CN115197181A - Method for synthesizing alkali metal furoate by solid phase method - Google Patents
Method for synthesizing alkali metal furoate by solid phase method Download PDFInfo
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- CN115197181A CN115197181A CN202210765791.1A CN202210765791A CN115197181A CN 115197181 A CN115197181 A CN 115197181A CN 202210765791 A CN202210765791 A CN 202210765791A CN 115197181 A CN115197181 A CN 115197181A
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- furoate
- carbonate
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- hydroxide
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- 238000000034 method Methods 0.000 title claims abstract description 32
- -1 alkali metal furoate Chemical class 0.000 title claims abstract description 18
- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 15
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 9
- 238000010532 solid phase synthesis reaction Methods 0.000 title claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000007790 solid phase Substances 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 12
- 239000002585 base Substances 0.000 claims abstract description 8
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims abstract description 6
- 150000008041 alkali metal carbonates Chemical class 0.000 claims abstract description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 11
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 claims description 6
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 4
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000026 rubidium carbonate Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 18
- 238000003786 synthesis reaction Methods 0.000 abstract description 12
- 239000001569 carbon dioxide Substances 0.000 abstract description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 9
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 239000002912 waste gas Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- CKFRRDULRPAXQT-UHFFFAOYSA-M C1=COC(=C1)C(=O)[O-].[Cs+] Chemical compound C1=COC(=C1)C(=O)[O-].[Cs+] CKFRRDULRPAXQT-UHFFFAOYSA-M 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000000498 cooling water Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 5
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 5
- LWYJTCLDMYROHH-UHFFFAOYSA-M potassium;furan-2-carboxylate Chemical compound [K+].[O-]C(=O)C1=CC=CO1 LWYJTCLDMYROHH-UHFFFAOYSA-M 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000021523 carboxylation Effects 0.000 description 2
- 238000006473 carboxylation reaction Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- KRBZFYNFUFQUFF-UHFFFAOYSA-M lithium;furan-2-carboxylate Chemical compound [Li+].[O-]C(=O)C1=CC=CO1 KRBZFYNFUFQUFF-UHFFFAOYSA-M 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HDCRDACZYDHUQX-UHFFFAOYSA-M sodium;furan-2-carboxylate Chemical compound [Na+].[O-]C(=O)C1=CC=CO1 HDCRDACZYDHUQX-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Furan Compounds (AREA)
Abstract
The invention provides a method for synthesizing alkali metal furoate by a solid phase method. The method uses furoic acid and alkali metal hydroxide and/or alkali metal carbonate as raw materials, the raw materials are mixed and ground in a solid phase reactor, and the raw materials are directly subjected to chemical reaction in a solid state to generate the alkali metal furoate. The reaction temperature is between room temperature and 120 ℃, and the pressure is between 0.005 and 0.1MPa. Solid bases include alkali metal hydroxides, alkali metal carbonates, and mixtures thereof. The alkali metal furoate synthesized by the method is used for synthesizing the 2, 5-furandicarboxylic acid by reacting with carbon dioxide. The synthesis method has the advantages of simple process, low energy consumption, less equipment investment, high yield and no generation of waste water, waste residue and waste gas, is a novel green chemical synthesis technology, and has better economic benefit, remarkable social benefit and wide industrial application prospect.
Description
Technical Field
The invention relates to a method for synthesizing alkali metal furoate by a solid phase method, belonging to the technical field of synthesis of bio-based chemical intermediates.
Background
Furoic acid (C) 5 H 4 O 3 Molecular weight 112) also known as 2-furancarboxylic acid, is an organic acid containing furan rings derived from biomass. From furoic acid and baseAlkali metal furoate generated by neutralization reaction and carbon dioxide are carboxylated to prepare 2, 5-furandicarboxylic acid (FDCA) which is a novel method for green and efficient synthesis of bulk chemicals from biomass sources. FDCA is an organic dibasic acid based on furan ring structure, has a 'rigid' plane structure, is an important novel bio-based platform compound, and can replace terephthalic acid raw materials to prepare novel bio-based polyester, polyamide, epoxy resin and polyurethane high polymer materials due to the similarity of the structure and chemical properties of the FDCA and terephthalic acid which is a petroleum derived chemical product. The high polymer material prepared by the method has excellent mechanical property and higher glass transition temperature and thermal deformation temperature, and can be applied to the fields of high-barrier packaging bottles and films, high-end nylon, bulletproof vests, high-end coatings, adhesives and the like. In addition, FDCA can be used as an organic synthesis intermediate, and can also be used for preparing various furan derivatives, and is used in the fields of biological medicine, fire safety, catalysts, plasticizers, cosmetics, food essence and the like.
