CN114907185B - Application of magnesium sulfate modified KIT-6 solid acid catalyst in borneol synthesis - Google Patents
Application of magnesium sulfate modified KIT-6 solid acid catalyst in borneol synthesis Download PDFInfo
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- CN114907185B CN114907185B CN202210528688.5A CN202210528688A CN114907185B CN 114907185 B CN114907185 B CN 114907185B CN 202210528688 A CN202210528688 A CN 202210528688A CN 114907185 B CN114907185 B CN 114907185B
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 title claims abstract description 62
- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- 229910052943 magnesium sulfate Inorganic materials 0.000 title claims abstract description 31
- 235000019341 magnesium sulphate Nutrition 0.000 title claims abstract description 31
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 title claims abstract description 29
- REPVLJRCJUVQFA-UHFFFAOYSA-N (-)-isopinocampheol Natural products C1C(O)C(C)C2C(C)(C)C1C2 REPVLJRCJUVQFA-UHFFFAOYSA-N 0.000 title claims abstract description 29
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229940116229 borneol Drugs 0.000 title claims abstract description 29
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000011973 solid acid Substances 0.000 title claims abstract description 26
- 238000003786 synthesis reaction Methods 0.000 title abstract description 5
- 230000015572 biosynthetic process Effects 0.000 title abstract description 4
- 238000001354 calcination Methods 0.000 claims abstract description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 58
- 238000003756 stirring Methods 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 241000779819 Syncarpia glomulifera Species 0.000 claims description 19
- 239000001739 pinus spp. Substances 0.000 claims description 19
- 229940036248 turpentine Drugs 0.000 claims description 19
- 235000006408 oxalic acid Nutrition 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 14
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 12
- 239000002808 molecular sieve Substances 0.000 claims description 11
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 8
- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 claims description 7
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 5
- 230000032050 esterification Effects 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000007127 saponification reaction Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 229940116315 oxalic acid Drugs 0.000 description 14
- 239000002243 precursor Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- 239000002202 Polyethylene glycol Substances 0.000 description 11
- 229920001223 polyethylene glycol Polymers 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 229940116411 terpineol Drugs 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000005411 L01XE02 - Gefitinib Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XGALLCVXEZPNRQ-UHFFFAOYSA-N gefitinib Chemical compound C=12C=C(OCCCN3CCOCC3)C(OC)=CC2=NC=NC=1NC1=CC=C(F)C(Cl)=C1 XGALLCVXEZPNRQ-UHFFFAOYSA-N 0.000 description 2
- 229960002584 gefitinib Drugs 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 102000001301 EGF receptor Human genes 0.000 description 1
- 108060006698 EGF receptor Proteins 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229940116316 dihydrate oxalic acid Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an application of a magnesium sulfate modified KIT-6 solid acid catalyst in borneol synthesis, wherein the catalyst is prepared by adopting a dipping-calcining method.
Description
Technical Field
The invention relates to an application of a magnesium sulfate modified KIT-6 solid acid catalyst in selective synthesis of borneol, belonging to the technical field of chemical industry.
Background
Borneol is a natural product with important application value, is considered to have the effects of inducing resuscitation, refreshing mind, relieving swelling and pain, clearing heat and detoxicating in traditional Chinese medicine, and has wide application in the fields of health care, food and the like. The medical value of the biological medicine is also widely studied in modern biomedicine, and Riming Yuan et al show in the journal ACS Applied Material that: the nano Natural Borneol (NBNPs) and gefitinib (epidermal growth factor receptor tyrosine kinase (EGFR-TK) inhibitor) have synergistic effect, so that the anticancer capability of the gefitinib is enhanced, and the in-vivo double toxicity of the two medicaments is reduced.
The adoption of chemical synthesis to obtain borneol is an economical and rapid way. Guo and the like use lanthanum modified sulfonated chiral mesoporous silicon as a catalyst, turpentine and anhydrous oxalic acid as raw materials to prepare borneol with 40.83% yield in a high selectivity manner, and the selectivity of the borneol is still low. Yang Yiwen, etc. in the form of solid acid S 2 O 8 2- /ZrO 2 NiO is used as a catalyst, borneol is synthesized through the esterification reaction of anhydrous oxalic acid and alpha-pinene, and the yield of the borneol in the reaction reaches 55.8 percent. Anhydrous oxalic acid is usually used as an esterifying agent when solid acid is used as a catalyst for synthesizing borneol, but commercial oxalic acid contains a small amount of water, and the commercial oxalic acid is used as a raw material and is subjected to secondary drying and is driedWhen the air is volatilized, a large amount of oxalic acid gas is volatilized, and the oxalic acid gas has great harm effect on the respiratory tract of a human body. Therefore, the market still needs a catalyst which can synthesize borneol with high selectivity under the condition of low requirement on the water content in oxalic acid.
