CN108640822B - Preparation method of 4-vinyl guaiacol and 4-vinyl guaiacol - Google Patents
Preparation method of 4-vinyl guaiacol and 4-vinyl guaiacol Download PDFInfo
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- CN108640822B CN108640822B CN201810381986.XA CN201810381986A CN108640822B CN 108640822 B CN108640822 B CN 108640822B CN 201810381986 A CN201810381986 A CN 201810381986A CN 108640822 B CN108640822 B CN 108640822B
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- YOMSJEATGXXYPX-UHFFFAOYSA-N 2-methoxy-4-vinylphenol Chemical compound COC1=CC(C=C)=CC=C1O YOMSJEATGXXYPX-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- KSEBMYQBYZTDHS-HWKANZROSA-M (E)-Ferulic acid Natural products COC1=CC(\C=C\C([O-])=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-M 0.000 claims abstract description 36
- KSEBMYQBYZTDHS-HWKANZROSA-N ferulic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-N 0.000 claims abstract description 36
- 229940114124 ferulic acid Drugs 0.000 claims abstract description 36
- KSEBMYQBYZTDHS-UHFFFAOYSA-N ferulic acid Natural products COC1=CC(C=CC(O)=O)=CC=C1O KSEBMYQBYZTDHS-UHFFFAOYSA-N 0.000 claims abstract description 36
- 235000001785 ferulic acid Nutrition 0.000 claims abstract description 36
- QURCVMIEKCOAJU-UHFFFAOYSA-N trans-isoferulic acid Natural products COC1=CC=C(C=CC(O)=O)C=C1O QURCVMIEKCOAJU-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000007787 solid Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 239000012043 crude product Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 239000003930 superacid Substances 0.000 claims abstract description 10
- 230000002378 acidificating effect Effects 0.000 claims description 34
- 238000006114 decarboxylation reaction Methods 0.000 claims description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910016287 MxOy Inorganic materials 0.000 claims description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 11
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 11
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 10
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 6
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 238000007670 refining Methods 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 33
- 239000000047 product Substances 0.000 abstract description 27
- 238000010924 continuous production Methods 0.000 abstract description 7
- 229920000642 polymer Polymers 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- PNJLLTZAEWRCRQ-UHFFFAOYSA-N 4-ethenyl-2-methoxyphenol Chemical compound COC1=CC(C=C)=CC=C1O.COC1=CC(C=C)=CC=C1O PNJLLTZAEWRCRQ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 244000223014 Syzygium aromaticum Species 0.000 description 1
- 235000016639 Syzygium aromaticum Nutrition 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 235000016213 coffee Nutrition 0.000 description 1
- 235000013353 coffee beverage Nutrition 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000013555 soy sauce Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 235000019605 sweet taste sensations Nutrition 0.000 description 1
- 235000013616 tea Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 235000014101 wine Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明属于4－乙烯基愈创木酚的制备技术领域，涉及4－乙烯基愈创木酚的制备方法及4－乙烯基愈创木酚。本发明提供的4－乙烯基愈创木酚的制备方法，包括以下步骤：在固定床反应器中装入固体超强酸催化剂，然后加热固定床反应器；向固定床反应器中输入阿魏酸和弱碱性有机溶剂的混合物；所述混合物在固体超强酸催化剂的作用下进行脱羧反应得到4－乙烯基愈创木酚粗产品，对粗产品进行精制，得到高纯度的4－乙烯基愈创木酚。本发明的方法易于实现连续化生产，工艺简单，提高了反应收率，并大大减少了聚合物的产生，提高了产品质量。The invention belongs to the technical field of preparation of 4-vinyl guaiacol, and relates to a preparation method of 4-vinyl guaiacol and 4-vinyl guaiacol. The preparation method of 4-vinylguaiacol provided by the present invention comprises the following steps: loading a solid superacid catalyst into a fixed bed reactor, then heating the fixed bed reactor; inputting ferulic acid into the fixed bed reactor A mixture of a weak alkaline organic solvent; the mixture is decarboxylated under the action of a solid superacid catalyst to obtain a crude 4-vinyl guaiacol product, and the crude product is refined to obtain a high-purity 4-vinyl guaiacol Cremoquinol. The method of the invention is easy to realize continuous production, the process is simple, the reaction yield is improved, the production of polymers is greatly reduced, and the product quality is improved.
