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CN-121991124-A - Small molecular organic phosphonate catalyst and preparation method and application thereof

CN121991124ACN 121991124 ACN121991124 ACN 121991124ACN-121991124-A

Abstract

The invention provides a small molecular organic phosphonate catalyst, a preparation method and application thereof, wherein the structure of the small molecular organic phosphonate catalyst is RPO 3 2‑ ·M 2+ 、RPO 3 2‑ ·2/3M 3+ 、RPO 3 2‑ ·1/2M 4+ 、RPO 3 2‑ ·2/5M 5+ 、 or RPO 3 2‑ ·1/3M 6+ , and the catalyst is used for preparing 5-hydroxymethylfurfural, has the advantages of mild reaction condition, high conversion rate and high yield, is beneficial to large-scale production, and has simple and convenient synthesis process, low cost and meets the economic applicability of industrial production.

Inventors

  • ZHU JINGYANG
  • LIU XIANGQIAN
  • TAO DAWEI

Assignees

  • 合肥单源催化科技有限公司

Dates

Publication Date
20260508
Application Date
20241108

Claims (10)

  1. 1. A small molecule organic phosphonate catalyst characterized in that the small molecule organic phosphonate catalyst has a structure of RPO 3 2- ·M 2+ 、RPO 3 2- ·2/3M 3+ 、RPO 3 2- ·1/2M 4+ 、RPO 3 2- ·2/5M 5+ 、 or RPO 3 2- ·1/3M 6+ ; Wherein R is a substituted or unsubstituted C 1-20 alkyl group, a substituted or unsubstituted C 2-20 alkenyl group, a substituted or unsubstituted C 4-20 cycloalkyl group, a substituted or unsubstituted C 6-10 aryl group, A substituted or unsubstituted C 4-10 heterocyclyl, a substituted or unsubstituted C 4-10 heteroaryl, said substituted C 1-20 alkyl being selected from the group consisting of halogen, OH, OC 1-20 alkyl, at least one of PO (OH) 2 、C 6-10 aryl, C 4-10 heterocyclyl or C 4-10 heteroaryl, said substituted C 4-20 cycloalkyl, Substituted C 6-10 aryl, substituted C 4-10 heterocyclyl, substituted C 4-10 heteroaryl, the substituents being selected from the group consisting of halogen, OH, C 1-20 alkyl, At least one of C 2-20 alkenyl, OC 1-20 alkyl, or PO (OH) 2 ; The M metal is selected from the IIA, IIIA, IVA, IB, IIB, IIIB, VB, VIB, VIIB, VIIIB subgroup metals.
  2. 2. The small molecule organic phosphonate catalyst of claim 1, wherein R is C 1-20 alkyl, C 2-20 alkenyl, C 6-10 aryl, C 6-10 aryl C 1-20 alkyl or substituted C 6-10 aryl, the substituents in the substituted C 6-10 aryl being selected from at least one of halogen, OH, C 1-20 alkyl, C 2-20 alkenyl or OC 1-20 alkyl; Preferably, R is selected from hexyl, tetradecyl, phenyl, halophenyl, C 2-6 alkenylphenyl, C 1-6 alkyloxyphenyl, benzyl, halobenzyl, or C 1-6 alkoxy-substituted benzyl; Preferably, M is selected from Fe, al, mg, zn, sn, ti, zr, nb, W, in, la, hf or Ta.
  3. 3. The small molecule organophosphonate catalyst according to claim 1 or 2, wherein the small molecule organophosphonate catalyst is a metal salt of an organophosphonic acid having the structure RPO (OH) 2 , wherein R is as defined in claim 1; Preferably, the organic phosphonic acid is selected from hexyl phosphonic acid, tetradecyl phosphonic acid, phenylphosphonic acid, substituted phenylphosphonic acid, benzyl phosphonic acid, substituted benzyl phosphonic acid or heterocyclic phosphonic acid, wherein the substitution refers to substitution by C 1-6 alkane or halogen; Preferably, the organic phosphonic acid is selected from any one of the following organic phosphoric acids: the metal is selected from any one of Fe, al, mg, zn, sn, ti, zr, nb, W, in, la, hf or Ta.
