CN114213369A - Synthesis method of furoic acid - Google Patents
Synthesis method of furoic acid Download PDFInfo
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- CN114213369A CN114213369A CN202111611655.9A CN202111611655A CN114213369A CN 114213369 A CN114213369 A CN 114213369A CN 202111611655 A CN202111611655 A CN 202111611655A CN 114213369 A CN114213369 A CN 114213369A
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- 239000002253 acid Substances 0.000 title claims abstract description 127
- 238000001308 synthesis method Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 108
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 69
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000003112 inhibitor Substances 0.000 claims abstract description 23
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 146
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 229940011182 cobalt acetate Drugs 0.000 claims description 19
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 19
- 229940071125 manganese acetate Drugs 0.000 claims description 19
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical group [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 16
- 238000001291 vacuum drying Methods 0.000 claims description 16
- 230000002194 synthesizing effect Effects 0.000 claims description 11
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 10
- 239000011572 manganese Chemical class 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical group [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- NKQIMNKPSDEDMO-UHFFFAOYSA-L barium bromide Chemical compound [Br-].[Br-].[Ba+2] NKQIMNKPSDEDMO-UHFFFAOYSA-L 0.000 claims description 3
- 229910001620 barium bromide Inorganic materials 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 claims description 2
- 229940044119 2-tert-butylhydroquinone Drugs 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 abstract description 16
- 238000001704 evaporation Methods 0.000 abstract description 16
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000012043 crude product Substances 0.000 description 56
- 239000000047 product Substances 0.000 description 32
- 238000005303 weighing Methods 0.000 description 30
- 238000002425 crystallisation Methods 0.000 description 17
- 230000008025 crystallization Effects 0.000 description 17
- 238000012360 testing method Methods 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 15
- 238000004064 recycling Methods 0.000 description 15
- 238000010025 steaming Methods 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 6
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000001868 cobalt Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 229940075581 sodium bromide Drugs 0.000 description 2
- 238000005705 Cannizzaro reaction Methods 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229940077484 ammonium bromide Drugs 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- 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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a synthesis method of furoic acid, which comprises the steps of adding an acetic acid aqueous solution, furfural, a polymerization inhibitor and a catalyst into a reaction kettle, reacting at the pressure of 1-10MPa and the temperature of 50-200 ℃ in an oxygen atmosphere, continuing to react for 0.5-2h after the pressure drop is less than 0.1MPa after the reaction lasts for 30min, cooling to the room temperature after the reaction is finished, and extracting and rotary evaporating to obtain the furoic acid. The method has the advantages of simple and convenient operation, reusable catalyst, environmental protection, higher yield and the like.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a synthesis method of furoic acid.
Background
Furoic acid is commonly used as a bactericide, as a plasticizer in the plastics industry, as a preservative in the food industry, as an additive in the paint industry, and the like. In addition, the furoic acid is also used for synthesizing spices, medicines and the like, and the prior process for synthesizing the furoic acid mainly comprises an oxidation method and a disproportionation method.
The oxidation method generally takes furfural as a raw material, is prepared by oxidizing oxidants such as potassium permanganate, sodium hypochlorite and the like, has high yield, but has violent reaction and difficult control, and the oxidant cannot be recycled and is not suitable for industrialization; or the catalyst is obtained by introducing oxygen or air for catalytic oxidation in the presence of catalysts such as copper oxide, silver oxide and the like, the method has low yield and complex operation, the catalyst is reduced in the reaction process to lose the catalytic action, and can be repeatedly used after being reactivated, so the economic benefit is low.
The disproportionation method is characterized in that furfural is used as a raw material under a strong alkaline condition to perform a Cannizzaro reaction to generate the same molar amount of furoic acid and furfuryl alcohol, but the product obtained by the method is difficult to separate and has a low yield, and the furfuryl alcohol can be generally prepared by directly catalyzing and reducing the furfural, and the yield can reach 98 percent, so the method has lower economic benefit.
Therefore, the development and research of a novel furoic acid preparation method which is simple and convenient to operate, has reusable catalyst, is environment-friendly and has high yield is urgently needed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for synthesizing furoic acid, which has the advantages of simple and convenient operation, reusable catalyst, environmental friendliness, higher yield and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for synthesizing furoic acid comprises the steps of adding a solvent acetic acid aqueous solution, furfural, a polymerization inhibitor and a catalyst into a reaction kettle, reacting under the conditions of 1-10MPa (preferably 3-5MPa) of pressure and 50-200 ℃ (preferably 100-.
