CN113735704B - Method for simultaneously synthesizing dodecanol ester and hexadecyl diester - Google Patents
Method for simultaneously synthesizing dodecanol ester and hexadecyl diester Download PDFInfo
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- -1 dodecanol ester Chemical class 0.000 title claims abstract description 125
- LQZZUXJYWNFBMV-UHFFFAOYSA-N ethyl butylhexanol Natural products CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 43
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003377 acid catalyst Substances 0.000 claims abstract description 28
- RXGUIWHIADMCFC-UHFFFAOYSA-N 2-Methylpropyl 2-methylpropionate Chemical compound CC(C)COC(=O)C(C)C RXGUIWHIADMCFC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 24
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 20
- 239000011973 solid acid Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 230000009471 action Effects 0.000 claims abstract description 8
- DCAYPVUWAIABOU-UHFFFAOYSA-N alpha-n-hexadecene Natural products CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 7
- 238000004821 distillation Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 238000000066 reactive distillation Methods 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000006872 improvement Effects 0.000 abstract description 4
- 230000010287 polarization Effects 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 4
- 230000009257 reactivity Effects 0.000 abstract description 4
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical group CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 6
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000003973 paint Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000005705 Cannizzaro reaction Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for simultaneously synthesizing dodecyl alcohol ester and hexadecyl diester, which comprises the following steps: s1, under the action of an acid catalyst, performing transesterification reaction on 2, 4-trimethyl-1, 3-pentanediol and isobutyl isobutyrate to generate dodecanol ester and hexadecane diester; s2, distilling off the isobutanol generated by the reaction in the transesterification reaction process, and removing impurities through a rectifying tower by distillation to finally obtain the products of dodecanol ester and hexadecane diester. The method for simultaneously synthesizing the dodecanol ester and the hexadecyl diester uses S 2 O 8 2‑ /ZrO 2 ‑Al 2 O 3 ‑Sc 2 O 3 Sc as a solid acid catalyst 2 O 3 Improve ZrO 2 ‑Al 2 O 3 Has improved pore volume, is beneficial to the improvement of reactivity, and Sc 2 O 3 The chemical state of the catalyst surface can be changed to improve the positive polarization degree of the elements on the catalyst surface, so that the activity and the service life of the catalyst are improved, and finally the yield of simultaneously synthesizing the dodecanol ester and the hexadecyl diester is improved.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to a method for simultaneously synthesizing dodecanol ester and hexadecyl diester.
Background
2, 4-trimethyl-1, 3-pentanediol monoisobutyrate (dodecanol ester) and 2, 4-trimethyl-1, 3-pentanediol diisobutyrate (hexadecane diester) are commonly used film forming aids for aqueous coatings. The coalescent is capable of softening the latex polymer particles, coalescing the particles together, and better forming a film. Besides reducing the minimum film forming temperature (MFT) of the emulsion paint, the film forming additive can also improve the weather resistance, the scrubbability, the color spreading performance of the coating and other paint film performances of the emulsion paint.
The most main method for synthesizing the dodecanol ester at present is an isobutyraldehyde alkaline catalysis method, namely, isobutyraldehyde is used as a raw material, and the dodecanol ester is generated through aldol condensation reaction and Cannizzaro reaction under the action of an alkaline catalyst. The dodecyl alcohol ester and the isobutyric acid are further subjected to esterification reaction under the condition of an acid catalyst to generate hexadecyl diester.
In the existing dodecanol ester production process, the main reaction is that isobutyraldehyde reacts through an alkaline catalyst to generate dodecanol ester, but partial side reaction is carried out to generate 2, 4-trimethyl-1, 3-pentanediol and 2, 4-trimethyl-3-hydroxy valeric acid and isobutyric acid at the same time, the 2, 4-trimethyl-3-hydroxy valeric acid and isobutyric acid further react with isobutanol to generate 2, 4-trimethyl-3-hydroxy valeric acid isobutyl ester and isobutyric acid isobutyl ester, wherein, the 2, 4-trimethyl-3-hydroxy isobutyl valerate can be separated to be used as a film forming auxiliary agent for water-based industrial paint, and the separation difficulty of the byproducts of the 2, 4-trimethyl-1, 3-pentanediol and isobutyl isobutyrate is high, and the product with high purity is more difficult to be changed into a product without too much economic benefit.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a method for simultaneously synthesizing dodecyl alcohol ester and hexadecyl diester, which is used for producing 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate (dodecyl alcohol ester) and 2, 4-trimethyl-1, 3-pentanediol diisobutyrate (hexadecyl diester) and isobutanol by reacting 2, 4-trimethyl-1, 3-pentanediol isobutyl isobutyrate and isobutanol under the condition of an acid catalyst, so that the economic benefit is improved.
