WO2013060173A1 - Nickel-based microporous material and preparation and application thereof - Google Patents

Abstract

A nickel-based microporous material, which is prepared is as follows: dispersing a nickel-containing precursor compound and a monobasic or polybasic organic acid separately in an organic solvent to prepare a mother solution with a certain concentration; at a temperature of 0°C-150°C, with stirring, at a mole proportion of Ni2+/-C00H (organic acid radical) being 20:1 to 1:10, mixing the mother solutions, reacting for 0.1 h to 72 h, and then transferring the mixture to a reactor, at a temperature of 0°C to 200°C, subjecting the mixture to crystallization for 1 h to 360 h; and separating, washing, and drying the precipitate to prepare the material. Further provided are a method for preparing the nickel-based microporous material, and an application of the nickel-based microporous material in an esterification and alcohol-water separation.

Description

 Nickel-based microporous material and preparation and application thereof

 The invention belongs to the field of material synthesis technology and its application in catalytic reaction and alcohol-water separation, and particularly relates to a method for preparing a nickel-based microporous material and the material in the catalytic esterification reaction and the separation of lower alcohol and water. Applications. Background technique

 Adsorption separation is a purification technology of a widely used chemical aqueous solution in the chemical industry. The adsorbent used is generally a solid porous material having a well-developed pore structure and a high specific surface area. Because of its physical and chemical structure, the adsorbent has a strong selective adsorption for certain substances and can therefore be used for the removal of trace impurities in the mixture. Commonly used adsorbents include activated carbon, silica gel, etc. Among them, activated carbon has a unique pore structure and surface functional groups, and has a strong surface hydrophobicity, so that it can absorb various substances from aqueous solution, and is widely used in the purification of aqueous solutions; A hard amorphous chain-like and network-like silicic acid polymer particle, which is a hydrophilic polar adsorbent, is mostly used for dry dehydration of air or gas. 4A molecular sieves are commonly used in the dewatering of chemicals. Although effective, they are less selective and deplete a large amount of chemicals while removing water.

 At present, alcohol is widely used, is a commonly used solvent, and is also an important raw material for organic synthesis. Lower alcohols are often used as solvents, antifreezes, extractants, and the like. The rapid development of modern technology has made the purity of alcohol in industrial production more and more demanding. The efficient alcohol-water separation technology can improve the purity of alcohol and significantly increase the yield and quality, thus meeting the growing demand of industrial production.

 In traditional chemical production, the alcohol-water separation is mostly carried out by distillation. However, some aqueous solutions of alcohols tend to remove water in the solution by ordinary distillation because of the close boiling point or easy formation of azeotropes with each other, and the purpose of separation is not achieved. The main processes currently used to increase the alcohol concentration in an alcohol-water system are: azeotropic distillation, extractive distillation, membrane distillation, pervaporation, membrane contactor separation, and the like.

 Among these methods, azeotropic distillation has been industrialized, with high quality and large output, but the investment is large and energy consumption is high. Extractive distillation is mainly used to separate complexes, near-boiling mixtures and other low relative volatility mixtures, but it has high energy consumption and often has residual extractant. In recent years, the development of membrane technology has been widely promoted and applied in chemical separation. It has also been used in the separation of alcohol-water systems. The main new technologies include membrane distillation, pervaporation and membrane contactors, but membrane preparation. Technology is not mature enough yet.

 Therefore, it is of great significance and broad application prospect to design and develop a porous adsorbent material which is easy to prepare, has good selectivity for water adsorption and can minimize the loss of alcohol.

In addition, porous materials have penetrated into every step of modern industrial production as a catalyst. Among them, the esterification reaction plays an important role. Esters are an important class of organic materials widely used in solvents, plasticizers, resins, coatings, flavors and fragrances, cosmetics, pharmaceuticals, surfactants and reaction intermediates. Esterification is the preparation of ester compounds. An important way. The traditional esterification reaction uses concentrated sulfuric acid as a catalyst. The method has many side reactions, complicated post-treatment process, serious equipment corrosion, and waste acid discharge polluting the environment. In recent years, catalytic esterification methods such as chemistry (solid acid, ionic liquid, etc.) catalysis, physical (microwave, magnetic field, etc.) catalysis, biological (enzyme) catalysis, and reaction processes have made great progress, resulting in esterification yield. Significantly improved, the quality of esterified products has also improved significantly. CN101049573A The preparation of an ionic liquid for esterification reaction has high reactivity. CN1323655 An oxide-supported solid acid catalyst is prepared by a coprecipitation method. In the esterification reaction of acetic acid with n-butanol, the yield of n-butyl acetate reaches 90%. CN101108360A discloses a preparation method of a silicon-tungsten and phosphotungstic heteropoly acid supported catalyst, which exhibits good activity and selectivity in the esterification reaction. CN101485998A uses organic phosphonic acid as a catalyst for esterification reaction, and the esterification rate reaches 90% or more.