Description
Technical Field
The invention belongs to the technical field of preparation of 4-vinyl guaiacol, and particularly relates to a preparation method of 4-vinyl guaiacol and 4-vinyl guaiacol.
Background
4-Vinylguaiacol (4-Vinylguaiacol, 4VG for short) and 2-Methoxy-4-vinylphenol (2-Methoxy-4-vinylphenol). The molecular formula is C9H10O2Density 1.11X 103kg/m3The melting point is 26-29 ℃, and the boiling point is 100 ℃/667 Pa. The product is colorless or light yellow oily liquid at normal temperature and pressure, and has fermented fragrance, slight sweet taste and slight phenol smell. The natural 4-vinyl guaiacol mainly exists in volatile matters of corn alcohol fermentation, has aromatic odor similar to clove, is a main aroma component determining the quality of food such as wine, soy sauce, tea, coffee, cheese and the like, is one of high-grade perfumes commonly used in the industries such as daily use chemicals, medicines, essence synthesis and the like, has the commercial value 40 times that of ferulic acid, and therefore has wide application value and development prospect.
At present, 4-vinyl guaiacol in the market is synthesized by a chemical method mostly, but the existing chemical synthesis process mainly has the following defects: (1) most of the reaction is intermittent reaction, continuous production cannot be realized, the operation is complex, the yield is low, and the quality of the obtained product is poor; (2) the reaction time is long, the reaction speed is slow, and generally 4 to 8 hours are needed; (3) 4-vinyl guaiacol which is a product obtained by the reaction is easy to polymerize into a dimer; (4) the used catalyst has poor catalytic effect, inconvenient use, short service life and long reaction period.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of 4-vinyl guaiacol, which is easy to realize continuous production, simple in process, improves the reaction yield, greatly reduces the generation of polymers and improves the product quality.
The second purpose of the invention is to provide 4-vinyl guaiacol, and the 4-vinyl guaiacol prepared by the method has high yield and good quality.
In order to achieve the purpose, the invention adopts the technical scheme that:
according to one aspect of the present invention, there is provided a method for preparing 4-vinylguaiacol, comprising the steps of:
filling a solid super acidic catalyst into the fixed bed reactor, and then heating the fixed bed reactor;
inputting a mixture of ferulic acid and a weakly basic organic solvent into a fixed bed reactor;
and (3) performing decarboxylation reaction on the mixture under the action of a solid super acidic catalyst to obtain a 4-vinyl guaiacol crude product, and refining the crude product to obtain the high-purity 4-vinyl guaiacol.
As a further preferable technical scheme, the solid super acidic catalyst comprises granular SO with the diameter phi of 2-8 mm4 2-/MxOyThe solid super acidic catalyst is preferably 4-6 mm in diameter phi.
As a further preferred embodiment, the SO4 2-/MxOyM in solid super acidic catalystxOyIs ZrO2、TiO2、SnO2An oxide or a composite oxide thereof.
According to a further preferable technical scheme, the heating temperature is 120-280 ℃, and the preferable temperature is 150-250 ℃.
As a further preferable technical solution, the weakly basic organic solvent includes a N-containing weakly basic organic solvent;
preferably, the weakly basic organic solvent comprises at least one of pyridine, pyrrole, N-dimethylformamide, N-dimethylacetamide, quinoline, and indole.
As a further preferable technical scheme, in the mixture of the ferulic acid and the weakly basic organic solvent, the mass ratio of the ferulic acid to the weakly basic organic solvent is 1: (1.5-8), preferably 1: (2-5).
As a further preferable technical scheme, the space velocity of the mixture input of the ferulic acid and the weakly alkaline organic solvent is 0.5-4.0 g/min, preferably 1.0-3.0 g/min.
According to a further preferable technical scheme, the diameter of the fixed bed reactor is 2-5 cm, the height of the fixed bed reactor is 70-100 cm, and preferably, the diameter of the fixed bed reactor is 3-4 cm, and the height of the fixed bed reactor is 80-90 cm.
As a further preferred embodiment, the refining comprises: the obtained crude product is decompressed to remove the solvent, and then is rectified to obtain the high-purity 4-vinyl guaiacol.