Specifically, the catalyst is one or a mixture of more than two of Co salt, Mn salt and Br salt.
Further, the Co salt can be selected from cobalt sulfate, cobalt chloride, cobalt acetate and the like, and cobalt acetate is preferred; the Mn salt can be selected from manganese nitrate, manganese chloride, manganese acetate and the like, and preferably manganese acetate; the bromine salt can be selected from sodium bromide, potassium bromide, barium bromide or ammonium bromide, preferably ammonium bromide.
Further preferably, the catalyst is a compound of Co salt, Mn salt and Br salt, and the addition amount of the catalyst is 0.7-1.5%, preferably 1.0-1.2% of the mass of the whole reaction system; co2+、Mn2+、Br-In a molar ratio of 1: 1: 0.1-1, preferably in a molar ratio of 1: 1: 0.2-0.5.
Specifically, the addition amount of the polymerization inhibitor is 0.2-0.3%, preferably 0.25% of the mass of the furfural; the polymerization inhibitor is one or more of hydroquinone, 2-tertiary butyl hydroquinone and 2, 5-di-tertiary butyl hydroquinone, and preferably 2-tertiary butyl hydroquinone.
Specifically, the mass concentration of the acetic acid aqueous solution is 70-80%, preferably 75%.
Further, the synthesis method of the furoic acid comprises the steps of extracting, decompressing and rotary steaming to obtain a crude furoic acid product, and decolorizing and drying the crude furoic acid product by using activated carbon to obtain a furoic acid product with the purity of more than 99%. The extract can be recycled. The reaction mother liquor (containing catalyst) can be repeatedly applied to the secondary kettle.
Specifically, the extractant used for extraction is any one of toluene, benzene, methyl isobutyl ketone and chloroform, and toluene is preferred. The usage amount of the extracting agent is about 15 percent of the total weight of the reaction system, the extraction is carried out for three times continuously,
specifically, the decolorizing condition of the crude furoic acid is that the crude furoic acid is stirred and refluxed for 0.5 to 1 hour at the temperature of between 75 and 80 ℃; the mass ratio of the crude furoic acid to the deionized water is 1: about 1 ℃ and the crystallization temperature is 0-5 ℃, and the crystallization mother liquor can be reused in the decolorization of the next batch. Drying under 40-60 deg.C (preferably 50 deg.C) for 5 hr or more.
Compared with the prior art, the method has the following beneficial effects:
1) the method fully utilizes the catalytic advantages of the composite catalyst, has good catalytic effect, and can be repeatedly used;
2) the method has the advantages of high reaction yield, good product quality, simple operation and easy industrialization;
3) the technical process of the method is environment-friendly.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited thereto.
In the following examples, 2-tert-butylhydroquinone was used as a polymerization inhibitor, and the raw materials used in the examples were all commercially available products that can be directly purchased.
Example 1:
a synthesis method of furoic acid comprises the following specific steps:
100g of acetic acid aqueous solution with the mass concentration of 75%, 40g of furfural, 0.1g of polymerization inhibitor and 1.40g of catalyst anhydrous cobalt acetate are sequentially added into a 200ml reaction kettle in one step, the stirring speed is 850r/min, after three times of oxygen replacement, the pressure is increased to 5MPa for leakage test, the temperature is slowly increased to 150 ℃ after the leakage test is confirmed, the reaction pressure is kept at 3-5MPa for continuous reaction, and the reaction is continued for 1h after the pressure drop is less than 0.1MPa after the reaction is carried out for 30 min. And (3) cooling to room temperature after the reaction is finished, extracting for 3 times by using 50g of toluene, carrying out rotary evaporation on the extract under reduced pressure, evaporating the toluene for recycling, separating out a crude furoic acid product, taking out the crude furoic acid product, and weighing. Decolorizing with active carbon (crude furoic acid at 78 deg.C under stirring and refluxing for 1h, mixing crude furoic acid with deionized water at a mass ratio of 1: 1 and a crystallization temperature of 0-5 deg.C), drying (vacuum drying at 50 deg.C for 5h) to obtain pure furoic acid, and weighing.