 At present, the solid acid catalyst replaces sulfuric acid for catalytic esterification reaction. Although it overcomes some shortcomings of sulfuric acid catalysis, such as serious corrosion and unfriendly environment, there are still some shortcomings, such as high reaction temperature, complicated preparation process and high cost. The catalyst is easily deactivated, difficult to regenerate, and poor in reactivity. For ionic liquids as catalysts, the reaction conditions are harsh, and the preparation of ionic liquids is complicated and the like is limited. Although the bio-enzyme catalysis is environmentally friendly and the reaction conditions are mild, the reaction time is longer and the yield is lower.

 Therefore, it is of great significance to develop a porous material which is easy to prepare, has a rich pore structure, has an adjustable pore size, and has high thermal stability. Such materials are in terms of adsorption separation, catalysis, electrode, magnetism, etc. Has potential application prospects. Summary of the invention

 The invention provides a preparation method of a nickel-based microporous material and its application in catalytic and adsorption separation. The material has large specific surface area, rich pore structure, high thermal stability and good solvent stability, high conversion rate, high selectivity and long catalyst life in catalytic esterification. It is recyclable, environmentally friendly, and has certain applications in alcohol-water separation. Separation operation is safe and low cost, and it can be used in large-scale alcohol-water separation process.

According to the technical solution of the present invention, a nickel-containing precursor compound and a mono- or polybasic organic acid are separately dispersed in an organic solvent to prepare a mother liquor of a certain concentration. At a synthesis temperature of 0 °C to 150 °C, the above mother liquor is mixed at a molar ratio of Ni ²⁺ / -COOH (organic acid radical) of 20:1 to 1:10 under stirring, and the reaction is 0.1! ! After ~ 72 h, transfer to the reaction kettle, at a temperature of 0 °C ~ 200 °C, crystallization 1 1! ~ 360 h. The nickel-based material is obtained by separating, washing, and drying the precipitate. The nickel-based material has a thermal stability of 300 to 400 ° C, which is superior to the heat-resistant temperature of the currently reported nickel-based composite material. The formation mechanism of the nickel-based microporous material may be that the amide organic solvent undergoes a hydrolysis reaction under the action of an organic acid, and slowly releases the formate ion; the formate ion and/or the organic acid ligand complex with the nickel ion , growing along a certain axial direction into a microporous nickel-based material having a regular pore structure.

 The choice of nickel-containing precursor compounds has a significant impact on the synthetic materials. Nickel oxide octahedrons are alternately joined to form a nickel-based material having a certain pore structure. The valence state of nickel ions in the precursor, the strength of the anion coordination, the solubility of the compound, etc., have an important influence on the specific surface area, pore structure and stability of the material. The nickel-containing precursor compound may be one or more of nickel nitrate, nickel chloride, nickel acetate, nickel sulfate, nickel oxalate, nickel acetylacetonate, nickel sulfamate, nickel stearate, preferably The nickel-containing precursor compound is: one or more of nickel nitrate, nickel chloride, nickel acetate, nickel sulfate, and nickel acetylacetonate. The most preferred nickel-containing precursor compounds are: nickel chloride, nickel acetate, and acetyl chloride. One or more of nickel pyruvate.

The pKa value of the organic mono- or polybasic acid is an important basis for selecting the acid, which helps to adjust the pH of the reaction system, promotes the slow hydrolysis of the amide organic solvent, and releases the formate ion. The molecular chain length of the organic acid ligand affects the morphology of the composite material as well as the pore size. By selecting different organic acids as ligands and complexing with nickel ions, the obtained microporous nickel-based material has an adjustable pore size of 0.4 nm to 2 nm and a specific surface area of 200 m ² g - ¹ to 400 m ² g- ^1. The specific surface area of the material with the zeolite molecular sieve structure is equivalent. The organic mono- or polybasic acid can be formic acid, acetic acid, propionic acid, 2-furancarboxylic acid, 2-picolinic acid, benzoic acid, p-methylbenzoic acid, oxalic acid, malonic acid, succinic acid, suberic acid, 2, 5-furandicarboxylic acid, 2, 5-pyridinedicarboxylic acid Or one or more of terephthalic acid and phthalic acid, preferably mono- or poly-organic acids are: acetic acid, 2-picolinic acid, benzoic acid, oxalic acid, 2, 5-furandicarboxylic acid, One or more of terephthalic acid, the most preferred monobasic or polybasic organic acid is: one or more of acetic acid, benzoic acid, 2, 5-furandicarboxylic acid.

 The amide organic solvent undergoes a hydrolysis reaction of a C-N bond under suitable temperature and acid-base conditions to form a free formate ion. Different amide compounds have different hydrolysis rates, which affect the structure and properties of the composite materials. The amide organic solvent may be one or more of formamide, N-methylformamide, N-ethylformamide, N,N-dimethylformamide, and N,N-diethylformamide. Preferred organic solvents are: one or more of N-methylformamide, hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-diethylformamide, hydrazine, hydrazine-diethylformamide The most preferred organic solvent is one or more of hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-diethylformamide.