According to another aspect of the present invention, there is also provided 4-vinylguaiacol prepared by the above-described method for preparing 4-vinylguaiacol.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method of the invention adopts a fixed bed reaction process to prepare the 4-vinyl guaiacol, and utilizes the principle that the amount of the catalyst is far larger than that of the fed materials to realize instant reaction, thereby reducing the time of self-contact of the product, further greatly reducing the generation of polymers which can not be detected almost, obviously improving the yield of the reaction, and obtaining the product with good quality and high purity; meanwhile, the fixed bed reaction process is adopted, so that the industrialized continuous production is easy to realize, the process is simple, and the operation difficulty of the reaction is reduced.
(2) The solid super acid is used as a catalyst, and high-temperature transient reaction is realized by virtue of the acidic decarboxylation of the solid super acid, so that the decarboxylation reaction is more thorough, the generation of polymers is reduced, the catalytic effect is good, the use is convenient, and the service life is short.
(3) The method adopts a weakly alkaline organic solvent as a solvent for dissolving ferulic acid, can promote the decarboxylation reaction, and has short reaction time and high production efficiency; and the problem that the decarboxylation reaction is slow by adopting a neutral or acidic solvent, or the decarboxylation is avoided by adopting a strong alkaline solvent when ferulic acid is combined into stable salt.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to embodiments and examples, but those skilled in the art will understand that the following embodiments and examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. Those who do not specify the conditions are performed according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In a first aspect, there is provided in at least one embodiment a method of preparing 4-vinylguaiacol, comprising the steps of:
filling a solid super acidic catalyst into the fixed bed reactor, and then heating the fixed bed reactor;
inputting a mixture of ferulic acid and a weakly basic organic solvent into a fixed bed reactor;
and (3) performing decarboxylation reaction on the mixture under the action of a solid super acidic catalyst to obtain a 4-vinyl guaiacol crude product, and refining the crude product to obtain the high-purity 4-vinyl guaiacol.
The invention mainly aims at the problems of low reaction temperature, low reaction speed, long reaction time (generally 4-8 hours), easy polymerization of the obtained product 4-vinyl guaiacol into dimer, low yield, complex operation and the like in the existing intermittent preparation process of a fluidized bed or a reaction kettle of 4-vinyl guaiacol. The method realizes high-temperature instant reaction by virtue of the acidic decarboxylation of the solid super acid, greatly reduces the generation of polymers, and obviously improves the reaction yield; meanwhile, the fixed bed reaction process is adopted, so that continuous production is easy to realize, and the operation difficulty of the reaction is reduced. Further, compared with the prior art, the method provided by the invention mainly has the following advantages:
(1) the method provided by the invention adopts a fixed bed reaction process to prepare the 4-vinyl guaiacol, utilizes the principle that the amount of the catalyst is far larger than that of the fed materials to realize instant reaction, reduces the time of self-contact of the product, further greatly reduces the generation of polymers which can not be detected almost, obviously improves the yield of the reaction, and obtains the product with good quality and high purity; meanwhile, the fixed bed reaction process is adopted, so that the industrialized continuous production is easy to realize, the process is simple, and the operation difficulty of the reaction is reduced. (2) The solid super acid is used as a catalyst, and high-temperature transient reaction is realized by virtue of the acidic decarboxylation of the solid super acid, so that the decarboxylation reaction is more thorough, the generation of polymers is reduced, the catalytic effect is good, the use is convenient, and the service life is short. (3) The method adopts a weakly alkaline organic solvent as a solvent for dissolving ferulic acid, can promote the decarboxylation reaction, and has short reaction time and high production efficiency; and the problem that the decarboxylation reaction is slow by adopting a neutral or acidic solvent, or the decarboxylation is avoided by adopting a strong alkaline solvent when ferulic acid is combined into stable salt.
In a preferred embodiment, the solid super acidic catalyst comprises granular SO with a diameter phi of 2-8 mm4 2-/MxOyThe solid super acidic catalyst is preferably 4-6 mm in diameter phi.
In a preferred embodiment, the SO4 2-/MxOyM in solid super acidic catalystxOyIs ZrO2、TiO2、SnO2An oxide or a composite oxide thereof.
The solid super acid is a novel catalytic material developed in recent years, and has better catalytic activity, selectivity and reusability for a plurality of chemical reactions. The catalyst has the advantages of easy separation from reactants, reusability, no corrosion to reactor, no environmental pollution, less catalyst pollution, simple preparation, good selectivity, etc.