Example 2:
a synthesis method of furoic acid comprises the following specific steps:
100g of acetic acid aqueous solution with the mass concentration of 75%, 40g of furfural, 0.1g of polymerization inhibitor and 1.40g of cobalt sulfate catalyst are sequentially added into a 200ml reaction kettle in one step, the stirring speed is 850r/min, after three times of oxygen replacement, the pressure is increased to 5MPa for leakage test, after the leakage is confirmed, the temperature is slowly increased to 150 ℃ after the leakage is confirmed, the reaction pressure is kept at 3-5MPa for continuous reaction, and after the reaction is carried out for 30min, the pressure drop is less than 0.1MPa, the reaction is continued for 1 h. Cooling to room temperature after the reaction is finished, extracting for 3 times by using 50g of toluene, decompressing and rotary steaming the extract, evaporating the toluene, recovering and recycling the toluene, separating out a crude product of the furoic acid, taking out the crude product of the furoic acid, weighing, decoloring by active carbon (the crude product of the furoic acid is stirred and refluxed for 1h at 78 ℃, the mass ratio of the crude product of the furoic acid to deionized water is about 1: 1, the crystallization temperature is 0-5 ℃), drying (vacuum drying for 5h at 50 ℃) to obtain a pure product of the furoic acid, and weighing.
Example 3:
a synthesis method of furoic acid comprises the following specific steps:
100g of acetic acid aqueous solution with the mass concentration of 75%, 40g of furfural, 0.1g of polymerization inhibitor and 1.40g of cobalt chloride as a catalyst are sequentially added into a 200ml reaction kettle in one step, the stirring speed is 850r/min, after three times of oxygen replacement, the pressure is increased to 5MPa for leakage test, after the leakage is confirmed, the temperature is slowly increased to 150 ℃ after the leakage is confirmed, the reaction pressure is kept at 3-5MPa for continuous reaction, and after the reaction is carried out for 30min, the pressure drop is less than 0.1MPa, the reaction is continued for 1 h. Cooling to room temperature after the reaction is finished, extracting for 3 times by using 50g of toluene, decompressing and rotary steaming the extract, evaporating the toluene, recovering and recycling the toluene, separating out a crude product of the furoic acid, taking out the crude product of the furoic acid, weighing, decoloring by active carbon (the crude product of the furoic acid is stirred and refluxed for 1h at 78 ℃, the mass ratio of the crude product of the furoic acid to deionized water is about 1: 1, the crystallization temperature is 0-5 ℃), drying (vacuum drying for 5h at 50 ℃) to obtain a pure product of the furoic acid, and weighing.
Examples 1 to 3 product results for the synthesis of furoic acid are given in the table below.
| Examples | Catalyst and process for preparing same | Reaction time | Product color | Purity of the product | Molar yield | Remarks for note |
| Example 1 | Acetic acid cobalt salt | 18h | Light yellow | 96.3％ | 45.2％ | Difficulty in decoloring |
| Example 2 | Cobalt sulfate | 19h | Light yellow | 95.2％ | 43.1％ | Difficulty in decoloring |
| Example 3 | Cobalt chloride | 19h | Light yellow | 95.8％ | 43.3％ | Difficulty in decoloring |
And (4) conclusion: as can be seen from the data of examples 1 to 3 above, the use of cobalt salts as catalysts results in more by-products, difficult decolorization, less colored products, and relatively best results with cobalt acetate, and thus cobalt acetate is preferred.
Example 4:
a synthesis method of furoic acid comprises the following specific steps:
100g of acetic acid aqueous solution with the mass concentration of 75%, 40g of furfural, 0.1g of polymerization inhibitor and 1.40g of manganese acetate serving as a catalyst are sequentially added into a 200ml reaction kettle in one step, the stirring speed is 850r/min, after three times of oxygen replacement, the pressure is increased to 5MPa for leakage test, the temperature is slowly increased to 150 ℃ after no leakage is confirmed, the reaction pressure is kept at 3-5MPa for continuous reaction, and the reaction is continued for 1h after the pressure drop is less than 0.1MPa after 30 min. Cooling to room temperature after the reaction is finished, extracting for 3 times by using 50g of toluene, decompressing and rotary steaming the extract, evaporating the toluene, recovering and recycling the toluene, separating out a crude product of the furoic acid, taking out the crude product of the furoic acid, weighing, decoloring by active carbon (the crude product of the furoic acid is stirred and refluxed for 1h at 78 ℃, the mass ratio of the crude product of the furoic acid to deionized water is about 1: 1, the crystallization temperature is 0-5 ℃), drying (vacuum drying for 5h at 50 ℃) to obtain a pure product of the furoic acid, and weighing.