  4. 4. A small molecule organophosphonate catalyst according to any one of claims 1-3, wherein the small molecule organophosphonate catalyst is one of the following organophosphonates: Zinc phenylphosphonate, tin (2-valent) phenylphosphonate, copper phenylphosphonate, iron phenylphosphonate, lanthanum phenylphosphonate, indium phenylphosphonate, tin (tetravalent) phenylphosphonate, titanium phenylphosphonate, zirconium phenylphosphonate, hafnium phenylphosphonate, niobium phenylphosphonate, tantalum phenylphosphonate, tungsten phenylphosphonate, zinc benzylphosphonate, tin (2-valent) benzylphosphonate, magnesium benzylphosphonate, copper benzylphosphonate, iron benzylphosphonate, aluminum benzylphosphonate, lanthanum benzylphosphonate, indium benzylphosphonate, tin (tetravalent) benzylphosphonate, titanium benzylphosphonate, zirconium benzylphosphonate, hafnium benzylphosphonate, niobium benzylphosphonate, tantalum benzylphosphonate, tungsten benzylphosphonate, zinc 4-methoxybenzylphosphonate, tin (2-valent) 4-methylbenzylphosphonate, copper 4-methylbenzylphosphonate, iron 4-methylbenzylphosphonate, aluminum 4-methylbenzylphosphonate, lanthanum 4-methylbenzylphosphonate, tin (2-valent) benzylphosphonic acid, zinc (2-chloro) 2- (2-chloro) benzylphosphonic acid, 2- (2-chloro) zinc benzylphosphonate, 2- (2-chloro) 2- (chloro) benzylphosphonic acid, 2-chloro) zinc (2-chloro) benzylphosphonic acid, 2- (2-chloro) 2- (2-chloro) benzylphosphonic acid, 2-chloro) zinc (2-chloro) phosphonate, magnesium 3- (bromobenzyl) phosphonate, copper 3- (bromobenzyl) phosphonate, iron 3- (bromobenzyl) phosphonate, aluminum 3- (bromobenzyl) phosphonate, tin 3- (bromobenzyl) phosphonate (tetravalent), titanium 3- (bromobenzyl) phosphonate, zirconium 3- (bromobenzyl) phosphonate, niobium 3- (bromobenzyl) phosphonate, zinc 4-vinylbenzyl phosphonate, tin 4-vinylbenzyl phosphonate (2-valent), magnesium 4-vinylbenzyl phosphonate, copper 4-vinylbenzyl phosphonate, iron 4-vinylbenzyl phosphonate, aluminum 4-vinylbenzyl phosphonate, tin 4-vinylbenzylphosphonate (tetravalent), titanium 4-vinylbenzylphosphonate, zirconium 4-vinylbenzylphosphonate, niobium 4-vinylbenzylphosphonate, iron 4-nitrobenzylphosphonate, tin 4-nitrobenzylphosphonate (tetravalent), titanium 4-nitrobenzylphosphonate, zinc hexylphosphonate, tin hexylphosphonate (2-valent), copper hexylphosphonate, iron hexylphosphonate, aluminum hexylphosphonate, tin hexylphosphonate (tetravalent), titanium hexylphosphonate, copper tetradecylphosphonate, iron tetradecylphosphonate, aluminum tetradecylphosphonate or titanium tetradecylphosphonate.
  5. 5. The method for preparing a small molecule organic phosphonate catalyst according to any one of claims 1-4, characterized in that the preparation method comprises the steps of: reacting organic phosphonic acid with a metal compound to prepare the micromolecular organic phosphonate catalyst; Wherein the metal is selected from group IIA, IIIA, IVA, IB, IIB, IIIB, VB, VIB, VIIB or group VIIIB metals.