Wherein, SO4 2-/MxOyThe solid super acidic catalyst is prepared by reacting SO4 2-Loaded on some metal oxides and prepared by roasting under certain temperature conditions. The invention adopts granular SO4 2-/MxOyThe solid-like super acidic catalyst has high catalytic activity, is convenient to recover and reuse, is easy to separate from a reaction system, can be suitable for fixed bed catalytic reaction and fluidized bed catalytic reaction, has wide application range, good application effect and long service life, and is beneficial to reducing the production cost, thereby solving the problems of poor catalytic effect, inconvenient use, short service life and the like of the catalyst adopted in the existing process for preparing the 4-vinyl guaiacol.
For SO of the invention4 2-/MxOyThe specific type of the solid super acidic catalyst is not particularly limited as long as it can effectively realize the acidic decarboxylation, and for example, it can be a granular solid super acidic catalyst disclosed in patent No. CN1189242C, in which Al is used as the basic carrier2O3、SiO2Oxide or Al2O3-SiO2The composite oxide and active carrier are ZrO2、TiO2、SnO2An oxide or a composite oxide thereof.
It will be appreciated that MxOyIs ZrO2、TiO2、SnO2Oxide or composite oxide thereof is represented byxOyMay be ZrO2Oxide, TiO2Oxides or SnO2Any one of the oxides may contain ZrO2、TiO2And SnO2A composite oxide of at least two of them.
For the above granular type SO4 2-/MxOyThe particle size of the solid-like super acid catalyst is not particularly limited, and may be, typically but not limited to, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm or 8 mm.
In a preferred embodiment, the heating temperature is 120 to 280 ℃, preferably 150 to 250 ℃.
Heating the fixed bed reactor filled with the solid super acidic catalyst to 120-280 ℃, and then feeding (inputting a mixed solution); it can be understood that the heating temperature is the reaction temperature of ferulic acid, and the reaction is carried out in the temperature range, which is helpful for improving the reaction rate and enhancing the reaction effect. Typically, but not by way of limitation, the heating temperature may be 120 ℃, 140 ℃, 150 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃, 240 ℃, 250 ℃, 260 ℃ or 280 ℃.
In a preferred embodiment, the weakly basic organic solvent comprises a N-containing weakly basic organic solvent;
preferably, the weakly basic organic solvent comprises at least one of pyridine, pyrrole, N-dimethylformamide, N-dimethylacetamide, quinoline, and indole.
The invention carries out a great deal of selection on solvents for dissolving ferulic acid, and a great deal of research and experiments show that the adoption of the alkalescent organic solvent can promote the decarboxylation reaction, and experiments prove that the adoption of the neutral or acidic solvent can slow the decarboxylation reaction and reduce the reaction efficiency, while the adoption of the strong alkaline organic solvent can combine ferulic acid with ferulic acid into stable salt which is not decarboxylated.
It should be noted that the present invention is not limited to a specific type of the weakly basic organic solvent, and includes, but is not limited to, at least one of pyridine, pyrrole, N-dimethylformamide, N-dimethylacetamide, quinoline, and indole, and the N-containing weakly basic organic solvent having a type property can be applied to the present invention.
In a preferred embodiment, in the mixture of ferulic acid and the weakly basic organic solvent, the mass ratio of ferulic acid to the weakly basic organic solvent is 1: (1.5-8), preferably 1: (2-5). Typically, but not by way of limitation, the mass ratio of ferulic acid to weakly basic organic solvent is 1: 1.5, 1: 2. 1: 3. 1: 4. 1: 5. 1: 6 or 1: 8. the mass ratio in the range can ensure that the ferulic acid is fully dissolved, can reduce the waste of raw materials and the energy consumption of later treatment, and can reduce the production cost while promoting the smooth reaction.
In a preferred embodiment, the space velocity of the mixture of ferulic acid and the weakly basic organic solvent is 0.5-4.0 g/min, preferably 1.0-3.0 g/min.
A pre-prepared mixture of ferulic acid and a weakly basic organic solvent is pumped into a fixed bed reactor at a mass space velocity of typically, but not exclusively, 0.5g/min, 1.0g/min, 2.0g/min, 3.0g/min or 4.0 g/min.
