CN113735704A - Method for simultaneously synthesizing dodecyl alcohol ester and hexadecyl diester - Google Patents
Method for simultaneously synthesizing dodecyl alcohol ester and hexadecyl diester Download PDFInfo
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- CN113735704A CN113735704A CN202111161027.5A CN202111161027A CN113735704A CN 113735704 A CN113735704 A CN 113735704A CN 202111161027 A CN202111161027 A CN 202111161027A CN 113735704 A CN113735704 A CN 113735704A
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- ester
- hexadecanediester
- dodecyl alcohol
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- diester
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- -1 dodecyl alcohol ester Chemical class 0.000 title claims abstract description 103
- LQZZUXJYWNFBMV-UHFFFAOYSA-N ethyl butylhexanol Natural products CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 38
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- RXGUIWHIADMCFC-UHFFFAOYSA-N 2-Methylpropyl 2-methylpropionate Chemical compound CC(C)COC(=O)C(C)C RXGUIWHIADMCFC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000002148 esters Chemical group 0.000 claims abstract description 24
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium(III) oxide Inorganic materials O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000002378 acidificating effect Effects 0.000 claims abstract description 16
- 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 14
- 239000011973 solid acid Substances 0.000 claims abstract description 13
- 230000009471 action Effects 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 238000001704 evaporation Methods 0.000 claims abstract description 4
- 230000008020 evaporation Effects 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 22
- 239000003377 acid catalyst Substances 0.000 claims description 14
- DCAYPVUWAIABOU-UHFFFAOYSA-N alpha-n-hexadecene Natural products CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 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
- 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
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- KESQFSZFUCZCEI-UHFFFAOYSA-N 2-(5-nitropyridin-2-yl)oxyethanol Chemical compound OCCOC1=CC=C([N+]([O-])=O)C=N1 KESQFSZFUCZCEI-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 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
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 238000000066 reactive distillation Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052593 corundum Inorganic materials 0.000 abstract description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 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
- 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
- 239000003973 paint Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- JKGWJYJTOABBAJ-UHFFFAOYSA-N 2-methylpropyl 3-hydroxy-2,2,4-trimethylpentanoate Chemical compound CC(C)COC(=O)C(C)(C)C(O)C(C)C JKGWJYJTOABBAJ-UHFFFAOYSA-N 0.000 description 2
- OJLBQZJKORZRDZ-UHFFFAOYSA-N 3-hydroxy-2,2,4-trimethylpentanoic acid Chemical compound CC(C)C(O)C(C)(C)C(O)=O OJLBQZJKORZRDZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 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
- PHIQHXFUZVPYII-ZCFIWIBFSA-O (R)-carnitinium Chemical compound C[N+](C)(C)C[C@H](O)CC(O)=O PHIQHXFUZVPYII-ZCFIWIBFSA-O 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 229960004203 carnitine Drugs 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
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 238000006467 substitution reaction Methods 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a method for simultaneously synthesizing dodecyl alcohol ester and hexadecyl diester, which comprises the following steps: s1, carrying out ester exchange reaction on 2,2, 4-trimethyl-1, 3-pentanediol and isobutyl isobutyrate under the action of an acidic catalyst to generate dodecyl alcohol ester and hexadecyl diester; s2, distilling isobutanol generated in the ester exchange reaction process, and removing impurities through a rectifying tower by evaporation to finally obtain the products of the dodecanol ester and the hexadecanediester. The method for simultaneously synthesizing the dodecyl alcohol ester and the hexadecyl diester adopts S2O8 2‑/ZrO2‑Al2O3‑Sc2O3As a solid acid catalyst, Sc2O3Improve ZrO2‑Al2O3And Sc, which increases pore volume and contributes to the improvement of reactivity2O3The chemical state of the surface of the catalyst can be changed, so that the degree of positive polarization of the surface elements of the catalyst is improved, the activity and the service life of the catalyst are improved, and the yield of the dodecacarbonate ester and the hexadecanediester synthesized simultaneously is finally improved.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to a method for simultaneously synthesizing dodecyl alcohol ester and hexadecyl diester.