Disclosure of Invention
Aiming at the market demand and the problems existing in the prior art, the invention provides a magnesium sulfate modified KIT-6 solid acid catalyst for synthesizing borneol by using oxalic acid with low water content and high selectivity, and the catalyst prepared by modifying a KIT-6 molecular sieve by magnesium sulfate can be used for synthesizing borneol with high selectivity under the condition of taking oxalic acid with low water content as an esterifying agent when catalyzing alpha-pinene to carry out esterification-saponification reaction.
The method takes a KIT-6 molecular sieve as a carrier, and adopts a magnesium sulfate solution impregnation method to obtain the magnesium sulfate modified KIT-6 solid acid catalyst.
The method comprises the following steps:
(1) Mixing polyethylene glycol (P123) with polyethylene glycol block polypropylene glycol block polyethylene glycol, water and concentrated hydrochloric acid, stirring for 4-10 h at 30-45 ℃ in a water bath, adding 1.0-3.0 g of n-butanol under stirring, and continuing stirring for 0.5-3 h at 30-45 ℃ in a constant-temperature water bath; 3-5 g of ethyl silicate is slowly dripped into the mixture after the stirring speed is regulated, stirring is continued for 15-30 hours, a mixture is obtained, the mixture is reacted for 15-30 hours at the constant temperature of 80-140 ℃ by a hydrothermal method, the mixture is taken out, after cooling, solid-liquid separation is carried out, after washing the solid with water and ethanol respectively to be neutral, a filter cake is dried for 3-10 hours at the temperature of 60-120 ℃, and calcination is carried out for 3-9 hours at the temperature of 300-900 ℃ to obtain the KIT-6 molecular sieve;
the mass ratio of the polyethylene glycol block polypropylene glycol block polyethylene glycol (P123) to the concentrated hydrochloric acid is 1.5-2.5:70:1-5;
the water comprises distilled water, deionized water and ultrapure water;
(2) Adding the KIT-6 molecular sieve into a magnesium sulfate aqueous solution with the concentration of 0.1-1.0 mol/L, then soaking for 6-12h under stirring, carrying out solid-liquid separation, washing, drying and calcining the solid to obtain a magnesium sulfate modified KIT-6 solid acid catalyst;
(3) Adding turpentine, a magnesium sulfate modified KIT-6 solid acid catalyst and oxalic acid into a reactor, and stirring and reacting for 7-10 hours at 90-120 ℃ to obtain an esterification product; and carrying out saponification reaction on the esterified product and an alcohol solution containing NaOH or KOH to obtain borneol, wherein the addition amount of the solid acid catalyst is 6-9% of the mass of turpentine, the molar ratio of alpha-pinene to oxalic acid in turpentine is 1:0.5-0.9, and the molar ratio of the esterified product to NaOH or KOH is 1:4-6.
The technical scheme of the invention has the following advantages:
1. when oxalic acid with low water content is used as a raw material, the borneol can be synthesized with high selectivity, the total borneol yield can reach 60.35%, the generation of by-product terpineol is effectively inhibited, and the problem that the commercial oxalic acid is dried for the second time and endangers human health is solved;
2. the preparation method has the advantages of simple preparation steps, no noble metal, cleanness, environmental protection and lower cost, and the catalyst can be recycled and reused.
Detailed Description
The present invention will be further described in detail by way of examples, which are not intended to limit the scope of the invention thereto, and in which the reagents are conventional commercial reagents or reagents prepared by conventional methods, and in which the methods are conventional unless otherwise specified.