In addition to the selection of suitable nickel-containing precursor compounds, organic acids and amides, the key to material synthesis is to rationally adjust the synthesis temperature, the concentration of the mother liquor, the molar ratio of Ni ²⁺ /-COOH (organic acid radicals), and the reaction time. , standing temperature and time, etc. A suitable synthesis temperature is from 0 ° C to 150 ° C, a preferred synthesis temperature is from 10 ° C to 130 ° C, and an optimum synthesis temperature is from 20 ° C to 50 ° C. The concentration of the suitable mother liquor is: Ni ²⁺ : 0.01~ 2.5 mol-L" ¹ , -COOH is 0.01~2.5 mol'lA. The preferred mother liquor concentration is: Ni ²⁺ : 0.1~ l.Omol-L" ¹ , -COOH is 0.1~l.Omo L- The optimum mother liquor concentration is: Ni ²⁺ : 0.1~0.5 mo L- -COOH is 0.1~ 0.5 mol-L ¹ suitable Ni ²⁺ / -COOH (organic acid radical) The molar ratio is from 20:1 to 1:10, and the preferred molar ratio of Ni ²⁺ / -COOH (organic acid radical) is: 10:1 to 1:5, optimal Ni ²⁺ / -COOH (organic acid radical) The molar ratio is: 5:1~1:2. The suitable reaction time is: 0.1h~72h, the preferred reaction time is: 0.51! ~ 30 h, the best reaction time is: lh ~ 5h. The suitable crystallization temperature is: 0 ° C ~ 200 ° C, the preferred crystallization temperature is: 20 ° C ~ 150 ° C, the optimum crystallization temperature is: 80 ° C ~ 150 ° C. The suitable crystallization time is: lh ~ 360h, the preferred crystallization time is: 10h~240h, the optimum crystallization time is: 24h~72h.

 The nickel-based material prepared by the above method is used as a catalyst for the esterification reaction. The reaction process is as follows: The prepared nickel-based material catalyst is added to a mixed system of an organic acid and an alcohol, and reacted under stirring to form a corresponding ester. The presence of acidic groups in the pores of the nickel-based catalyst, such as surface hydroxyl groups, carboxylic acid groups, etc., is the active center for catalyzing the esterification reaction. And because of the uniform distribution and high density of such groups, it exhibits better activity and selectivity. Another feature of this material is its high stability. In the preparation process, the microporous nickel-based material forms a three-dimensional stereo structure, which is connected by a metal-oxygen bond, has a stable structure and a rich pore structure, and can be recycled by simple separation after the reaction. Suitable organic acids are formic acid, acetic acid, propionic acid, stearic acid, palmitic acid, lactic acid, n-butyric acid, isobutyric acid, malonic acid, succinic acid, adipic acid, pimelic acid, benzoic acid, water. One or more of salicylic acid, cinnamic acid, syringic acid, p-hydroxybenzoic acid, o-toluic acid, m-toluic acid, vanillic acid, terephthalic acid, 2, 5-furan dicarboxylic acid. Suitable alcohols are methanol, ethanol, propanol, butanol, pentanol, butanol, n-hexanol, heptanol, octanol, benzyl alcohol, ethylene glycol, glycerol, isopropanol, tert-butanol, secondary One or more of butanol, isoamyl alcohol, octanol, 2-methyl-1-pentanol, 2-methoxybenzyl alcohol.

 The specific implementation steps of catalyzing the esterification reaction using the nickel-based material are as follows:

In the liquid phase, when a nickel-based catalytic material having a concentration of 50 g'mol- ^{1 to} 500 g'mol- ¹ (-COOH) is used as a catalyst, the molar ratio of alcohol (-OH) to acid (-COOH) is 1~100, stir, heat the reaction at 50 °C ~ 200 °C! ~ 40 h, centrifugation, chromatographic detection. The chromatographic detection conversion rate is 92%~100%, and the selectivity is 95%~100%. After the catalyst is recovered, it can be recycled after drying, and the number of cycles is more than 3 times. The nickel-based material is used for alcohol-water separation, and the alcohol-water system is mixed with the material to achieve the purpose of increasing the alcohol concentration in the alcohol-water system, and the material is mixed with the alcohol-water system, and then The alcohol-water mixture is separated and the water in the alcohol-water mixture is adsorbed by the material.

 The nickel-based material prepared by the above method is used as an adsorbent material, and is formed by grinding under a certain pressure, and sieving a certain size of particles (indicated as mesh number), and contacting the alcohol-water mixture to be separated into the different manner. The material, under the action of no pressure or a certain pressure, takes the separated sample, and the separated alcohol-water sample is detected by chromatography. The nickel-based microporous catalyst has a large amount of unsaturated groups in the pores, such as a large amount of oxygen, and oxygen has an active lone pair of electrons, which is an active center of action with polar molecules in the alcohol-water separation process. Secondly, the Ni in the skeleton is also in an unsaturated state and can adsorb a large amount of water. Another feature of the nickel-based material is its high stability, its connection through metal-oxygen bonds, and its stable structure. Even if a large amount of heat is generated during the adsorption process, it will be stable. After the reaction, it can be recycled by simple separation. In addition, the pore size of the material can be controlled by selecting a suitable mono- or dibasic acid. Therefore, the separation process uses the shape-selection effect of the pore size, and utilizes the difference in size between the water molecule and the alcohol molecule to ensure the adsorption amount of the alcohol. At the same time, the adsorption of water is increased as much as possible to achieve a good alcohol-water separation effect. The pressure used for molding the material is 5 MPa to 30 MPa, and the preferred pressure is 5 MPa to 20 MPa; the optimum pressure is 5 MPa to 10 MPa. The size of the material (expressed as the mesh number) is 30 to 540; the preferred size (expressed as the mesh number) is: 100 to 400; the optimum size (expressed as the mesh number) is: 100 to 200. The injection method can be pressure injection, upper in and lower, lower in and out, horizontal injection and direct adsorption. The lower alcohol used may be one or more of ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, cyclohexanol; the quality of the water system of the lower alcohol is 80 %~99%.