In a preferred embodiment, the diameter of the fixed bed reactor is 2-5 cm, and the height is 70-100 cm, preferably, the diameter is 3-4 cm, and the height is 80-90 cm.
It should be noted that the size of the fixed bed reactor is not specially limited, and the fixed bed reactor can be selectively designed according to actual production requirements; the fixed bed reactor can be of a single-tube type or other forms. Typically, but not by way of limitation, the fixed bed reactor may have a diameter of 2cm, 3cm, 3.5cm, 4cm or 5cm and a height of 70cm, 80cm, 90cm or 100 cm.
In a preferred embodiment, the refining comprises: the obtained crude product is decompressed to remove the solvent, and then is rectified to obtain the high-purity 4-vinyl guaiacol.
In a preferred embodiment, the preparation method of the 4-vinyl guaiacol comprises the following steps:
(a) charging granular SO with a diameter phi of 4-6 mm into an adiabatic fixed bed reactor with a diameter of 3.5cm and a height of 80cm4 2-/MxOy200g of quasi-solid super acidic catalyst; the SO4 2-/MxOyM in solid super acidic catalystxOyIs ZrO2、TiO2、SnO2An oxide or a composite oxide thereof;
(b) the mass ratio of ferulic acid to weakly alkaline organic solvent is 1: (2-5) dissolving ferulic acid to obtain a mixture; wherein the alkalescent organic solvent is an N-containing alkalescent organic solvent and comprises at least one of pyridine, pyrrole, N-dimethylformamide, N-dimethylacetamide, quinoline and indole;
(c) heating a fixed bed reactor to 150-250 ℃;
(d) inputting a mixture of ferulic acid and a weakly alkaline organic solvent into a fixed bed reactor through a pump at a mass airspeed of 1.0-3.0 g/min;
(d) the mixture is decarboxylated under the action of a solid super acidic catalyst to obtain a crude product (solution) containing 4-vinyl guaiacol, the crude product is subjected to reduced pressure to remove the solvent, and then rectification is carried out to obtain the high-purity 4-vinyl guaiacol.
The GC purity of the product is 98.5 to 99.5 percent by gas chromatography analysis; the molar yield of the product is calculated to be 90-95%.
From the above, the preparation method of the invention has the advantages of short reaction time, mild reaction conditions, high product yield, simple production process, improved product quality and production efficiency, reduced preparation cost, easy realization of the industrial continuous production, high efficiency and clean effect of the 4-vinyl guaiacol, and laying a foundation for the industrial application thereof.
In a second aspect, there is provided in some embodiments a 4-vinyl guaiacol, the 4-vinyl guaiacol being prepared using the above-described 4-vinyl guaiacol preparation method.
The 4-vinyl guaiacol prepared by the method has high yield, good quality and wide market application prospect.
The present invention will be further described with reference to specific examples and comparative examples.
Example 1
A preparation method of 4-vinyl guaiacol comprises the following steps:
(a) charging granular SO with a diameter phi of 4-6 mm into an adiabatic fixed bed reactor with a diameter of 3.5cm and a height of 80cm4 2-/MxOy200g of quasi-solid super acidic catalyst; the SO4 2-/MxOyM in solid super acidic catalystxOyIs ZrO2、TiO2、SnO2An oxide or a composite oxide thereof;
(b) the mass ratio of ferulic acid to weakly alkaline organic solvent is 1: 2 dissolving ferulic acid to obtain a mixture; wherein the alkalescent organic solvent is pyridine;
(c) heating a fixed bed reactor to 150 ℃;
(d) inputting a mixture of ferulic acid and a weakly alkaline organic solvent into a fixed bed reactor through a pump at a mass space velocity of 1.5 g/min;
(d) the mixture is subjected to decarboxylation reaction under the action of a solid super acidic catalyst to obtain a crude product containing 4-vinyl guaiacol, the crude product is subjected to reduced pressure to remove a solvent, and then rectification is performed to obtain the high-purity 4-vinyl guaiacol.
The GC purity of the product is 99.1 percent by gas chromatography analysis; the molar yield of the product was calculated to be 91%.
Example 2
A method for preparing 4-vinylguaiacol, which is different from the method of example 1 in that:
in the step (b), the alkalescent organic solvent is N, N-dimethylacetamide, and the mass ratio of the ferulic acid to the alkalescent organic solvent is 1: 3;
in the step (c), the temperature is 150 ℃;
in the step (d), the mass space velocity is 1.8 g/min.