Background
2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate (dodecanol ester) and 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate (hexadecanediester) are common film-forming aids for waterborne coatings. The coalescent softens the latex polymer particles, causing the particles to coalesce and fuse together, better forming a film. The film-forming assistant can reduce the minimum film-forming temperature (MFT) of the latex paint, and can also improve the paint film performances of the latex paint, such as weather resistance, scrubbability, color development of a coating and the like.
The main method for synthesizing the dodecyl alcohol ester at present is an isobutyraldehyde alkaline catalysis method, namely, isobutyraldehyde is used as a raw material and is carried out under the action of an alkaline catalyst, and the dodecyl alcohol ester is generated through an aldol condensation reaction and a carnitine zaro reaction. The dodecyl alcohol ester and isobutyric acid are further subjected to esterification reaction under the condition of an acidic catalyst to generate the hexadecyl diester.
In the existing twelve-carbon alcohol ester production process, the main reaction is that isobutyraldehyde reacts through a basic catalyst to generate twelve-carbon alcohol ester, but 2,2, 4-trimethyl-1, 3-pentanediol and 2,2, 4-trimethyl-3-hydroxyvaleric acid and isobutyric acid are generated simultaneously along with partial side reactions, 2,2, 4-trimethyl-3-hydroxyvaleric acid and isobutyric acid further react with isobutanol to generate 2,2, 4-trimethyl-3-hydroxyvaleric acid isobutyl ester and isobutyric acid isobutyl ester, wherein the 2,2, 4-trimethyl-3-hydroxyvaleric acid isobutyl ester can be separated to be used as a film forming aid for aqueous industrial paint, and the separation difficulty of partial byproducts of the 2,2, 4-trimethyl-1, 3-pentanediol and the isobutyric acid isobutyl ester is large, the conversion into high-purity products is difficult and has no economic benefit.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for simultaneously synthesizing dodecyl alcohol ester and hexadecyl diester, wherein 2,2, 4-trimethyl-1, 3-pentanediol and isobutyl isobutyrate are reacted under the condition of an acidic catalyst to produce 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate (dodecyl alcohol ester), 2, 4-trimethyl-1, 3-pentanediol diisobutyrate (hexadecyl diester) and isobutanol, so that the economic benefit is improved.
The technical scheme adopted by the invention is as follows:
a method for simultaneously synthesizing a dodecanol ester and a hexadecanediester, wherein: the method comprises the following steps:
s1, carrying out ester exchange reaction on 2,2, 4-trimethyl-1, 3-pentanediol and isobutyl isobutyrate under the action of an acidic catalyst to generate dodecyl alcohol ester and hexadecyl diester;
s2, distilling isobutanol generated in the ester exchange reaction process, and removing impurities through a rectifying tower by evaporation to finally obtain the products of the dodecanol ester and the hexadecanediester.
Preferably, the method for simultaneously synthesizing the dodecyl alcohol ester and the hexadecyl diester comprises the following steps: the acidic catalyst is an inorganic strong acid or solid acid catalyst, and the dosage of the acidic catalyst is 0.3-1.0% of the total mass of the feed.