 The method for preparing the alcohol-water separation by using the nickel-based material prepared by the above method is as follows: The prepared nickel-based microporous material is formed by grinding at a pressure of 5 MPa to 30 MPa, and is sieved to obtain particles of a certain size (representing For the purpose of the number), the alcohol-water mixture to be separated is contacted with the material in different ways, and the composition is 80% by pressure injection, upper and lower, lower, upper and lower, horizontal injection and direct adsorption. 99% of the alcohol-water mixture is introduced into the packed column, and the concentration of the alcohol can be increased from the initial concentration of 80% to 99% to 99%-99.99%, and the separation effect is good.

 After the adsorbing material absorbs water molecules for drying treatment, it is repeatedly used as an adsorbing material for increasing the alcohol concentration in the low-carbon alcohol water system.

 The separation of the adsorbent material from the alcohol-water mixture can be carried out by centrifugation or filtration.

The invention has the advantages that a nickel-based microporous material with good thermal stability, large specific surface area and uniform pore diameter is prepared. The obtained microporous nickel formate material has a specific surface area of 200 m ² g - ¹ to 400 m ² g and a specific surface area of the zeolite structural material, a pore diameter of 0.4 nm to 2 nm, and a decomposition temperature of 300 ° C to 400 ° C. Thermal stability is much higher than formate crystal materials. The preparation method is simple, the synthesis control is easy, and the pore size can be controlled by selecting an appropriate mono- or dibasic acid. Such microporous nickel formate materials are suitable for use in catalysis, separation, adsorption, electrode, magnetics and the like.

The material has good application in catalytic esterification reaction, the reaction system is simple, no additional solvent is needed; the catalyst can be centrifuged and can be recycled; the catalytic conversion exhibits high conversion rate and high selectivity; Sexually, for most alcohols and organic acids can be catalytically converted to the corresponding esters. The nickel-based microporous material has certain application in alcohol-water separation, safe operation, low cost, easy availability of equipment, and can be used for the separation process of large-scale alcohol; the adsorbent is easy to recycle, and can be recycled after simple drying; In the process, the loss of alcohol is small and the adsorption efficiency is high; the method has good universality, and the separation energy is good for most of the low-carbon alcohol-water systems. It shows very good results. DRAWINGS

 BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic illustration of the different manner in which a low carbon alcohol-water system is fed to a packed column when a nickel based microporous material is applied to the alcohol-water separation. The injection mode shown in the figure is (1) from top to bottom; mode (2) is from bottom to top; mode (3) is pressure injection; mode (4) is horizontal injection. detailed description

 In order to further explain the present invention, several specific embodiments are given below, but the present invention is not limited to these embodiments.

 Example 1:

6 g of nickel chloride hexahydrate and 3 g of 2,5-furandic acid were separately added to 2.5 L of N,dimethylformamide and 400 mL of N,N-dimethylformamide in an organic solvent to dissolve; Thereafter, the above two solutions were mixed at 140 ° C and stirred for 72 hours to prepare a mother liquid. The above mother liquid was placed in a reaction vessel, sealed, and crystallized at 180 ° C for 56 hours, taken out, centrifuged, washed, and dried to obtain a nickel-based material. The 0.06 g sample was accurately weighed and degassed under vacuum at 150 ° C for 12 h, and subjected to physical adsorption under N ₂ to obtain an adsorption-desorption curve. The specific surface area of the sample was determined by the BET method, and its specific surface area was 203.6 m ² g ¹ . The pore size distribution of the sample was calculated by the BJH method with a pore size of 0.61 nm ± 0.15 nm. The sample was stably present at 300 ° C as measured by hot weight-differential heat under air.

 Example 2:

 29.6 g of nickel sulfate hexahydrate and 25.35 g of malonic acid were separately added to an organic solvent of 250 mL of N-ethylformamide and 1.95 L of N-formamide, and dissolved; after being dissolved, mixed at 80 ° C The above two solutions were stirred for 36 h to prepare a mother liquor. The above mother liquid was placed in a reaction vessel, sealed, and crystallized at 100 ° C for 100 h, taken out, centrifuged, washed, and dried to obtain a nickel-based material having a specific surface area of 412.1 !^^. It is 0.58 nm ± 0.10 nm. The sample 280 was measured by thermogravimetry-differential heat under air. C was previously stable.