The GC purity of the product is 99.4 percent by gas chromatography analysis; the molar yield of the product was calculated to be 93%.
Example 3
A method for preparing 4-vinylguaiacol, which is different from the method of example 1 in that:
in the step (b), the alkalescent organic solvent is indole, and the mass ratio of the ferulic acid to the alkalescent organic solvent is 1: 5;
in the step (c), the temperature is 220 ℃;
in the step (d), the mass space velocity is 2.6 g/min.
The GC purity of the product is 99.2 percent by gas chromatography analysis; the molar yield of the product was calculated to be 92%.
Example 4
A method for preparing 4-vinylguaiacol, which is different from the method of example 1 in that:
in the step (b), the alkalescent organic solvent is quinoline, and the mass ratio of the ferulic acid to the alkalescent organic solvent is 1: 4;
in the step (c), the temperature is 200 ℃;
in the step (d), the mass space velocity is 3.0 g/min.
The GC purity of the product is 99.3 percent by gas chromatography analysis; the molar yield of the product was calculated to be 95%.
Comparative example 1
A method for preparing 4-vinylguaiacol, which is different from the method of example 1 in that:
this comparative example replaces the solid super acidic catalyst in example 1 with an alumina catalyst.
The GC purity of the product is 88 percent by gas chromatographic analysis; the molar yield of the product was calculated to be 65%.
Comparative example 2
A method for preparing 4-vinylguaiacol, which is different from the method of example 1 in that:
this comparative example replaces the weakly basic organic solvent pyridine of example 1 with the strongly basic solvent sodium hydroxide.
The molar yield of the product was calculated to be 0.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of 4-vinyl guaiacol is characterized by comprising the following steps:
filling a solid super acidic catalyst into the fixed bed reactor, and then heating the fixed bed reactor;
inputting a mixture of ferulic acid and a weakly basic organic solvent into a fixed bed reactor;
performing decarboxylation reaction on the mixture under the action of a solid super acidic catalyst to obtain a 4-vinyl guaiacol crude product, and refining the crude product to obtain high-purity 4-vinyl guaiacol;
the solid super acidic catalyst comprises granular SO with the diameter phi = 2-8 mm4 2-/MxOyA quasi-solid super acidic catalyst;
the SO4 2-/MxOyM in solid super acidic catalystxOyIs ZrO2、TiO2、SnO2An oxide or a composite oxide thereof;
the heating temperature is 120-280 ℃;
the weakly basic organic solvent comprises at least one of pyridine, pyrrole, N-dimethylformamide, N-dimethylacetamide, quinoline and indole.
2. The method for preparing 4-vinylguaiacol as claimed in claim 1, wherein the solid super acid catalyst has a diameter of Φ = 4-6 mm.
3. The method of claim 1, wherein the heating temperature is 150 to 250 ℃.
4. The method for producing 4-vinylguaiacol as claimed in claim 1, wherein the mass ratio of ferulic acid to the weakly basic organic solvent in the mixture of ferulic acid and the weakly basic organic solvent is 1: (1.5-8).
5. The method for producing 4-vinylguaiacol as claimed in claim 1, wherein the mass ratio of ferulic acid to the weakly basic organic solvent is 1: (2-5).
6. The method of preparing 4-vinylguaiacol as claimed in claim 1, wherein the space velocity of the mixture of ferulic acid and the weakly basic organic solvent is 0.5 to 4.0 g/min.
7. The method of preparing 4-vinylguaiacol as claimed in claim 1, wherein the space velocity of the mixture of ferulic acid and the weakly basic organic solvent is 1.0 to 3.0g/min in terms of mass space velocity.
8. The method of claim 1, wherein the fixed bed reactor has a diameter of 2 to 5cm and a height of 70 to 100 cm.
9. The method of claim 1, wherein the fixed bed reactor has a diameter of 3 to 4cm and a height of 80 to 90 cm.
10. The method of producing 4-vinylguaiacol according to any one of claims 1 to 9, wherein the purification comprises: the obtained crude product is decompressed to remove the solvent, and then is rectified to obtain the high-purity 4-vinyl guaiacol.
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