Currently, the FDCA synthesis route is mainly a 5-Hydroxymethylfurfural (HMF) route and a furoic acid route. The HMF route has been reported in a large number of documents and patents, but has the following problems: (1) the raw material HMF has small reserve, difficult and unstable preparation, and very expensive cost; (2) the HMF oxidation requires the use of expensive noble metal catalysts and has low conversion and difficult product separation. Therefore, the method is not suitable for large-scale industrial production at present, thereby limiting the application of FDCA and downstream products thereof. The furoic acid is obtained by oxidizing biomass-derived furfural, the source is wide, the price is low, the furoic acid is easy to obtain, FDCA can be synthesized by taking the furoic acid and carbon dioxide as raw materials, high-value utilization of biomass resources and chemical conversion of industrial waste gas carbon dioxide can be realized, and the synthesis cost of FDCA is effectively reduced, so that the industrialization process of FDCA is accelerated, the dependence on petroleum resources is gradually eliminated in the bio-based high polymer material industry, and the sustainable development of the whole high polymer material industry is promoted.
The reaction of furoic acid and alkali to produce furoate is an important step in preparing FDCA by furoic acid process. The document "Carbon dioxide cleavage via carbonate-catalyzed C-H carboxylation" (Aaindeeta Banerjee, nature, 2016, 531) reports the synthesis of FDCA starting from furoic acid: firstly, reacting furoic acid with cesium carbonate to generate cesium furoate, then reacting cesium furoate with carbon dioxide to generate FDCA cesium salt, and then acidifying with hydrochloric acid to obtain an FDCA product. Wherein, the synthesis of the cesium furoate is an intermediate product for preparing FDCA, and comprises the steps of taking water as a medium, reacting the furoic acid with cesium carbonate in an aqueous solution, then evaporating and concentrating, and drying at 150 ℃ to obtain a cesium furoate product. The disadvantages of the aqueous solution method for synthesizing the cesium furoate are that: (1) the evaporation concentration requires a large amount of energy; (2) generating wastewater in the preparation process; (3) Low production efficiency, large equipment investment and high production cost. The alkali metal furoate represented by cesium furoate is an important intermediate for preparing FDCA, the synthesis process is a key step for preparing FDCA by a furoic acid method, the defects of an aqueous solution method are overcome, and the synthesis of the alkali metal furoate with high efficiency and low energy consumption is an important way for reducing the production cost of FDCA synthesized by taking furoic acid and carbon dioxide as raw materials and promoting the industrialization process of FDCA.
The invention content is as follows:
the invention aims to provide a solid-phase synthesis method of alkali metal furoate, and the synthesized alkali metal furoate is used for preparing 2, 5-furandicarboxylic acid by carboxylation with carbon dioxide. The method mixes and grinds furoic acid and alkali metal hydroxide or carbonate in a solid phase reactor, and directly carries out chemical reaction to synthesize the alkali metal furoate in a solid state, is a 'green' chemical synthesis technology, and can overcome the defects of high energy consumption, low production efficiency, large wastewater amount and the like of the existing aqueous solution method.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for synthesizing alkali metal furoate by a solid phase method is characterized by comprising the following steps: mixing, grinding and reacting the furoic acid and the solid base in a solid phase reactor for 1 to 10 hours at the temperature of between room temperature and 120 ℃ and under the pressure of between 0.005 and 0.15MPa.
The solid base includes alkali metal hydroxides, alkali metal carbonates and mixtures thereof.
The alkali metal hydroxide is any one or a mixture of sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide and rubidium hydroxide, and the alkali metal carbonate is any one or a mixture of sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate and rubidium carbonate.
The molar ratio of the furoic acid to the solid base is =1 to 2, preferably 1.05 to 1.65.
The solid phase reactor is any one of an upright ball mill, a horizontal ball mill or a double-screw extruder.
The reaction time for the solid-phase mixing and grinding is preferably 3 to 6 hours.