 Example 3:

59.5 g of nickel stearate and 16.9 g of oxalic acid were separately added to 380 mL of N,N-diethylformamide and 250 mL of N,N-diethylformamide in an organic solvent to dissolve; after dissolution, The above two solutions were mixed at 120 ° C and stirred for 48 hours to prepare a mother liquor. The above mother liquid was placed in a reaction vessel, sealed, and crystallized at 60 ° C for 260 h, taken out, centrifuged, washed, and dried to obtain a nickel-based material having a specific surface area of 259.5 m ² g. It is 1.8 nm ± 0.15 nm. The sample was stably present at 200 ° C by thermogravimetry-differential heat under air.

 Example 4:

96 g of nickel acetate tetrahydrate and 23.9 g of 2,5-furandic acid were separately added to an organic solvent of 2.5 LN,N-dimethylformamide and 2 LN,N-dimethylformamide to dissolve; Thereafter, the above two solutions were mixed at 25 ° C and stirred for 2.5 h to prepare a mother liquid. The above mother liquid was placed in a reaction vessel, sealed, and taken out at 140 ° C for 48 hours, then taken out, centrifuged, washed, and dried to obtain a nickel-based material having a specific surface area of 252.1 m ² g. 0.48 nm ± 0.05 nm. The sample was stably present at 250 °C by thermogravimetry-differential heat under air.

 Example 5

Add 23.8 g of nickel chloride hexahydrate and 12.2 g of benzoic acid to 200 mL of N-ethylformamide and 50 In the organic solvent of mL N-ethylformamide, it is dissolved; after being dissolved, the above two solutions are mixed at 60 ° C and stirred for 5 h to prepare a mother liquor. The above mother liquid was placed in a reaction vessel, sealed, and crystallized at 50 ° C for 100 h, taken out, centrifuged, washed, and dried to obtain a nickel-based material having a specific surface area of 361.3 m ² ^. It is 1.4 nm ± 0.03 nm. The sample 300 was measured by thermogravimetry-differential heat under air. C was previously stable.

 Example 6:

27.6 g of nickel sulfate hexahydrate and 33.2 g of terephthalic acid were separately added to 700 mL of N,N-diethylformamide and 8 LN,N-diethylformamide in an organic solvent, and dissolved; The above two solutions were mixed at 110 ° C and stirred for 7.5 h to prepare a mother liquor. The above mother liquid was placed in a reaction vessel, sealed, and crystallized at 70 ° C for 56 h, taken out, centrifuged, washed, and dried to obtain a nickel-based material having a specific surface area of 252.5 m ² g. It is 0.63 nm ± 0.10 nm. The sample was stably present at 280 °C by thermogravimetry-differential heat under air.

 Example 7

62.6 g of nickel stearate and 3 g of malonic acid were respectively added to an organic solvent of 10 LN, N-dimethylformamide and 400 mL of N,N-dimethylformamide, and dissolved; after being dissolved, The above two solutions were mixed at 45 ° C and stirred for 12 h to prepare a mother liquor. The above mother liquid was placed in a reaction vessel, sealed, and crystallized at 100 ° C for 48 h, taken out, centrifuged, washed, and dried to obtain a nickel-based material having a specific surface area of 332.1 m ² g. 1.5 nm ± 0.05 nm. The sample 270 was previously stably present by the thermogravimetry-differential heat under air.

 Example 8

41.2 g of nickel oxalate dihydrate and 24.0 g of acetic acid were respectively added to an organic solvent of 500 mL of N-ethylformamide and 200 mL of N-ethylformamide, and dissolved; after being dissolved, the mixture was mixed at 30 ° C. The two solutions were stirred for 24 h to prepare a mother liquor. The above mother liquid was placed in a reaction vessel, sealed, and crystallized at 110 ° C for 200 h, taken out, centrifuged, washed, and dried to obtain a nickel-based material having a specific surface area of 253.4 m ² ^. It is 0.50 nm ± 0.01 nm. The sample was stably present at 200 ° 通过 by the thermogravimetry-differential heat under air.

 Example 9

 74.7 g of nickel acetate tetrahydrate and 81 g of oxalic acid were respectively added to an organic solvent of 1.2 LN, N-diethylformamide and 4 LN,N-diethylformamide, and dissolved; after being dissolved, at 25 The above two solutions were mixed at ° C and stirred for 2.5 h to prepare a mother liquor. The above mother liquid was placed in a reaction vessel, sealed, and crystallized at 140 ° C for 72 hours, taken out, centrifuged, washed, and dried to obtain a nickel-based material having a specific surface area of 242.3 !^^. It is 0.58 nm ± 0.10 nm. The sample 280 was previously stable by the thermogravimetry-difference heat under air.

 Example 10

31 g of nickel acetylacetonate and 61.5 g of 2-picolinic acid were respectively added to an organic solvent of 800 mL of formamide and 10 L of formamide, and dissolved; after being dissolved, the above two solutions were mixed at 90 ° C to prepare Mother liquor, stirred for 24 h. The reaction vessel containing the above mixture was sealed, and after crystallization for 56 hours at 90 ° C, it was taken out, centrifuged, washed, and dried to obtain a nickel-based material having a specific surface of 377.5 m ² g and a pore diameter of 1.69 nm ± 0.05 nm. The sample was stably present before 290 °C by thermogravimetry-differential heat under air.

