refined castor oil has dark color and color number of 4, the glyceryl triacetate is colorless transparent liquid, the solidifying point reaches below-30 deg.C, and the color number of the mixture is 2. Because of the difference in specific gravity and viscosity between the two, if the two are not subjected to transesterification, the two components will be separated from each other after mixing, and will not be separated from each other after reaction.
Example 6
The reactants are as follows: stearic acid and pentaerythritol.
The feeding proportion of reactants is as follows: 320 g of stearic acid, 80 g of pentaerythritol and 400 g of the total.
Catalyst: sodium hypophosphite, the material feeding amount: 2 g.
The operation is as follows: firstly putting reactants into a reaction bottle, then adding a catalyst, introducing nitrogen after closing, starting stirring, heating to 210 ℃ under stirring, reacting for 90 minutes, continuously heating to 230 ℃, reacting for 120 minutes, and reacting for 210 minutes to finish the reaction. Cooling to 100 ℃, turning off nitrogen and stirring, and pouring the product into a clean porcelain plate.
And (3) determination: acid value of the product: 0.98KOHmg/g; cobalt iron color comparison: no. 3.
Description of the invention: the acid value of stearic acid is 200-210 KOHmg/g, and the acid value of the product is lower than 1 through esterification reaction, which shows that the sodium hypophosphite has the function of the catalyst and has the same function as a stannous catalyst.
In the experimental process, the effect of preventing the color of the material from deepening is better when the mass of the sodium hypophosphite in the composite catalyst is larger than that of the sodium phosphite.
The example 1 of the present invention is an esterification reaction of an acid and an alcohol, the examples 2 and 3 are transesterification reactions of an ester and an alcohol, and the examples 4 and 5 are transesterification reactions of an ester and an ester, which illustrate that the composite catalyst of the present invention is suitable for the esterification reaction of an acid and an alcohol, the transesterification reactions of an ester and an ester, and the transesterification reactions of an ester and an alcohol.
The data of the above examples and comparative examples show that the acid value of the product after esterification is less than 2KOHmg/g, and the quality standard of the esterified product is satisfied. And the acid value of each proportion is higher than that of the corresponding embodiment, the higher the acid value is, the incomplete reaction is shown, the part with the higher acid value is not completely reacted, and the lower the acid value is, the more complete reaction is shown, so that the composite catalyst has better catalytic effect.
The color number of the material after reaction in each embodiment of the invention is obviously lower than that of the material after reaction by using the alkali catalyst sodium hydroxide in the corresponding comparative example, which shows that the composite catalyst of the invention prevents the alkali catalyst from oxidizing reactants at higher temperature and causes the problem of deepening the color of the material.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments of the present invention, and the embodiments are within the scope of the present invention.
Claims (9)
1. The composite catalyst is characterized by comprising an alkali catalyst and an antioxidant, wherein the antioxidant is sodium phosphite and/or sodium hypophosphite.
2. The composite catalyst according to claim 1, wherein the mass ratio of the antioxidant to the base catalyst is 1:3-4.
3. The composite catalyst according to claim 1 or 2, wherein the mass ratio of the antioxidant to the base catalyst is 1:3.
4. The composite catalyst according to claim 1 or 2, wherein the base catalyst comprises one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
5. The composite catalyst according to claim 1, wherein when the antioxidant is sodium phosphite and sodium hypophosphite, the mass ratio of the sodium phosphite to the sodium hypophosphite is 0.3-0.7.
6. The composite catalyst according to claim 5, wherein the mass ratio of sodium phosphite to sodium hypophosphite is 1:1.
7. Use of the composite catalyst of any one of claims 1 to 6 in esterification or transesterification reactions.
8. The use according to claim 7, wherein the amount of the composite catalyst added is 0.4 to 0.5% of the total mass of the reactants.
9. Use according to claim 7, wherein the transesterification reaction comprises a transesterification reaction or an ester-alcohol exchange reaction.
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CN106749118A (en) * | 2016-11-23 | 2017-05-31 | 张家港格瑞特化学有限公司 | The smooth caprylate emulsifying agent of sorb |
CN110304996A (en) * | 2019-06-28 | 2019-10-08 | 浙江锦润生物科技有限公司 | A kind of removal methods of base catalyst |
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US4297290A (en) * | 1980-07-17 | 1981-10-27 | Ici Americas Inc. | Process for preparing sorbitan esters |
CN104371097A (en) * | 2014-10-30 | 2015-02-25 | 南京威尔化工有限公司 | Preparation method of controllable-composition polyoxyethylene sorbitol (sorbitan) fatty acid ester |
CN106749118A (en) * | 2016-11-23 | 2017-05-31 | 张家港格瑞特化学有限公司 | The smooth caprylate emulsifying agent of sorb |
CN110304996A (en) * | 2019-06-28 | 2019-10-08 | 浙江锦润生物科技有限公司 | A kind of removal methods of base catalyst |
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