The temperature of the solid phase mixing and grinding reaction is preferably controlled to be 40-90 ℃.
The solid phase mixing and grinding reaction pressure is preferably 0.01-0.10 MPa.
The invention is characterized in that: the furoic acid and solid alkali are mixed and ground in a solid phase reactor and directly react to synthesize the alkali metal furoate in a solid state. The alkali metal furoate synthesized by the method is used for synthesizing the 2, 5-furandicarboxylic acid by reacting with carbon dioxide. The synthesis method has the advantages of simple process, low energy consumption, less equipment investment, high yield and no generation of waste water, waste residue and waste gas, is a novel green chemical synthesis technology, and has better economic benefit, remarkable social benefit and wide industrial application prospect.
The specific implementation mode is as follows:
in order that the present invention may be more readily understood, the following detailed description of the invention is given by way of example only, and is not intended to limit the scope of the invention.
[ example 1 ]
560g (5 mol) of furoic acid and 220g (5.5 mol) of sodium hydroxide are added into an attritor mill, nitrogen is replaced, the rotating speed is adjusted to 200 r/min, the temperature is kept between 40 and 60 ℃ by utilizing cooling water, the vacuum pumping is carried out, the system pressure is kept to be 0.03MPa, the grinding reaction is carried out for 5 hours, and then the drying is carried out at 80 ℃ to obtain the sodium conate product. The yield of the sodium furoate is 96.5 percent.
[ example 2 ]
560g (5 mol) of furoic acid and 294g (5.25 mol) of potassium hydroxide are added into an attritor mill, nitrogen is replaced, the rotating speed is adjusted to 300 r/min, the temperature is kept below 30 ℃ by utilizing cooling water, vacuum pumping is carried out, the system pressure is kept to be 0.05MPa, grinding reaction is carried out for 3 hours, and then drying is carried out at 80 ℃ to obtain a potassium furoate product. The yield of the potassium furoate is 97.5 percent.
[ example 3 ]
Adding 280g (2.5 mol) of furoic acid and 375g (2.5 mol) of cesium hydroxide into an attritor mill, replacing with nitrogen, adjusting the rotating speed to 220 r/min, keeping the temperature below 90 ℃ by using cooling water, vacuumizing, keeping the system pressure at 0.005MPa, grinding for reacting for 4 hours, and then drying at 120 ℃ to obtain a cesium furoate product. Cesium furoate yield 99.5%.
[ example 4 ]
1680g (15 mol) of furoic acid, 728g (13 mol) of potassium hydroxide, 750g (5 mol) of cesium hydroxide and 3912g (12 mol) of cesium carbonate are added into a horizontal ball mill, nitrogen gas is replaced, the rotating speed is adjusted to 50 r/min, the temperature is kept below 80 ℃ by cooling water, vacuum pumping is carried out, the system pressure is kept below 0.02MPa, grinding reaction is carried out for 10 hours, and then drying is carried out at 80 ℃ to obtain a mixed product of potassium furoate and cesium furoate. The total yield of furoate is 99.9%.
[ example 5 ]
Adding 2240g (20 mol) of furoic acid, 4140g (30 mol) of potassium carbonate and 1630g (5 mol) of cesium carbonate into a horizontal ball mill, replacing with nitrogen, adjusting the rotation speed to 50 revolutions per minute, vacuumizing, keeping the system pressure below 0.01MPa, keeping the temperature below 90 ℃ by using cooling water, grinding for 6 hours, and drying at 90 ℃ to obtain a mixed product of potassium furoate and cesium furoate. The total yield of furoate is 99.8%.
[ example 6 ]
2240g (20 mol) of furoic acid, 1590g (15 mol) of sodium carbonate, 3912g (12 mol) of cesium carbonate and 402g (3 mol) of lithium hydroxide are added into a horizontal ball mill, nitrogen gas is replaced, the rotating speed is adjusted to 50 r/min, vacuum pumping is carried out, the system pressure is kept below 0.08MPa, the temperature is kept below 80 ℃ by utilizing cooling water, grinding reaction is carried out for 8 hours, and then drying is carried out at 80 ℃ to obtain a mixed product of potassium furoate, cesium furoate and lithium furoate. The total yield of furoate is 98.5%.