Example 5:
a synthesis method of furoic acid comprises the following specific steps:
100g of acetic acid aqueous solution with the mass concentration of 75%, 40g of furfural, 0.1g of polymerization inhibitor and 1.40g of manganese nitrate serving as a catalyst are sequentially added into a 200ml reaction kettle in one step, the stirring speed is 850r/min, after three times of oxygen replacement, the pressure is increased to 5MPa for leakage test, the temperature is slowly increased to 150 ℃ after leakage is confirmed, the reaction pressure is kept at 3-5MPa for continuous reaction, and the reaction is continued for 1h after the pressure drop is less than 0.1MPa after 30 min. Cooling to room temperature after the reaction is finished, extracting for 3 times by using 50g of toluene, decompressing and rotary steaming the extract, evaporating the toluene, recovering and recycling the toluene, separating out a crude product of the furoic acid, taking out the crude product of the furoic acid, weighing, decoloring by active carbon (the crude product of the furoic acid is stirred and refluxed for 1h at 78 ℃, the mass ratio of the crude product of the furoic acid to deionized water is about 1: 1, the crystallization temperature is 0-5 ℃), drying (vacuum drying for 5h at 50 ℃) to obtain a pure product of the furoic acid, and weighing.
Example 6:
a synthesis method of furoic acid comprises the following specific steps:
100g of acetic acid aqueous solution with the mass concentration of 75%, 40g of furfural, 0.1g of polymerization inhibitor and 1.40g of manganese chloride serving as a catalyst are sequentially added into a 200ml reaction kettle in one step, the stirring speed is 850r/min, after three times of oxygen replacement, the pressure is increased to 5MPa for leakage test, the temperature is slowly increased to 150 ℃ after no leakage is confirmed, the reaction pressure is kept at 3-5MPa for continuous reaction, and the reaction is continued for 1h after the pressure drop is less than 0.1MPa after 30 min. Cooling to room temperature after the reaction is finished, extracting for 3 times by using 50g of toluene, decompressing and rotary steaming the extract, evaporating the toluene, recovering and recycling the toluene, separating out a crude product of the furoic acid, taking out the crude product of the furoic acid, weighing, decoloring by active carbon (the crude product of the furoic acid is stirred and refluxed for 1h at 78 ℃, the mass ratio of the crude product of the furoic acid to deionized water is about 1: 1, the crystallization temperature is 0-5 ℃), drying (vacuum drying for 5h at 50 ℃) to obtain a pure product of the furoic acid, and weighing.
Examples 4 to 6 the results of the synthesis of furoic acid are given in the table below.
| Examples | Catalyst and process for preparing same | Reaction time | Product color | Purity of the product | Molar yield | Remarks for note |
| Example 4 | Manganese acetate | 20h | Light yellow | 94.1％ | 43.0％ | Difficulty in decoloring |
| Example 5 | Manganese nitrate | 20h | Light yellow | 93.5％ | 40.1％ | Difficulty in decoloring |
| Example 6 | Manganese chloride | 20h | Light yellow | 93.3％ | 40.5％ | Difficulty in decoloring |
And (4) conclusion: from the data of examples 4 to 6 above, it is seen that the use of manganese salt as catalyst, which is preferred, results in more reaction by-products, lower yield, and difficult discoloration of the product, and relatively optimal effect of manganese acetate.
Example 7:
a synthesis method of furoic acid comprises the following specific steps:
100g of acetic acid aqueous solution with the mass concentration of 75%, 40g of furfural, 0.1g of polymerization inhibitor, 1.42g (8.0mmol) of anhydrous cobalt acetate and 0.082g (0.80mmol) of sodium bromide are sequentially added into a 200ml reaction kettle in one step, the stirring speed is 850r/min, after three times of oxygen replacement, the pressure is increased to 5MPa for leakage test, after leakage is confirmed, the temperature is slowly increased to 150 ℃, the reaction pressure is kept at 3-5MPa for continuous reaction, and the reaction is continued for 1h after 30min pressure drop is less than 0.1 MPa. Cooling to room temperature after the reaction is finished, extracting for 3 times by using 50g of toluene, decompressing and rotary steaming the extract, evaporating the toluene, recovering and recycling the toluene, separating out a crude product of the furoic acid, taking out the crude product of the furoic acid, weighing, decoloring by active carbon (the crude product of the furoic acid is stirred and refluxed for 1h at 78 ℃, the mass ratio of the crude product of the furoic acid to deionized water is about 1: 1, the crystallization temperature is 0-5 ℃), drying (vacuum drying for 5h at 50 ℃) to obtain a pure product of the furoic acid, and weighing.