Example 1: the preparation method of the magnesium sulfate modified KIT-6 solid acid catalyst and the method for synthesizing borneol are as follows:
(1) Mixing 2.5g of polyethylene glycol block polypropylene glycol block polyethylene glycol (P123), 70g of distilled water and 1.5g of concentrated hydrochloric acid, stirring in a constant-temperature water bath at 30 ℃ for 10 hours, uniformly dispersing a template agent, dripping 2.0g of n-butanol under 1000 revolutions per minute of stirring, and continuing stirring in the constant-temperature water bath at 30 ℃ for 3 hours; 3.0g of ethyl silicate is slowly dripped into the kettle at a stirring speed of 1500 rpm, stirring is continued for 25 hours to obtain precursor sol, the precursor sol is poured into a 100mL hydrothermal reaction kettle for reacting at a constant temperature of 100 ℃ for 25 hours, the precursor sol is taken out, the precursor sol is naturally cooled, the white solid is obtained after filtration, the solid is respectively washed with water and ethanol until the solid is neutral, the solid is dried in an air blast manner in a constant temperature drying box at 100 ℃ for 4 hours to remove water and ethanol, and then the precursor sol is calcined for 6 hours after the temperature is increased to 600 ℃ at 1 ℃/min to obtain the KIT-6 molecular sieve;
(2) Adding 2g of KIT-6 molecular sieve into 0.5mol/L magnesium sulfate solution, soaking and stirring for 9h at 35 ℃ in water bath, drying at 80 ℃ for 5h after solid-liquid separation, and calcining for 4h at 500 ℃ to obtain a magnesium sulfate modified KIT-6 solid acid catalyst;
(3) Adding turpentine and magnesium sulfate modified KIT-6 solid acid catalyst into a reactor (the addition amount of the catalyst is 7% of the mass of turpentine), adding dihydrated oxalic acid according to the molar ratio of alpha-pinene to oxalic acid in turpentine of 1:0.7, and then stirring and reacting for 8 hours in an oil bath at 100 ℃ to obtain an esterification product; saponifying the esterified product and an ethanol solution containing NaOH with the mass concentration of 20% at 80 ℃, wherein the mol ratio of the esterified product to the NaOH is 1:5, so as to prepare a borneol-containing solution; the conversion of turpentine was 100%, the total selectivity of borneol was 60.35%, and the selectivity of terpineol was 4.7%.
Example 2: the preparation method of the magnesium sulfate modified KIT-6 solid acid catalyst and the method for synthesizing borneol are as follows:
(1) Mixing 1.5g of polyethylene glycol block polypropylene glycol block polyethylene glycol (P123), 70g of deionized water and 3g of concentrated hydrochloric acid, stirring for 7h in a constant-temperature water bath at 40 ℃, uniformly dispersing a template agent, dripping 1.0g of n-butanol under stirring at 1000 revolutions per minute, and stirring for 2h in a constant-temperature water bath at 40 ℃; 3.0g of ethyl silicate is slowly dripped into the kettle at a stirring speed of 1500 rpm, stirring is continued for 15 hours to obtain precursor sol, the precursor sol is poured into a 100mL hydrothermal reaction kettle for reacting for 30 hours at a constant temperature of 80 ℃, the precursor sol is taken out, water is rapidly cooled, the solid is obtained through centrifugation, white solid is obtained after being washed by water and ethanol respectively until the solid is neutral, the solid is dried in vacuum in a vacuum drying box at 60 ℃ for 10 hours to remove water and ethanol, and the precursor sol is directly heated to 300 ℃ and then calcined for 9 hours to obtain the KIT-6 molecular sieve;
(2) Adding 2g of KIT-6 molecular sieve into 0.1mol/L magnesium sulfate solution, soaking and stirring for 6h at room temperature, performing solid-liquid separation, drying at 80 ℃ for 6h, and calcining at 300 ℃ for 8h to obtain a magnesium sulfate modified KIT-6 solid acid catalyst;
(3) Adding turpentine and a magnesium sulfate modified KIT-6 solid acid catalyst into a reactor (the addition amount of the magnesium sulfate modified KIT-6 solid acid catalyst is 6% of the mass of turpentine), adding anhydrous oxalic acid according to the proportion of alpha-pinene to anhydrous oxalic acid in the turpentine being 1:0.9, and then stirring and reacting for 10 hours in an oil bath at 90 ℃ to obtain an esterified product; saponifying the esterified product and an ethanol solution containing NaOH with the mass concentration of 20% at 75 ℃, wherein the mol ratio of the esterified product to the NaOH is 1:4, so as to prepare a borneol-containing solution; the conversion of turpentine was 100%, the total selectivity of borneol was 54.71%, and the selectivity of terpineol was 1.3%.