  6. 6. The method of claim 5, wherein the metal is selected from Fe, al, mg, zn, sn, ti, zr, nb, W, in, la, hf or Ta; Preferably, the metal compound is selected from a metal salt, a metal hydroxide or a metal oxide; Preferably, the metal salt is selected from the group consisting of chloride, nitrate, sulfate or carbonate of a metal; Preferably, the preparation method comprises the following two conditions of adding a metal compound solution into an organic phosphonic acid solution, adjusting the pH value of the system to be 4-6, and reacting to obtain the micromolecular organic phosphonate catalyst; Or II, adding a metal compound into a solvent, and then adding organic phosphonic acid to react to obtain the micromolecular organic phosphonate catalyst; Preferably, in the method I, the solvent in the metal compound solution is water, and the solvent in the organic phosphonic acid solution is water; Preferably, the reaction in process I is carried out at room temperature for a period of 0.5 to 10 hours; preferably, after the reaction in the method I is finished, filtering the reaction solution, washing with deionized water, adding the wet product into water, stirring for 4-5 hours at 40-60 ℃, cooling, filtering and drying to obtain the micromolecular organic phosphonate catalyst; Preferably, the solvent in method II is water; preferably, the reaction in method II is carried out at room temperature for a period of 0.5-10 hours; Preferably, after the reaction in the method II is finished, the reaction solution is filtered, washed by deionized water and dried to obtain the micromolecular organic phosphonate catalyst.
  7. 7. A method for preparing 5-hydroxymethylfurfural, which is characterized in that biomass raw materials are used as raw materials, and dehydration reaction is carried out in the presence of an organic phosphonate catalyst and a cocatalyst, wherein the organic phosphonate catalyst is the organic phosphonate catalyst according to any one of claims 1-4.
  8. 8. The method of claim 7, wherein the mass ratio of catalyst to biomass feedstock is 0.01-1.0:1; Preferably, the biomass raw material is fructose and/or glucose; Preferably, the mass percentage content of the biomass raw material in the reaction system is 5-20%, preferably 10%.
  9. 9. The method according to claim 7 or 8, characterized in that the mass ratio of the co-catalyst to biomass feedstock is 0.01-1.0:1; preferably, the promoter is sodium chloride and/or potassium chloride.
  10. 10. The process according to claim 7 or 8, characterized in that the dehydration reaction is carried out in a solvent, which is an aqueous or non-aqueous phase system; preferably, the aqueous phase system is a mixture of water and an organic solvent; Preferably, the organic solvent in the aqueous phase system is any one or a combination of at least two of methyl isobutyl ketone, n-butanol, sec-butanol, tetrahydrofuran, 2-methyltetrahydrofuran, gamma valerolactone, acetone or acetonitrile; preferably, the volume ratio of the water phase to the organic solvent phase in the water-containing phase system is (0.1-1): 1; Preferably, the solvent of the anhydrous phase system is selected from any one or a mixture of at least two of dimethyl sulfoxide, dimethylformamide and dimethylacetamide; Preferably, the temperature of the reaction is 80-200 ℃ and the reaction time is 1min-2h; preferably, the reaction is carried out at a pressure of 0.5 to 2.0 Mpa; Preferably, the reaction is carried out with stirring at a speed of 300rpm to 1000rpm; Preferably, the reaction is operated using a continuous flow, the temperature of the continuous flow reaction is 80 ℃ to 200 ℃, and the reaction time is 1min to 2h; preferably, the continuous flow reaction is carried out at a pressure of 0.5 to 2.0 Mpa; Preferably, the ratio of flow rates of the aqueous phase to the organic phase during the continuous flow operation is from 1:1 to 1:10.