 Example 11:

71.6 g of nickel chloride hexahydrate and 17.7 g of succinic acid were separately added to an organic solvent of 860 mL of N,N-dimethylformamide and 200 mL of N,N-dimethylformamide, and dissolved; The above two solutions were mixed at 80 ° C to prepare a mother liquor, and the reactor containing the above mixture was sealed at 36 ho, and then crystallized at 130 ° C for 48 h, taken out, centrifuged, washed, dried. , made of nickel-based material, the specific surface is 289.6 !^^, The pore size is 0.86 nm ± 0.17 nm. The sample 210 was previously stable by the thermogravimetry-differential heat under air. Example 12

 39.5 g of nickel sulfate hexahydrate and 1.68 g of 2-furancarboxylic acid were separately added to 500 mL of N,N-diethylformamide and 100 mL of N,N-diethylformamide in an organic solvent to dissolve; The above two solutions were mixed at 140 ° C to prepare a mother liquid, and the reaction vessel containing the above mixture was sealed at 7.5 ho, and after crystallization at 170 ° C for 72 h, it was taken out, centrifuged, washed, and dried. A nickel-based material having a specific surface area of 233.2!^^ and a pore diameter of 0.49 nm ± 0.08 nm was obtained. The sample 300 was previously stable by the thermogravimetry-differential heat under air.

 Example 13

Add 25 g of nickel stearate and 9.84 g of 2-picolinic acid to 100 mL of N-ethylformamide and 400 mL of N-ethylformamide in an organic solvent, and dissolve; after dissolving, mix at 105 °C. The above two solutions were prepared into a mother liquor and stirred for 20 h. The reaction vessel containing the above mixture was sealed, and after crystallization at 130 ° C for 320 h, it was taken out, centrifuged, washed, and dried to obtain a nickel-based material having a specific surface of 263.5 m ² ^ and a pore diameter of 0.43 nm. ±0.12 nm. The sample 280 was measured by thermogravimetry - differential heat under air. C was previously stable.

 Example 14

 Adding 296 g of nickel acetylacetonate and 11.7 g of 2,5-furandic acid to an organic solvent of 2.30 LN, N-dimethylformamide and 3 LN,N-dimethylformamide, respectively, to dissolve; Thereafter, the above two solutions were mixed at 20 ° C to prepare a mother liquid, which was stirred for 2.5 h. The reaction vessel containing the above mixture was sealed, and after crystallization at 110 ° C for 200 hours, it was taken out, centrifuged, washed, and dried to obtain a nickel-based material having a specific surface of 354.2 ° C. and a pore diameter of 1.61 nm. ±0.06 nm. The sample 260 was measured by hot weight-differential heat under air. C was previously stable.

 Example 15

 220 g of nickel oxalate dihydrate and 450 g of acetic acid were separately added to an organic solvent of 1.2 L of N-methylformamide and 2 L of N-methylformamide, and dissolved; after being dissolved, the above two were mixed at 125 °C. The solution was made into a mother liquor and stirred for 12 h. The reaction vessel containing the above mixture was sealed, and after crystallization for 144 hours at 60 ° C, it was taken out, centrifuged, washed, and dried to obtain a nickel-based material having a specific surface area of 298.6 ° C, a pore diameter of 0.55 nm. ± 0.15 nm. The sample 250 was measured by hot weight-differential heat under air. C was previously stable.

 Example 16:

Adding 514 g of nickel acetylacetonate and 60 g of 2,5-furandic acid to 10 LN,N-diethylformamide and 80 LN,N-diethylformamide in an organic solvent, and dissolving; The above two solutions were mixed at 65 ° C to prepare a mother liquor, which was stirred for 13 hours. The reaction vessel containing the above mixture was sealed, and after crystallization at 160 ° C for 100 h, it was taken out, centrifuged, washed, and dried to obtain a nickel-based material having a specific surface of 203.5 m ² ^ and a pore diameter of 0.52 nm. ± 0.16 nm. The sample 270 was previously stably present by the thermogravimetry-differential heat under air.

 Example 17

 595 g of nickel chloride hexahydrate and 538 g of malonic acid were separately added to an organic solvent of 50 L of formamide and 23 L of formamide, and dissolved; after being dissolved, the above two solutions were mixed at 45 ° C to prepare The mother liquor was stirred for 24 ho. The reaction vessel containing the above mixture was sealed, and after crystallization for 144 hours at 110 ° C, it was taken out, centrifuged, washed, and dried to obtain a nickel-based material having a specific surface area of 256.71 μm. It is 0.65 nm ± 0.08 nm. The sample was stable before 300 °0 by the thermogravimetry-differential heat under air.

 Example 18

629 g of nickel stearate and 112 g of 2-furancarboxylic acid were separately added to an organic solvent of 6.7 LN, N-dimethylformamide and 2 LN,N-dimethylformamide, and dissolved; after being dissolved, Mix the above two solutions at 40 °C, The mother liquor was prepared and stirred for 3.5 h. The reaction vessel containing the above mixture was sealed, taken out at 130 ° C for 48 h, taken out, centrifuged, washed, and dried to obtain a nickel-based material having a specific surface area of 211.2 m ² g and a pore diameter of 0.57 nmi0. .ll nm. The sample 260 was measured by thermogravimetry - differential heat under air. C was previously stable.