The technical scheme adopted by the invention is as follows:
a method for simultaneously synthesizing dodecyl alcohol ester and hexadecyl diester, wherein: the method comprises the following steps:
s1, under the action of an acid catalyst, performing transesterification reaction on 2, 4-trimethyl-1, 3-pentanediol and isobutyl isobutyrate to generate dodecanol ester and hexadecane diester;
s2, distilling off the isobutanol generated by the reaction in the transesterification reaction process, and removing impurities through a rectifying tower by distillation to finally obtain the products of dodecanol ester and hexadecane diester.
Preferably, the method for simultaneously synthesizing the dodecyl alcohol ester and the hexadecyl diester comprises the following steps: the acid catalyst is an inorganic strong acid or solid acid catalyst, and the dosage of the acid catalyst is 0.3-1.0% of the total mass of the material.
Preferably, the method for simultaneously synthesizing the dodecyl alcohol ester and the hexadecyl diester comprises the following steps: the inorganic strong acid is selected from one or more of sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, phosphoric acid and nitric acid.
Preferably, the method for simultaneously synthesizing the dodecyl alcohol ester and the hexadecyl diester comprises the following steps: the solid acid catalyst is S 2 O 8 2- /ZrO 2 -Al 2 O 3 -Sc 2 O 3 The atomic weight ratio of Zr/Al substance is 2-10:1,
ZrO (ZrO) 2 Adding proper amount of Al 2 O 3 S to help stabilize oxide surfaces 2 O 8 2- Changing the acid site type of the surface and increasing the number of effective acid sites of the catalyst; zrO in composite oxide 2 -Al 2 O 3 The presence of Al increases the number of acid active sites Al-O-Zr bonds which form to enhance the SO on the oxide surface 4 2- So that the catalyst exhibits good activity and stability in the reaction; sc (Sc) 2 O 3 Improve ZrO 2 -Al 2 O 3 Has improved pore volume, is beneficial to the improvement of reactivity, and Sc 2 O 3 The chemical state of the catalyst surface can be changed to improve the positive polarization degree of the catalyst surface element, thereby improving the activity and the service life of the catalyst.
Preferably, the method for simultaneously synthesizing the dodecyl alcohol ester and the hexadecyl diester comprises the following steps: the S is 2 O 8 2- /ZrO 2 -Al 2 O 3 -Sc 2 O 3 The preparation method of the (C) comprises the following steps:
s11, respectively preparing zirconium sulfate and aluminum sulfate into mass fractions6-8% aqueous solution, and sulfuric acid solution is used to dissolve Sc accounting for 10-15% of the total mass of oxide 2 O 3 And mixing with a zirconium sulfate aqueous solution to obtain a mixture I;
s12, respectively adding ammonium nitrate into the mixture I and aluminum sulfate, respectively precipitating to obtain hydroxide precipitates of zirconium and aluminum, and mixing the two precipitates when the pH value is 8-12 to obtain a mixture II;
s13, aging the mixture II at 80-85 ℃ for 8-10 hours, washing, suction filtering and drying at 80-100 ℃ for 3-5 hours;
s14, adding the powder obtained in the step S13 into ammonium persulfate to be soaked for 12-16 hours, and performing suction filtration, drying and roasting after soaking to obtain S 2 O 8 2- /ZrO 2 -Al 2 O 3 -Sc 2 O 3 。
Preferably, the method for simultaneously synthesizing the dodecyl alcohol ester and the hexadecyl diester comprises the following steps: the roasting temperature in the step S14 is 650-700 ℃ and the roasting time is 3-5 h.
Preferably, the method for simultaneously synthesizing the dodecyl alcohol ester and the hexadecyl diester comprises the following steps: the temperature of the transesterification reaction in the step S1 is 150-190 ℃ and the reaction time is 3-10 h.
Preferably, the method for simultaneously synthesizing the dodecyl alcohol ester and the hexadecyl diester comprises the following steps: step S2, removing an acidic catalyst from the generated dodecanol ester and hexadecyl diester, and separating by common rectification to obtain 2, 4-trimethyl-1, 3-pentanediol diisobutyrate and 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate; the common rectification temperature is 125-185 ℃, and the pressure is-0.075-0.1 MPa.