Example 8:
a synthesis method of furoic acid comprises the following specific steps:
100g of acetic acid aqueous solution with the mass concentration of 75%, 40g of furfural, 0.1g of polymerization inhibitor, 1.38g (8.0mmol) of manganese acetate and 0.082g (0.80mmol) of sodium bromide are sequentially added into a 200ml reaction kettle in one step, the stirring speed is 850r/min, after three times of oxygen replacement, the pressure is increased to 5MPa for leakage test, after leakage is confirmed, the temperature is slowly increased to 150 ℃ after leakage is confirmed, the reaction pressure is kept at 3-5MPa for continuous reaction, and the reaction is continued for 1h after 30min of pressure drop is less than 0.1 MPa. Cooling to room temperature after the reaction is finished, extracting for 3 times by using 50g of toluene, decompressing and rotary steaming the extract, evaporating the toluene, recovering and recycling the toluene, separating out a crude product of the furoic acid, taking out the crude product of the furoic acid, weighing, decoloring by active carbon (the crude product of the furoic acid is stirred and refluxed for 1h at 78 ℃, the mass ratio of the crude product of the furoic acid to deionized water is about 1: 1, the crystallization temperature is 0-5 ℃), drying (vacuum drying for 5h at 50 ℃) to obtain a pure product of the furoic acid, and weighing.
Example 9:
a synthesis method of furoic acid comprises the following specific steps:
100g of acetic acid aqueous solution with the mass concentration of 75%, 40g of furfural, 0.1g of polymerization inhibitor, 0.71g (4.0mmol) of anhydrous cobalt acetate and 0.69g (4.0mmol) of manganese acetate are sequentially added into a 200ml reaction kettle in one step, the stirring speed is 850r/min, after three times of oxygen replacement, the pressure is increased to 5MPa for leakage test, after leakage is confirmed, the temperature is slowly increased to 150 ℃ after leakage is confirmed, the reaction pressure is kept at 3-5MPa for continuous reaction, and after 30min, the reaction is continued for 1h when the pressure drop is less than 0.1 MPa. Cooling to room temperature after the reaction is finished, extracting for 3 times by using 50g of toluene, decompressing and rotary steaming the extract, evaporating the toluene, recovering and recycling the toluene, separating out a crude product of the furoic acid, taking out the crude product of the furoic acid, weighing, decoloring by active carbon (the crude product of the furoic acid is stirred and refluxed for 1h at 78 ℃, the mass ratio of the crude product of the furoic acid to deionized water is about 1: 1, the crystallization temperature is 0-5 ℃), drying (vacuum drying for 5h at 50 ℃) to obtain a pure product of the furoic acid, and weighing.
Example 10:
a synthesis method of furoic acid comprises the following specific steps:
100g of acetic acid aqueous solution with the mass concentration of 75%, 40g of furfural, 0.1g of polymerization inhibitor, 0.71g (4.0mmol) of anhydrous cobalt acetate, 0.69g (4.0mmol) of manganese acetate and 0.082g (0.80mmol) of sodium bromide are sequentially added into a 200ml reaction kettle at one time, the stirring speed is 850r/min, the pressure is increased to 5MPa for leakage test after three times of oxygen replacement, the temperature is slowly increased to 150 ℃ after leakage test is confirmed, the reaction pressure is kept at 3-5MPa for continuous reaction, and the reaction is continued for 1h after the pressure drop is less than 0.1MPa after 30min of reaction. Cooling to room temperature after the reaction is finished, extracting for 3 times by using 50g of toluene, decompressing and rotary steaming the extract, evaporating the toluene, recovering and recycling the toluene, separating out a crude product of the furoic acid, taking out the crude product of the furoic acid, weighing, decoloring by active carbon (the crude product of the furoic acid is stirred and refluxed for 1h at 78 ℃, the mass ratio of the crude product of the furoic acid to deionized water is about 1: 1, the crystallization temperature is 0-5 ℃), drying (vacuum drying for 5h at 50 ℃) to obtain a pure product of the furoic acid, and weighing.