Example 3: the preparation method of the magnesium sulfate modified KIT-6 solid acid catalyst and the method for synthesizing borneol are as follows:
(1) Mixing 2.0g of polyethylene glycol block polypropylene glycol block polyethylene glycol (P123), 70g of ultrapure water and 4g of concentrated hydrochloric acid, stirring for 4 hours in a constant-temperature water bath at 45 ℃, uniformly dispersing a template agent, dripping 3.0g of n-butanol under 1000 revolutions per minute of stirring, and continuing stirring in the constant-temperature water bath at 40 ℃ for 2 hours; 3.5g of ethyl silicate is slowly dripped into the kettle at a stirring speed of 1500 rpm, stirring is continued for 20 hours to obtain precursor sol, the precursor sol is poured into a 100mL hydrothermal reaction kettle for reacting at a constant temperature of 120 ℃ for 30 hours, the precursor sol is taken out, after the precursor sol is quickly cooled by water, white solid is obtained by centrifugation, after the solid is respectively washed to be neutral by water and ethanol, the solid is dried in a drying box at 120 ℃ in a windless manner for 3 hours to remove water and ethanol, and the precursor sol is heated to 700 ℃ at a speed of 5 ℃/min and then calcined for 7 hours to obtain the KIT-6 molecular sieve;
(2) Adding 2g of KIT-6 molecular sieve into 1.0mol/L magnesium sulfate solution, soaking and stirring for 10h at 20 ℃ in water bath, drying for 5h at 80 ℃ after solid-liquid separation, and calcining for 3h at 700 ℃ to obtain a magnesium sulfate modified KIT-6 solid acid catalyst;
adding turpentine and a magnesium sulfate modified KIT-6 solid acid catalyst into a reactor (the adding amount of the magnesium sulfate modified KIT-6 solid acid catalyst is 9% of the mass of turpentine), adding dihydrate oxalic acid according to the proportion of the mole ratio of alpha-pinene to oxalic acid in turpentine being 1:0.5, and then stirring and reacting for 7 hours in an oil bath at 120 ℃ to obtain an esterification product; saponifying the esterified product with ethanol solution containing 20% KOH at 80deg.C, wherein the mol ratio of the esterified product to KOH is 1:5, to obtain solution containing borneol; the conversion of turpentine was 100%, the total selectivity of borneol was 57.87%, and the selectivity of terpineol was 6.39%.
Claims (4)
1. Application of magnesium sulfate modified KIT-6 solid acid catalyst in synthesizing borneol;
the magnesium sulfate modified KIT-6 solid acid catalyst is prepared by adding a KIT-6 molecular sieve into a magnesium sulfate aqueous solution, stirring and impregnating for 6-12h, carrying out solid-liquid separation, washing, drying and calcining the solid.
2. The use according to claim 1, characterized in that: the calcination temperature is 300-700 ℃.
3. The use according to claim 1, characterized in that: the concentration of the magnesium sulfate aqueous solution is 0.1 to 1.0mol/L.
4. The use according to claim 1, characterized in that: adding turpentine, a magnesium sulfate modified KIT-6 solid acid catalyst and oxalic acid into a reactor, and stirring and reacting for 7-10 hours at 90-120 ℃ to obtain an esterification product; and (3) carrying out saponification reaction on the esterified product and an alcohol solution containing NaOH or KOH to obtain borneol, wherein the addition amount of the magnesium sulfate modified KIT-6 solid acid catalyst is 6-9% of the mass of turpentine, the molar ratio of alpha-pinene to oxalic acid in turpentine is 1:0.5-0.9, and the molar ratio of the esterified product to NaOH or KOH is 1:4-6.
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| CN104817431A (en) * | 2015-03-31 | 2015-08-05 | 河北金木药业集团有限公司 | Borneol synthesis method |
| CN108286886A (en) * | 2018-03-28 | 2018-07-17 | 梧州黄埔化工药业有限公司 | A kind of method and apparatus of oxalic acid drying |
| CN109395771A (en) * | 2018-09-26 | 2019-03-01 | 昆明理工大学 | A kind of esterification-saponification catalyst and its preparation method and application |
| CN110818530A (en) * | 2019-10-23 | 2020-02-21 | 郭仪 | Method for preparing borneol |
| CN113181967A (en) * | 2021-04-28 | 2021-07-30 | 昆明理工大学 | Application of titanium sulfonate modified KIT-6 solid acid catalyst in borneol synthesis |
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| CN109395771A (en) * | 2018-09-26 | 2019-03-01 | 昆明理工大学 | A kind of esterification-saponification catalyst and its preparation method and application |
| CN110818530A (en) * | 2019-10-23 | 2020-02-21 | 郭仪 | Method for preparing borneol |
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