 Example 19

 211 g of nickel sulfate hexahydrate and 15.9 g of succinic acid were separately added to 4 LN,N-diethylformamide and 1.8 LN,N-diethylformamide in an organic solvent to dissolve; after dissolution, at 25 The above two solutions were mixed at ° C to prepare a mother liquor, which was stirred for 1 hour. The reaction vessel containing the above mixture was sealed, and after crystallization for 56 hours at 90 ° C, it was taken out, centrifuged, washed, and dried to obtain a nickel-based material having a specific surface of 256.2 ° C and a pore diameter of 0.42 nm ± 0.12 nm. The sample 280 was previously stable by the thermogravimetry-difference heat under air.

 Example 20

115.7 g of nickel acetylacetonate and 175.5 g of 2,5-furandic acid were separately added to 1 LN-methylformamide and 1.50 L of N-methylformamide in an organic solvent to dissolve; after dissolution, at 35 ° C The above two solutions are mixed underneath to prepare a mother liquor, and the reaction vessel containing the above mixture is sealed by stirring for 15 ho, and after crystallization at 140 ° C for 24 hours, it is taken out, centrifuged, washed, and dried to obtain a nickel-based material. , its specific surface is 239.5 m ² g and the pore size is 0.43 nm ± 0.08 nm. The sample was stably present at 280 ° 通过 by the thermogravimetry-differential heat under air.

 Example 21:

 109.8 g of nickel oxalate dihydrate and 66.8 g of terephthalic acid were separately added to an organic solvent of 2 LN,N-dimethylformamide and 2.3 LN,N-dimethylformamide, and dissolved; after being dissolved, The above two solutions were mixed at 30 ° C to prepare a mother liquor, which was stirred for 72 hours. The reaction vessel containing the above mixture was sealed, crystallized at 50 ° C for 72 h, taken out, centrifuged, washed, and dried to obtain a nickel-based material having a specific surface area of 221.3!^^ and a pore diameter of 0.46 nm. ±0.03 nm. The sample 290 was measured by thermogravimetry-differential heat under air. C was previously stable.

 Example 22

231.3 g of nickel acetylacetonate and 140.3 g of benzoic acid were respectively added to an organic solvent of 6 L of N-ethylformamide and 500 mL of N-ethylformamide, and dissolved; after being dissolved, the above two were mixed at 120 °C. a solution, made into a mother liquor, stirred for 2.5 ho. The reaction vessel containing the above mixture was sealed, and after crystallization at 80 ° C for 48 h, it was taken out, centrifuged, washed, and dried to obtain a nickel-based material having a specific surface. It is 312.1 m ¹ and has a pore size of 0.93 nm ± 0.05 nm. The sample 300 was previously stably present by the thermogravimetry-differential heat under air.

 Example 23

 Add 125 g of nickel chloride hexahydrate and 66.4 g of terephthalic acid to an organic solvent of 2.1 LN-methylformamide and 2 L1N-methylformamide, respectively; dissolve; after dissolving, mix at 130 °C The above two solutions were prepared into a mother liquor and stirred for 10 h. The reaction vessel containing the above mixture was sealed, and after crystallization for 320 hours at 150 ° C, it was taken out, centrifuged, washed, and dried to obtain a nickel-based material having a specific surface area of 257.6 ° C. and a pore diameter of 0.77 nm ± 0.04 nm. The sample 230 was previously stable by the thermogravimetry-differential heat under air.

 Example 24

Adding 197.3 g of nickel sulfate hexahydrate and 8 g of malonic acid to 15 LN,N-dimethylformamide and 1 LN,N-dimethylformamide in an organic solvent, and dissolving; The above two solutions were mixed at ° C to prepare a mother liquor, which was stirred for 3.5 h. The reaction vessel containing the above mixture was sealed, and after crystallization for 100 hours at 200 ° C, it was taken out, centrifuged, washed, and dried to obtain a nickel-based material having a specific surface of 367.5 m ² ^ and a pore diameter of 0.91 nm. ±0.08 nm. The sample 280 was measured by thermogravimetry - differential heat under air. C was previously stable.

Example 25 140.85 g of nickel stearate and 12 g of acetic acid were separately added to 750 mL of formamide and 200 mL of formamide in an organic solvent to dissolve; after being dissolved, the above two solutions were mixed at 130 ° C to prepare a mother liquor, and stirred. 4 ho The reaction vessel containing the above mixture was sealed, and after crystallization at 140 ° C for 24 hours, it was taken out, centrifuged, washed, and dried to obtain a nickel-based material having a specific surface of 285.31^^ and a pore diameter of 0.56 nm. ± 0.06 nm. The sample was stably present before 260 ° 0 by the thermogravimetry-differential heat under air.