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 S2O8 2-/ZrO2-Al2O3-Sc2O3The atomic weight ratio of Zr/Al substance is 2-10: 1,
ZrO 2 is mixed with2Adding a proper amount of Al2O3S to help stabilize oxide surface2O8 2-Changing the acid site type of the surface and increasing the number of effective acid sites of the catalyst; ZrO in composite oxides2-Al2O3The formation of Al-O-Zr bonds, the presence of Al increasing the number of acid active sites, can enhance the SO on the oxide surface4 2-So that the catalyst shows good activity and stability in the reaction; sc (Sc)2O3Improve ZrO2-Al2O3And Sc, which increases pore volume and contributes to the improvement of reactivity2O3Capable of modifying the surface of the catalystThe chemical state improves the positive polarization degree of the surface elements of the catalyst, 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: said S2O8 2-/ZrO2-Al2O3-Sc2O3The preparation method 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 oxides by using sulfuric acid solutions2O3Mixing the mixture with a zirconium sulfate aqueous solution to obtain a first mixture;
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 until the pH value is 8-12 to obtain a mixture II;
s13, aging the mixture II at 80-85 ℃ for 8-10 h, washing, filtering, and drying at 80-100 ℃ for 3-5 h;
s14, adding the powder obtained in the step S13 into ammonium persulfate to be soaked for 12-16 h, and performing suction filtration, drying and roasting after soaking to obtain S2O8 2-/ZrO2-Al2O3-Sc2O3。
Preferably, the method for simultaneously synthesizing the dodecyl alcohol ester and the hexadecyl diester comprises the following steps: in the step S14, the roasting temperature 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 ester exchange 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: in the step S2, removing acid catalysts from the generated dodecyl alcohol ester and hexadecyl diester, and separating by ordinary rectification to obtain 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate and 2,2, 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 S2, directly carrying out reactive distillation on the generated dodecyl alcohol ester and the generated hexadecane diester without removing an acid catalyst to obtain the dodecyl alcohol ester and the hexadecane 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 dodecyl alcohol ester and the hexadecyl diester adopts S2O8 2-/ZrO2-Al2O3-Sc2O3As a solid acid catalyst, Sc2O3Improve ZrO2-Al2O3And Sc, which increases pore volume and contributes to the improvement of reactivity2O3The chemical state of the surface of the catalyst can be changed, so that the degree of positive polarization of the surface elements of the catalyst is improved, the activity and the service life of the catalyst are improved, and the yield of the dodecacarbonate ester and the hexadecanediester synthesized simultaneously is finally improved.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Main reaction:
1. esters of dodecane with alcohols
Side reaction:
aiming at the problems that the separation difficulty of the byproducts of 2,2, 4-trimethyl-1, 3-pentanediol and isobutyl isobutyrate is high and the byproducts become high-purity products, the invention innovatively provides that 2,2, 4-trimethyl-1, 3-pentanediol and isobutyl isobutyrate react under the condition of an acidic catalyst to produce 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate (dodecyl alcohol ester), 2, 4-trimethyl-1, 3-pentanediol diisobutyrate (hexadecyl diester) and isobutanol.
Example 1
A method for simultaneously synthesizing a dodecanol ester and a hexadecanediester, wherein: the method comprises the following steps:
s1, carrying out ester exchange reaction on 2,2, 4-trimethyl-1, 3-pentanediol and isobutyl isobutyrate under the action of an acidic catalyst to generate dodecyl alcohol ester and hexadecyl diester, wherein the acidic catalyst is p-toluenesulfonic acid, and the dosage of the acidic catalyst is 0.3% of the total mass of the materials;
s2, distilling isobutanol generated in the reaction process out in the ester exchange reaction process, removing impurities through a rectifying tower in a distilling mode, finally obtaining products of dodecyl alcohol ester and hexadecane diester, removing acid catalysts from the generated dodecyl alcohol ester and hexadecane diester, and separating through ordinary rectification to obtain 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate and 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate; the common rectification temperature is 125 ℃, the pressure is-0.075 MPa, the temperature of the ester exchange reaction is 150 ℃, and the reaction time is 10 h.
Example 2
A method for simultaneously synthesizing a dodecanol ester and a hexadecanediester, wherein: the method comprises the following steps:
s1, carrying out an ester exchange reaction on 2,2, 4-trimethyl-1, 3-pentanediol and isobutyl isobutyrate under the action of an acidic catalyst to generate dodecyl alcohol ester and hexadecyl diester, wherein the temperature of the ester exchange reaction is 170 ℃, and the reaction time is 8 h;
s2, distilling isobutanol generated in the reaction process out in the ester exchange reaction process, removing impurities through a rectifying tower in a distilling mode, finally obtaining products of dodecyl alcohol ester and hexadecane diester, removing acid catalysts from the generated dodecyl alcohol ester and hexadecane diester, and separating through ordinary rectification to obtain 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate and 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate; the ordinary rectification temperature is 160 ℃, and the pressure is-0.085 MPa.