Preferably, the method for simultaneously synthesizing the dodecyl alcohol ester and the hexadecyl diester comprises the following steps: and step S2, directly carrying out reactive distillation on the generated dodecanol ester and hexadecyl diester without removing an acid catalyst to obtain the dodecanol ester and hexadecyl diester, wherein the reactive distillation temperature is 125-185 ℃ and the pressure is-0.075-0.099 MPa.
The invention has the advantages that:
the method for simultaneously synthesizing the dodecanol ester and the hexadecyl diester uses S 2 O 8 2- /ZrO 2 -Al 2 O 3 -Sc 2 O 3 Sc as a solid acid catalyst 2 O 3 Improve ZrO 2 -Al 2 O 3 Has improved pore volume, is beneficial to the improvement of reactivity, and Sc 2 O 3 The chemical state of the catalyst surface can be changed to improve the positive polarization degree of the elements on the catalyst surface, so that the activity and the service life of the catalyst are improved, and finally the yield of simultaneously synthesizing the dodecanol ester and the hexadecyl diester is improved.
Detailed Description
The invention will be further illustrated with reference to specific examples.
The main reaction:
1. dodecanol ester
Side reaction:
aiming at the problems that the separation difficulty of the byproducts of 2, 4-trimethyl-1, 3-pentanediol and isobutyl isobutyrate is high and the high purity product is changed into high-purity product, the invention innovatively provides the method for producing 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate (dodecyl alcohol ester) and 2, 4-trimethyl-1, 3-pentanediol diisobutyrate (hexadecyl diester) and isobutyl alcohol by reacting 2, 4-trimethyl-1, 3-pentanediol isobutyl isobutyrate with isobutyl isobutyrate under the condition of an acid catalyst.
Example 1
A method for simultaneously synthesizing dodecyl alcohol ester and hexadecyl diester, wherein: the method comprises the following steps:
s1, carrying out transesterification on 2, 4-trimethyl-1, 3-pentanediol and isobutyl isobutyrate under the action of an acid catalyst to generate dodecanol ester and hexadecyl diester, wherein the acid catalyst is p-toluenesulfonic acid, and the dosage of the acid catalyst is 0.3% of the total mass of the fed materials;
s2, distilling off isobutanol generated by the reaction in the transesterification reaction process, removing impurities through a rectifying tower, finally obtaining products of dodecyl alcohol ester and hexadecyl diester, removing an acid catalyst from the generated dodecyl alcohol ester and hexadecyl diester, and separating through common rectification to obtain 2, 4-trimethyl-1, 3-pentanediol diisobutyrate and 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate; the common rectification temperature is 125 ℃, the pressure is-0.075 MPa, the temperature of the transesterification reaction is 150 ℃, and the reaction time is 10 hours.
Example 2
A method for simultaneously synthesizing dodecyl alcohol ester and hexadecyl diester, wherein: the method comprises the following steps:
s1, under the action of an acid catalyst, carrying out transesterification on 2, 4-trimethyl-1, 3-pentanediol and isobutyl isobutyrate to generate dodecanol ester and hexadecyl diester, wherein the temperature of the transesterification is 170 ℃, and the reaction time is 8 hours;
s2, distilling off isobutanol generated by the reaction in the transesterification reaction process, removing impurities through a rectifying tower, finally obtaining products of dodecyl alcohol ester and hexadecyl diester, removing an acid catalyst from the generated dodecyl alcohol ester and hexadecyl diester, and separating through common rectification to obtain 2, 4-trimethyl-1, 3-pentanediol diisobutyrate and 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate; the common rectification temperature is 160 ℃, and the pressure is-0.085 MPa.