Examples 7 to 10 the results of the synthesis of furoic acid are given in the table below.
From the data of examples 1, 4 and 7 to 10 above it can be seen that:
1) the comparison of the results of the examples 1 and 7 shows that the cobalt acetate is used as a catalyst, and a small amount of sodium bromide is added, so that the reaction speed can be obviously accelerated, the byproducts are reduced, the reaction yield is improved, and the purification of the product is facilitated;
2) the comparison of the results of the embodiments 4 and 8 also shows that, when manganese acetate is used as a catalyst and a small amount of sodium bromide is added, the reaction speed can be obviously accelerated, the byproducts are reduced, the reaction yield is improved, and the purification of the product is facilitated;
3) the comparison of the results of examples 1, 4 and 9 shows that under the condition of the same addition amount, cobalt and manganese have a certain synergistic catalytic action and have obvious positive effect compared with the single addition of cobalt salt or manganese salt;
4) the results of example 10 illustrate that: the effect of the concerted catalysis of cobalt acetate, manganese acetate and sodium bromide is the best. Thus, a composite catalyst of cobalt acetate, manganese acetate and sodium bromide is preferred.
Example 11:
a synthesis method of furoic acid comprises the following specific steps:
100g of acetic acid aqueous solution with the mass concentration of 75%, 40g of furfural, 0.1g of polymerization inhibitor, 0.71g (4.0mmol) of anhydrous cobalt acetate, 0.69g (4.0mmol) of manganese acetate and 0.095g (0.8mmol) of potassium bromide are sequentially added into a 200ml reaction kettle at one time, the stirring speed is 850r/min, after three times of oxygen replacement, the pressure is increased to 5MPa for leakage test, after leakage is confirmed, the temperature is slowly increased to 150 ℃, the reaction pressure is kept at 3-5MPa for continuous reaction, and the reaction is continued for 1h after the pressure drop is less than 0.1MPa after 30 min. Cooling to room temperature after the reaction is finished, extracting for 3 times by using 50g of toluene, decompressing and rotary steaming the extract, evaporating the toluene, recovering and recycling the toluene, separating out a crude product of the furoic acid, taking out the crude product of the furoic acid, weighing, decoloring by active carbon (the crude product of the furoic acid is stirred and refluxed for 1h at 78 ℃, the mass ratio of the crude product of the furoic acid to deionized water is about 1: 1, the crystallization temperature is 0-5 ℃), drying (vacuum drying for 5h at 50 ℃) to obtain a pure product of the furoic acid, and weighing.
Example 12:
a synthesis method of furoic acid comprises the following specific steps:
100g of acetic acid aqueous solution with the mass concentration of 75%, 40g of furfural, 0.1g of polymerization inhibitor, 0.71g (4.0mmol) of anhydrous cobalt acetate, 0.69g (4.0mmol) of manganese acetate and 0.119g (0.4mmol) of barium bromide are sequentially added into a 200ml reaction kettle at one time, the stirring speed is 850r/min, after three times of oxygen replacement, the pressure is increased to 5MPa for leakage test, after leakage is confirmed, the temperature is slowly increased to 150 ℃ after leakage is confirmed, the reaction pressure is kept at 3-5MPa for continuous reaction, and the reaction is continued for 1h after the pressure drop is less than 0.1MPa after 30 min. Cooling to room temperature after the reaction is finished, extracting for 3 times by using 50g of toluene, decompressing and rotary steaming the extract, evaporating the toluene, recovering and recycling the toluene, separating out a crude product of the furoic acid, taking out the crude product of the furoic acid, weighing, decoloring by active carbon (the crude product of the furoic acid is stirred and refluxed for 1h at 78 ℃, the mass ratio of the crude product of the furoic acid to deionized water is about 1: 1, the crystallization temperature is 0-5 ℃), drying (vacuum drying for 5h at 50 ℃) to obtain a pure product of the furoic acid, and weighing.