Description

Small molecular organic phosphonate catalyst and preparation method and application thereof Technical Field The invention belongs to the technical field of catalysts, and relates to a small molecular organic phosphonate catalyst, a preparation method and application thereof. Background Due to the non-renewable nature of fossil resources, the contradiction between the non-sustainability of traditional industries that use fossil resources as raw materials and the environmental protection requirements and sustainable development of today's society is becoming evident. The biomass resource is a resource with wide application prospect and sustainable development. The replacement of current petroleum-based chemicals with biomass-based preparation chemicals is an important solution. The 5-Hydroxymethylfurfural (HMF) is an important Biomass-based platform molecule, and chemicals derived from the HMF are widely applied to the fields of energy sources, fuels, medicines, chemical industry, materials and the like in recent years, and are one of the Biomass-based platform chemicals with the most application prospect in the report of Top Value ADDED CHEMICAL from Biomass by the U.S. department of energy. After the first report of the preparation of HMF in 1895, the study of this compound was subsequently carried out by scientists in various countries. In order to achieve efficient conversion of fructose to 5-HMF, the design and development of the catalyst is critical, and a large number of students are devoted to developing high performance catalysts. Initially, many studies on the reaction of dehydrating carbohydrates such as fructose to prepare HMF have used homogeneous acid catalysts such as inorganic acids, organic acids, lewis acids and salt compounds, and in 2007 Zhao et al found that many Lewis acids have very high catalytic activity on the dehydration of fructose to prepare 5-hydroxymethylfurfural (Metal chlorides in ionic liquid solvents convert sugars to 5-hydroxymethylfurfural,Science,316：1597-1600)., and when CrCl2、CrCl3、FeCl2、CuCl2、VCl3、MoCl3、PdCh、PtCh、RuCl3 and RhCl 3 are used as catalysts, the yield of 5-hydroxymethylfurfural in ionic liquid [ EMIMICI ] varies from 63% to 83%. The homogeneous catalyst has higher catalytic efficiency, but has the problems of equipment corrosion, environmental pollution, difficult product separation and the like, so searching for an efficient green catalyst to replace the efficient green catalyst becomes a key problem for researching the preparation of HMF by dehydration of fructose. With the progressive depth of research, researchers have developed heterogeneous catalysts including strong acid cation exchange resins, molecular sieves, heteropolyacids, metal organic framework compounds (Metal organic Frameworks, MOFs), and the like. For example CN 108997275A uses Amberlyst 15 to catalyze fructose in ethanol systems to produce HMF. However, such commercial resin-type catalysts are expensive and have poor thermal stability in the aqueous phase, and the maximum use temperature in the liquid phase must not exceed 120 ℃. CN 110642812A uses H Beta molecular sieve, CN 107001305B uses titanium oxide TiO 2 supported on silica to catalyze the dehydration of fructose to produce HMF. The catalyst has weak acidity and low catalytic efficiency. Metal phosphates are generally poorly water soluble and tend to exhibit dual acidic functions at elevated temperatures. Thus, the metal phosphate hasThe acid site can be used as a catalyst for preparing a furyl platform compound. Carlini group found that fructose conversion was achieved using cubic zirconium phosphate as catalyst at 100 °c 50％(Niobic acid and niobium phosphate as highly acidic viable catalysts in aqueous medium:Fructose dehydration reaction.Catal.Today,2006,118:373). Compared with a homogeneous catalyst, a heterogeneous catalyst has the advantages of high cost, complex preparation process, low mass transfer efficiency, easy deactivation and far lower reaction efficiency than a liquid acid catalyst, so that the industrial production of HMF is greatly limited. 5-Hydroxymethylfurfural (HMF) is generally unstable under synthetic production conditions, accompanied by numerous side reactions, leading to higher levels of impurities and humus (Humins). The continuous reaction extraction is considered as the technology with the most industrial prospect, and the solvent which is insoluble in water and has high selectivity to the 5-hydroxymethylfurfural is utilized to continuously extract the 5-hydroxymethylfurfural from an aqueous phase reaction system by means of the solvent, so that the rapid separation of products and aqueous phase is realized, the side reaction is greatly reduced, and the yield of the 5-hydroxymethylfurfural is further improved. In view of the above, we have a need to combine the advantages of both homogeneous and heterogeneous catalysts, and have devised catalysts that can use continuous reactions to achieve high select