The acid catalyst is a solid acid catalyst, the dosage of the acid catalyst is 0.5% of the total mass of the material, and the solid acid catalyst is S 2 O 8 2- /ZrO 2 -Al 2 O 3 -Sc 2 O 3 ；
The S is 2 O 8 2- /ZrO 2 -Al 2 O 3 -Sc 2 O 3 The preparation method of the (C) comprises the following steps:
s11, respectively preparing zirconium sulfate and aluminum sulfate into aqueous solutions with the mass fraction of 6%, and dissolving Sc accounting for 10% of the total mass of the oxide by using sulfuric acid solution 2 O 3 And mixing with a zirconium sulfate aqueous solution to obtain a mixture I;
s12, respectively adding ammonium nitrate into the mixture I and aluminum sulfate, respectively precipitating to obtain hydroxide precipitates of zirconium and aluminum, and mixing the two precipitates when the pH value is 8-12 to obtain a mixture II;
s13, aging the mixture II at 80 ℃ for 10 hours, and then washing, suction filtering and drying at 80 ℃ for 5 hours;
s14, adding the powder obtained in the step S13 into ammonium persulfate, soaking for 12 hours, performing suction filtration, drying, roasting at 650 ℃ for 5 hours to obtain S 2 O 8 2- /ZrO 2 -Al 2 O 3 -Sc 2 O 3 。
Example 3
A method for simultaneously synthesizing dodecyl alcohol ester and hexadecyl diester, wherein: the method comprises the following steps:
s1, under the action of an acid catalyst, carrying out transesterification on 2, 4-trimethyl-1, 3-pentanediol and isobutyl isobutyrate to generate dodecanol ester and hexadecyl diester, wherein the temperature of the transesterification is 190 ℃, and the reaction time is 3 hours;
s2, distilling out isobutanol generated by the reaction in the transesterification reaction process, removing impurities through a rectifying tower, finally obtaining the products of dodecyl alcohol ester and hexadecyl diester, and directly carrying out reactive rectification on the generated dodecyl alcohol ester and hexadecyl diester without removing an acid catalyst to obtain the dodecyl alcohol ester and hexadecyl diester, wherein the reactive rectification temperature is 185 ℃, and the pressure is-0.099 MPa.
The acid catalyst is a solid acid catalyst,the dosage of the acid catalyst is 1.0% of the total mass of the fed materials; the solid acid catalyst is S 2 O 8 2- /ZrO 2 -Al 2 O 3 -Sc 2 O 3 。
The S is 2 O 8 2- /ZrO 2 -Al 2 O 3 -Sc 2 O 3 The preparation method of the (C) comprises the following steps:
s11, respectively preparing zirconium sulfate and aluminum sulfate into 8% aqueous solutions by mass, and dissolving Sc accounting for 15% of the total mass of the oxide by using sulfuric acid solution 2 O 3 And mixing with a zirconium sulfate aqueous solution to obtain a mixture I;
s12, respectively adding ammonium nitrate into the mixture I and aluminum sulfate, respectively precipitating to obtain hydroxide precipitates of zirconium and aluminum, and mixing the two precipitates when the pH value is 8-12 to obtain a mixture II;
s13, aging the mixture II at 85 ℃ for 8 hours, washing, suction filtering and drying at 100 ℃ for 3 hours;
s14, adding the powder obtained in the step S13 into ammonium persulfate, soaking for 12-16 hours, performing suction filtration, drying and roasting after soaking, wherein the roasting temperature of S14 is 700 ℃ and the roasting time is 3 hours to obtain S 2 O 8 2- /ZrO 2 -Al 2 O 3 -Sc 2 O 3 。
Comparative example 1
A method for simultaneously synthesizing dodecyl alcohol ester and hexadecyl diester, wherein: the method comprises the following steps:
s1, under the action of an acid catalyst, carrying out transesterification on 2, 4-trimethyl-1, 3-pentanediol and isobutyl isobutyrate to generate dodecanol ester and hexadecyl diester, wherein the temperature of the transesterification is 170 ℃, and the reaction time is 8 hours;
s2, distilling off isobutanol generated by the reaction in the transesterification reaction process, removing impurities through a rectifying tower, finally obtaining products of dodecyl alcohol ester and hexadecyl diester, removing an acid catalyst from the generated dodecyl alcohol ester and hexadecyl diester, and separating through common rectification to obtain 2, 4-trimethyl-1, 3-pentanediol diisobutyrate and 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate; the common rectification temperature is 160 ℃, and the pressure is-0.085 MPa.