Example 13:
a synthesis method of furoic acid comprises the following specific steps:
100g of acetic acid aqueous solution with the mass concentration of 75%, 40g of furfural, 0.1g of polymerization inhibitor, 0.71g (4.0mmol) of anhydrous cobalt acetate, 0.69g (4.0mmol) of manganese acetate and 0.078g (0.8mmol) of ammonium bromide are sequentially added into a 200ml reaction kettle at one time, the stirring speed is 850r/min, after three times of oxygen replacement, the pressure is increased to 5MPa for leakage test, after leakage is confirmed, the temperature is slowly increased to 150 ℃, the reaction pressure is kept at 3-5MPa for continuous reaction, and the reaction is continued for 1h after the pressure drop is less than 0.1MPa after 30 min. Cooling to room temperature after the reaction is finished, extracting for 3 times by using 50g of toluene, decompressing and rotary steaming the extract, evaporating the toluene, recovering and recycling the toluene, separating out a crude product of the furoic acid, taking out the crude product of the furoic acid, weighing, decoloring by active carbon (the crude product of the furoic acid is stirred and refluxed for 1h at 78 ℃, the mass ratio of the crude product of the furoic acid to deionized water is about 1: 1, the crystallization temperature is 0-5 ℃), drying (vacuum drying for 5h at 50 ℃) to obtain a pure product of the furoic acid, and weighing.
Examples 10 to 13 the results of the synthesis of furoic acid are given in the table below.
And (4) conclusion: from the data of the above examples 10 to 13, it can be seen that: cobalt acetate, manganese acetate and different bromine salts are compounded as catalysts, the catalytic effects are slightly different, and ammonium bromide is preferred.
Example 14:
a synthesis method of furoic acid comprises the following specific steps:
100g of acetic acid aqueous solution with the mass concentration of 75%, 40g of furfural, 0.1g of polymerization inhibitor, 0.71g (4.0mmol) of anhydrous cobalt acetate, 0.69g (4.0mmol) of manganese acetate and 0.048g (0.49mmol) of ammonium bromide are sequentially added into a 200ml reaction kettle in one step, the stirring speed is 850r/min, after three times of oxygen replacement, the pressure is increased to 5MPa for leakage test, after leakage is confirmed, the temperature is slowly increased to 150 ℃, the reaction pressure is kept at 3-5MPa for continuous reaction, and the reaction is continued for 1h after the pressure drop is less than 0.1MPa after 30 min. Cooling to room temperature after the reaction is finished, extracting for 3 times by using 50g of toluene, decompressing and rotary steaming the extract, evaporating the toluene, recovering and recycling the toluene, separating out a crude product of the furoic acid, taking out the crude product of the furoic acid, weighing, decoloring by active carbon (the crude product of the furoic acid is stirred and refluxed for 1h at 78 ℃, the mass ratio of the crude product of the furoic acid to deionized water is about 1: 1, the crystallization temperature is 0-5 ℃), drying (vacuum drying for 5h at 50 ℃) to obtain a pure product of the furoic acid, and weighing.
Example 15:
a synthesis method of furoic acid comprises the following specific steps:
100g of acetic acid aqueous solution with the mass concentration of 75%, 40g of furfural, 0.1g of polymerization inhibitor, 0.71g (4.0mmol) of anhydrous cobalt acetate, 0.69g (4.0mmol) of manganese acetate and 0.125g (1.27mmol) of ammonium bromide are sequentially added into a 200ml reaction kettle at one time, the stirring speed is 850r/min, after three times of oxygen replacement, the pressure is increased to 5MPa for leakage test, after no leakage is confirmed, the temperature is slowly increased to 150 ℃, the reaction pressure is kept at 3-5MPa for continuous reaction, and after 30min, the reaction is continued for 1h when the pressure drop is less than 0.1 MPa. Cooling to room temperature after the reaction is finished, extracting for 3 times by using 50g of toluene, decompressing and rotary steaming the extract, evaporating the toluene, recovering and recycling the toluene, separating out a crude product of the furoic acid, taking out the crude product of the furoic acid, weighing, decoloring by active carbon (the crude product of the furoic acid is stirred and refluxed for 1h at 78 ℃, the mass ratio of the crude product of the furoic acid to deionized water is about 1: 1, the crystallization temperature is 0-5 ℃), drying (vacuum drying for 5h at 50 ℃) to obtain a pure product of the furoic acid, and weighing.
Examples 13 to 15 the results of the synthesis of furoic acid are given in the table below.