The acid catalyst is solid acid catalyst, the dosage of the acid catalyst is 0.5 percent of the total mass of the feed, and the solid acid catalyst is S2O8 2-/ZrO2-Al2O3-Sc2O3；
Said S2O8 2-/ZrO2-Al2O3-Sc2O3The preparation method comprises the following steps:
s11, respectively preparing zirconium sulfate and aluminum sulfate into aqueous solutions with mass fractions of 6%, and dissolving Sc accounting for 10% of the total mass of the oxides by using sulfuric acid solutions2O3Mixing the mixture with a zirconium sulfate aqueous solution to obtain a first mixture;
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 until the pH value is 8-12 to obtain a mixture II;
s13, aging the mixture II at 80 ℃ for 10h, washing, filtering, and drying at 80 ℃ for 5 h;
s14, adding the powder obtained in the step S13 into ammonium persulfate to be soaked for 12 hours, carrying out suction filtration, drying and roasting at the roasting temperature of 650 ℃ for 5 hours to obtain S2O8 2-/ZrO2-Al2O3-Sc2O3。
Example 3
A method for simultaneously synthesizing a dodecanol ester and a hexadecanediester, wherein: the method comprises the following steps:
s1, carrying out an ester exchange reaction on 2,2, 4-trimethyl-1, 3-pentanediol and isobutyl isobutyrate under the action of an acidic catalyst to generate dodecyl alcohol ester and hexadecyl diester, wherein the temperature of the ester exchange reaction is 190 ℃, and the reaction time is 3 h;
s2, distilling isobutanol generated in the ester exchange reaction process, removing impurities through a rectifying tower by evaporation, and finally obtaining products of the dodecyl alcohol ester and the hexadecane diester, wherein the generated dodecyl alcohol ester and the hexadecane diester are directly subjected to reactive rectification without removing acid catalysts to obtain the dodecyl alcohol ester and the hexadecane diester, and the reactive rectification temperature is 185 ℃ and the pressure is-0.099 MPa.
The acid catalyst is a solid acid catalyst, and the dosage of the acid catalyst is 1.0 percent of the total mass of the feed; the solid acid catalyst is S2O8 2-/ZrO2-Al2O3-Sc2O3。
Said S2O8 2-/ZrO2-Al2O3-Sc2O3The preparation method comprises the following steps:
s11, respectively preparing zirconium sulfate and aluminum sulfate into aqueous solutions with mass fractions of 8%, and dissolving Sc accounting for 15% of the total mass of the oxides by using sulfuric acid solutions2O3Mixing the mixture with a zirconium sulfate aqueous solution to obtain a first mixture;
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 until the pH value is 8-12 to obtain a mixture II;
s13, aging the mixture II at 85 ℃ for 8h, washing, filtering, and drying at 100 ℃ for 3 h;
s14, adding the powder obtained in the step S13 into ammonium persulfate to be soaked for 12-16 h, performing suction filtration, drying and roasting, wherein the roasting temperature of S14 is 700 ℃, and the roasting time is 3h to obtain S2O8 2-/ZrO2-Al2O3-Sc2O3。
Comparative example 1
A method for simultaneously synthesizing a dodecanol ester and a hexadecanediester, wherein: the method comprises the following steps:
s1, carrying out an ester exchange reaction on 2,2, 4-trimethyl-1, 3-pentanediol and isobutyl isobutyrate under the action of an acidic catalyst to generate dodecyl alcohol ester and hexadecyl diester, wherein the temperature of the ester exchange reaction is 170 ℃, and the reaction time is 8 h;
s2, distilling isobutanol generated in the reaction process out in the ester exchange reaction process, removing impurities through a rectifying tower in a distilling mode, finally obtaining products of dodecyl alcohol ester and hexadecane diester, removing acid catalysts from the generated dodecyl alcohol ester and hexadecane diester, and separating through ordinary rectification to obtain 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate and 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate; the ordinary rectification temperature is 160 ℃, and the pressure is-0.085 MPa.