[ example 7 ]
Adding 3360g (30 mol) of furoic acid, 13040g (40 mol) of cesium carbonate and 923g (7.25 mol) of rubidium hydroxide into a double-screw extruder, replacing with nitrogen, adjusting the rotation speed to 100 revolutions per minute, keeping the system pressure to be 0.10MPa and the temperature to be 100 ℃, mixing and reacting for 2 hours, and then drying at the vacuum temperature of 120 ℃ to obtain a mixed product of cesium furoate and rubidium furoate. The total yield of furoate is 98.0%.
[ example 8 ]
2800g (25 mol) of furoic acid, 13040g (40 mol) of cesium carbonate and 244g (1 mol) of lithium carbonate are added into a double-screw extruder, nitrogen gas is replaced, the rotation speed is adjusted to 100 revolutions per minute, the system pressure is maintained at 0.12MPa, the temperature is maintained at 110 ℃, mixing reaction is carried out for 1.5 hours, and then drying is carried out at the vacuum temperature of 120 ℃ to obtain a mixed product of cesium furoate and lithium furoate. The total yield of furoate is 98.4%.
[ example 9 ]
Adding 2856g (25.5 mol) of furoic acid, 13040g (40 mol) of cesium carbonate and 232g (1 mol) of rubidium carbonate into a double-screw extruder, replacing with nitrogen, adjusting the rotating speed to 100 revolutions per minute, keeping the system pressure to be 0.15MPa and the temperature to be 120 ℃, mixing and reacting for 1 hour, and then drying at the vacuum temperature of 120 ℃ to obtain a mixed product of cesium furoate and rubidium furoate. The total yield of furoate is 99.2%.
What has been described above is merely a preferred example of the present invention. It should be noted that other equivalent variations and modifications can be made by those skilled in the art in light of the technical teaching provided by the present invention, and should be considered as the protection scope of the present invention.
Claims (9)
1. A method for synthesizing alkali metal furoate by a solid phase method is characterized by comprising the following steps: mixing, grinding and reacting the furoic acid and the solid base in a solid phase reactor for 1 to 10 hours at the temperature of between room temperature and 120 ℃ and under the pressure of between 0.005 and 0.15MPa.
2. The process of claim 1, wherein the solid base comprises an alkali metal hydroxide, an alkali metal carbonate, and mixtures thereof.
3. The method of claim 2, wherein the selected alkali metal hydroxide is any one of sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, rubidium hydroxide or a mixture thereof; the selected alkali metal carbonate is any one of sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate and rubidium carbonate or a mixture of the sodium carbonate, the potassium carbonate, the cesium carbonate, the lithium carbonate and the rubidium carbonate.
4. The method according to claim 1, wherein the molar ratio of furoic acid to solid base is = 1.
5. The method as set forth in claim 1, wherein the molar ratio of furoic acid to solid base is = 1.05-1.65.
6. The method of claim 1, wherein the solid phase reactor is any one of an attritor mill, a horizontal ball mill, or a twin screw extruder.
7. The method of claim 1, wherein the solid phase mixing and milling reaction time is 3 to 6 hours.
8. The method of claim 1, wherein the solid phase mixing and milling reaction temperature is 40 to 90 ℃.
9. The method according to claim 1, wherein the pressure of the solid-phase mixing and milling reaction is 0.01 to 0.10MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210765791.1A CN115197181B (en) | 2022-07-01 | Method for synthesizing alkali metal furoate by solid phase method |
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|---|---|---|---|
| CN202210765791.1A CN115197181B (en) | 2022-07-01 | Method for synthesizing alkali metal furoate by solid phase method |
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| CN115197181A true CN115197181A (en) | 2022-10-18 |
| CN115197181B CN115197181B (en) | 2024-05-14 |
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| CN101357319A (en) * | 2007-08-01 | 2009-02-04 | 北京农学院 | Solid phase reactor |
| CN101357885A (en) * | 2007-08-01 | 2009-02-04 | 北京农学院 | Method for synthesizing sodium succinate through solid phase reaction |
| CN103553723A (en) * | 2013-11-08 | 2014-02-05 | 翁莹冰 | Solid-phase synthesis method of phosphate-phosphite compound fertilizers |
| CN113480502A (en) * | 2021-08-06 | 2021-10-08 | 吉林省中科聚合工程塑料有限公司 | Preparation method of furoic acid |
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