The acid catalyst is a solid acid catalyst, the dosage of the acid catalyst is 0.5% of the total mass of the material, and the solid acid catalyst is S 2 O 8 2- /ZrO 2 -Al 2 O 3 ；
The S is 2 O 8 2- /ZrO 2 -Al 2 O 3 The preparation method of the (C) comprises the following steps:
s11, respectively preparing zirconium sulfate and aluminum sulfate into aqueous solutions with mass fractions of 6%;
s12, respectively adding ammonium nitrate into zirconium sulfate and aluminum sulfate, respectively precipitating to obtain hydroxide precipitates of zirconium and aluminum, and mixing the two precipitates when the pH value is 8-12 to obtain a mixture II;
s13, aging the mixture II at 80 ℃ for 10 hours, and then washing, suction filtering and drying at 80 ℃ for 5 hours;
s14, adding the powder obtained in the step S13 into ammonium persulfate, soaking for 12 hours, performing suction filtration, drying, roasting at 650 ℃ for 5 hours to obtain S 2 O 8 2- /ZrO 2 -Al 2 O 3 。
The results of the performance tests of examples 1-3 and comparative example 1 are shown below as Table 1
TABLE 1
| Example 1 | Example 2 | Example 3 | Comparative example 1 | |
| Conversion rate | 78％ | 92.1 | 93.5 | 82.1 |
| Yield is good | 62％ | 85.7％ | 90.2％ | 71.4 |
The method for simultaneously synthesizing the dodecanol ester and the hexadecyl diester uses S 2 O 8 2- /ZrO 2 -Al 2 O 3 -Sc 2 O 3 Sc as a solid acid catalyst 2 O 3 Improve ZrO 2 -Al 2 O 3 Has improved pore volume, is beneficial to the improvement of reactivity, and Sc 2 O 3 The chemical state of the catalyst surface can be changed to improve the positive polarization degree of the elements on the catalyst surface, so that the activity and the service life of the catalyst are improved, and finally the yield of simultaneously synthesizing the dodecanol ester and the hexadecyl diester is improved.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same, and although the present invention has been described in detail with reference to examples, it should be understood by those skilled in the art that modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and all such modifications and equivalents are intended to be encompassed in the scope of the claims of the present invention.
Claims (7)
1. A method for simultaneously synthesizing dodecanol ester and hexadecyl diester is characterized in that: the method comprises the following steps:
s1, under the action of an acid catalyst, performing transesterification reaction on 2, 4-trimethyl-1, 3-pentanediol and isobutyl isobutyrate to generate dodecanol ester and hexadecane diester;
s2, distilling off isobutanol generated by the reaction in the transesterification reaction process, and removing impurities through a rectifying tower by distillation to finally obtain products of dodecanol ester and hexadecane diester;
the acid catalyst is a solid acid catalyst, and the solid acid catalyst is S 2 O 8 2- /ZrO 2 -Al 2 O 3 -Sc 2 O 3 。
2. The method for simultaneously synthesizing dodecyl alcohol ester and hexadecyl diester according to claim 1, wherein: the dosage of the acid catalyst is 0.3-1.0% of the total mass of the material.
3. The method for simultaneously synthesizing dodecyl alcohol ester and hexadecyl diester according to claim 1, wherein: the S is 2 O 8 2- /ZrO 2 -Al 2 O 3 -Sc 2 O 3 The preparation method of the (C) comprises the following steps:
s11, respectively preparing zirconium sulfate and aluminum sulfate into aqueous solutions with mass fractions of 6-8%, and dissolving Sc accounting for 10-15% of the total mass of the oxide by using sulfuric acid solution 2 O 3 And mixing with a zirconium sulfate aqueous solution to obtain a mixture I;
s12, respectively adding ammonium nitrate into the mixture I and aluminum sulfate, respectively precipitating to obtain hydroxide precipitates of zirconium and aluminum, and mixing the two precipitates when the pH value is 8-12 to obtain a mixture II;
s13, aging the mixture II at 80-85 ℃ for 8-10 hours, washing, suction filtering and drying at 80-100 ℃ for 3-5 hours;
s14, adding the powder obtained in the step S13 into ammonium persulfate to be soaked for 12-16 hours, and performing suction filtration, drying and roasting after soaking to obtain S 2 O 8 2- /ZrO 2 -Al 2 O 3 -Sc 2 O 3 。
4. A method for simultaneously synthesizing dodecyl ester and hexadecyl diester according to claim 3, characterized in that: the roasting temperature in the step S14 is 650-700 ℃ and the roasting time is 3-5 h.
5. The method for simultaneously synthesizing dodecyl alcohol ester and hexadecyl diester according to claim 1, wherein: the temperature of the transesterification reaction in the step S1 is 150-190 ℃ and the reaction time is 3-10 h.
6. The method for simultaneously synthesizing dodecyl alcohol ester and hexadecyl diester according to claim 1, wherein: step S2, removing an acidic catalyst from the generated dodecanol ester and hexadecyl diester, and separating by common rectification to obtain 2, 4-trimethyl-1, 3-pentanediol diisobutyrate and 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate; the common rectification temperature is 125-185 ℃, and the pressure is-0.075-0.1 MPa.
7. The method for simultaneously synthesizing dodecyl alcohol ester and hexadecyl diester according to claim 1, wherein: and step S2, directly carrying out reactive distillation on the generated dodecanol ester and hexadecyl diester without removing an acid catalyst to obtain the dodecanol ester and hexadecyl diester, wherein the reactive distillation temperature is 125-185 ℃ and the pressure is-0.075-0.099 MPa.
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