The acid catalyst is solid acid catalyst, the dosage of the acid catalyst is 0.5 percent of the total mass of the feed, and the solid acid catalyst is S2O8 2-/ZrO2-Al2O3；
Said S2O8 2-/ZrO2-Al2O3The preparation method 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 until the pH value is 8-12 to obtain a mixture II;
s13, aging the mixture II at 80 ℃ for 10h, washing, filtering, and drying at 80 ℃ for 5 h;
s14, adding the powder obtained in the step S13 into ammonium persulfate to be soaked for 12 hours, carrying out suction filtration, drying and roasting at the roasting temperature of 650 ℃ for 5 hours to obtain S2O8 2-/ZrO2-Al2O3。
The results of the performance tests of examples 1-3 and comparative example 1 are set forth below, as in Table 1
TABLE 1
| Example 1 | Example 2 | Example 3 | Comparative example 1 | |
| Conversion rate | 78％ | 92.1 | 93.5 | 82.1 |
| Yield of | 62％ | 85.7％ | 90.2％ | 71.4 |
The method for simultaneously synthesizing the dodecyl alcohol ester and the hexadecyl diester adopts S2O8 2-/ZrO2-Al2O3-Sc2O3As a solid acid catalyst, Sc2O3Improve ZrO2-Al2O3And Sc, which increases pore volume and contributes to the improvement of reactivity2O3The chemical state of the surface of the catalyst can be changed, so that the degree of positive polarization of the surface elements of the catalyst is improved, the activity and the service life of the catalyst are improved, and the yield of the dodecacarbonate ester and the hexadecanediester synthesized simultaneously is finally improved.
Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, 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 or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (9)
1. A method for simultaneously synthesizing dodecyl alcohol ester and hexadecyl diester is characterized in that: the method comprises the following steps:
s1, carrying out ester exchange reaction on 2,2, 4-trimethyl-1, 3-pentanediol and isobutyl isobutyrate under the action of an acidic catalyst to generate dodecyl alcohol ester and hexadecyl diester;
s2, distilling isobutanol generated in the ester exchange reaction process, and removing impurities through a rectifying tower by evaporation to finally obtain the products of the dodecanol ester and the hexadecanediester.
2. The process for the simultaneous synthesis of dodecanol ester and hexadecanediester according to claim 1, wherein: the acidic catalyst is an inorganic strong acid or solid acid catalyst, and the dosage of the acidic catalyst is 0.3-1.0% of the total mass of the feed.
3. The process for the simultaneous synthesis of dodecanol ester and hexadecanediester according to claim 2, wherein: the inorganic strong acid is selected from one or more of sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, phosphoric acid and nitric acid.
4. The process for the simultaneous synthesis of dodecanol ester and hexadecanediester according to claim 2, wherein: the solid acid catalyst is S2O8 2-/ZrO2-Al2O3-Sc2O3。
5. The method for simultaneously synthesizing dodecanol ester and hexadecanediester according to claim 4, wherein: said S2O8 2-/ZrO2-Al2O3-Sc2O3The preparation method 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 oxides by using sulfuric acid solutions2O3Mixing the mixture with a zirconium sulfate aqueous solution to obtain a first mixture;
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 until the pH value is 8-12 to obtain a mixture II;
s13, aging the mixture II at 80-85 ℃ for 8-10 h, washing, filtering, and drying at 80-100 ℃ for 3-5 h;
s14, adding the powder obtained in the step S13 into ammonium persulfate to be soaked for 12-16 h, and performing suction filtration, drying and roasting after soaking to obtain S2O8 2-/ZrO2-Al2O3-Sc2O3。
6. The method for simultaneously synthesizing dodecanol ester and hexadecanediester according to claim 5, wherein: in the step S14, the roasting temperature is 650-700 ℃, and the roasting time is 3-5 h.
7. The process for the simultaneous synthesis of dodecanol ester and hexadecanediester according to claim 1, wherein: the temperature of the ester exchange reaction in the step S1 is 150-190 ℃, and the reaction time is 3-10 h.
8. The process for the simultaneous synthesis of dodecanol ester and hexadecanediester according to claim 1, wherein: in the step S2, removing acid catalysts from the generated dodecyl alcohol ester and hexadecyl diester, and separating by ordinary rectification to obtain 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate and 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate; the common rectification temperature is 125-185 ℃, and the pressure is-0.075-0.1 MPa.
9. The process for the simultaneous synthesis of dodecanol ester and hexadecanediester according to claim 1, wherein: and S2, directly carrying out reactive distillation on the generated dodecyl alcohol ester and the generated hexadecane diester without removing an acid catalyst to obtain the dodecyl alcohol ester and the hexadecane diester, wherein the reactive distillation temperature is 125-185 ℃, and the pressure is-0.075-0.099 MPa.
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