And (4) conclusion: from the data of the above examples 13 to 15, it can be seen that: when anhydrous cobalt acetate, manganese acetate and ammonium bromide with different dosages are compounded to be used as a catalyst, the reaction yield is reduced due to the fact that the proportion of the ammonium bromide is too low, and obvious positive influence is avoided when the proportion of the ammonium bromide is too high, so that the Co is recommended to be selected and used2+、Mn2+、Br-The mol ratio of each component is 1: 1: 0.2.
next, the reusability of the catalyst was verified, and the aqueous phase of the reaction solution after extraction with toluene contained acetic acid, a catalyst and a small amount of furoic acid, and the catalyst was slightly lost, so the catalyst was prepared as a mixed solution, and about 5% of the first-pot amount of the catalyst was added each time, and about 5% of the first-pot amount of the acetic acid solution was added, and the reaction conditions of example 13 were performed, and the results are summarized in the following table.
From the experimental data of the above table, the following conclusions can be drawn:
1) the catalyst can be continuously applied to more than 10 kettles under the condition that about 5 percent of the catalyst in the first kettle is added in each kettle and about 5 percent of the acetic acid solution in the first kettle is added simultaneously, and the activity is not obviously reduced;
2) the result is slightly fluctuated due to the operation problem, and belongs to a normal phenomenon;
3) the reaction yield is continuously reduced when reaching the 12 th kettle, the reaction yield is continuously applied according to 5 per mill addition amount, and the reaction yield is continuously reduced, which shows that the activity of the catalyst is obviously reduced;
4) from the 15 th kettle, increasing the catalyst addition amount to 10 per mill of the first kettle for reuse, wherein the reaction yield is obviously increased, the catalyst is continuously added according to the addition amount, the reaction yield is gradually reduced, and unqualified products appear in the 19 th kettle;
5) in order to ensure the reaction efficiency and the reaction yield, the reaction solvent and the catalyst are recommended to be replaced when the catalyst is applied to the tenth kettle.
The above-described embodiment is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications are possible without departing from the technical scope of the present invention as set forth in the claims.
Claims (9)
1. A synthesis method of furoic acid is characterized in that acetic acid aqueous solution, furfural, polymerization inhibitor and catalyst are added into a reaction kettle, reaction is carried out under the conditions of pressure of 1-10MPa and temperature of 50-200 ℃ in oxygen atmosphere, reaction is continued for 0.5-2h after 30min pressure drop is less than 0.1MPa, the reaction is cooled to room temperature after the reaction is finished, and the furoic acid is obtained through extraction and rotary evaporation.
2. The method for synthesizing furoic acid according to claim 1, wherein said catalyst is one or a mixture of two or more of Co salt, Mn salt and Br salt.
3. The method for synthesizing furoic acid according to claim 2, wherein said Co salt is selected from cobalt sulfate, cobalt chloride, or cobalt acetate; the Mn salt is selected from manganese nitrate, manganese chloride or manganese acetate; the bromine salt is selected from sodium bromide, potassium bromide, barium bromide or ammonium bromide.
4. The method for synthesizing furoic acid according to claim 3, wherein the catalyst is a compound of Co salt, Mn salt and Br salt, and the amount of the catalyst is 0.7-1.5% of the mass of the whole reaction system; co2+、Mn2+、Br-In a molar ratio of 1: 1: 0.1-1.
5. The method for synthesizing furoic acid according to claim 1, wherein the amount of the polymerization inhibitor added is 0.2-0.3% of the mass of the furfural, and the polymerization inhibitor is one or more of hydroquinone, 2-tert-butylhydroquinone and 2, 5-di-tert-butylhydroquinone.
6. The method for synthesizing furoic acid according to claim 1, wherein the mass concentration of the aqueous solution of acetic acid is 70-80%.
7. The method for synthesizing furoic acid according to claim 1, wherein the crude furoic acid is obtained by extraction, reduced pressure rotary evaporation, decolorized by activated carbon, and dried to obtain a furoic acid product with purity of more than 99%.
8. The method for synthesizing furoic acid according to claim 7, wherein the extractant selected for extraction is any one of toluene, benzene, methyl isobutyl ketone, and chloroform.
9. The process for the synthesis of furoic acid according to claim 7, wherein the decolorizing conditions are stirring reflux at 75-80 ℃ for 0.5-1 h; the drying condition is vacuum drying at 40-60 deg.C for more than 5 hr.
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