 Example 26

Adding 257 g of nickel acetylacetonate and 156 g of 2,5-furandic acid to an organic solvent of 2.5 LN,N-diethylformamide and 1 LN,N-diethylformamide, respectively, to dissolve; Thereafter, the above two solutions were mixed at 90 ° C to prepare a mother liquid, which was stirred for 8 hours. The reaction vessel containing the above mixture was sealed, and after crystallization for 30 hours at 30 ° C, it was taken out, centrifuged, washed, and dried to obtain a nickel-based material having a specific surface of 277.9 m ² ^ and a pore diameter of 0.78 nm ± 0.12 nm. The sample 280 was previously stable by the thermogravimetry-differential heat under air.

 Example 27

91.5 g of nickel oxalate dihydrate and 16.6 g of 2-picolinic acid were separately added to 2 L of N-methylformamide and 2.7 L of N-methylformamide in an organic solvent to dissolve; after dissolution, mixed at 25 ° C The above two solutions were prepared into a mother liquor and stirred for 5 hours. The reaction vessel containing the above mixture was sealed, and after crystallization at 190 ° C for 350 h, it was taken out, centrifuged, washed, and dried to obtain a nickel-based material having a specific surface of 299.5 m ² ^ and a pore diameter of 0.69 nm. ±0.10 nm. The sample 260 was previously stable by the thermogravimetry-differential heat under air.

 Example 28

 96 g of nickel acetate tetrahydrate and 23.9 g of 2,5-furanic acid were separately dispersed in 2.5 L and 2 L of N,dimethylformamide to prepare a mother liquor. The above mother liquor was mixed at 25 ° C under stirring, and after reacting for 2.5 h, it was transferred to a reaction vessel and sealed, and crystallized at 140 ° C for 48 h. The nickel-based catalyst was obtained by separating, washing, and drying the precipitate. A nickel-based catalyst is used as a catalyst for the esterification reaction. 60 g of the above catalyst was placed in a reaction flask together with 4 mol of acetic acid and 80 mol of n-hexanol and 800 mL of cyclohexane, stirred, and heated at 85 ° C for 10 h, centrifuged, and chromatographically detected. The chromatographic detection conversion rate reached 96% with a selectivity of 97%.

 Example 29

 Add 14.5 g of nickel sulfate hexahydrate and 18 g of terephthalic acid to 400 mL of N,N-diethylformamide and 5 LN,N-diethylformamide in an organic solvent, and dissolve; The above two solutions were mixed at 100 ° C and stirred for 8.5 h to prepare a mother liquor. The above mother liquid was placed in a reaction vessel, sealed, and crystallized at 140 ° C for 72 hours, taken out, centrifuged, washed, and dried to obtain a nickel-based material. A microporous nickel-based catalyst is used as a catalyst for the esterification reaction. 57 g of the above catalyst was placed in a reaction flask together with 1.8 mol of acetic acid, 80.4 mol of n-hexanol and 500 mL of cyclohexane, stirred, and heated at 70 ° C for 5 h, centrifuged, and chromatographically detected. The chromatographic detection conversion rate was 92% and the selectivity was 100%.

 Example 30

28.6 g of nickel chloride hexahydrate and 9.96 g of isophthalic acid were separately added to 240 mL of N-ethylformamide and 60 mL of N-ethylformamide in an organic solvent to dissolve; after dissolution, at 40 ° C, The above two solutions were mixed and stirred for 8 hours to prepare a mother liquor. The above mother liquid was placed in a reaction vessel, sealed, and crystallized at 150 ° C for 48 hours, taken out, centrifuged, washed, and dried to obtain a nickel-based material. A nickel-based catalyst is used as a catalyst for the esterification reaction. 60 g of the above catalyst was placed in a reaction flask together with 3 mol of acetic acid and 60 mol of n-hexanol and 1 L of cyclohexane, stirred, and heated at 90 ° C for 7 h, centrifuged, and chromatographically detected. Chromatographic detection of conversion rate of 94%, selectivity of 99%.

 Example 31

 62.6 g of nickel stearate and 4.5 g of 2,5-furandic acid were respectively added to 10 LN, N-diethylformamide and 400 mL of N,N-diethylformamide in an organic solvent, and dissolved; After dissolving, the above two solutions were mixed at 55 ° C and stirred for 3 h to prepare a mother liquor. The above mother liquid was placed in a reaction vessel, sealed, and crystallized at 120 ° C for 72 hours, taken out, centrifuged, washed, and dried to obtain a nickel-based material. A nickel-based catalyst is used as a catalyst for the esterification reaction. 110 g of the above catalyst was placed in a reaction flask together with 10 mol of acetic acid and 17 mol of n-hexanol and 700 mL of cyclohexane, stirred, and heated at 80 ° C for 8 h, centrifuged, and chromatographically detected. The chromatographic detection conversion rate reached 95% with a selectivity of 95%.

 Example 32

 41.2 g of nickel oxalate dihydrate and 48.0 g of benzoic acid were separately added to an organic solvent of 1 LN-ethylformamide and 2 LN-ethylformamide, and dissolved; after being dissolved, the above two were mixed at 40 ° C The solution was stirred for 4 h to prepare a mother liquor. The above mother liquid was placed in a reaction vessel, sealed, and crystallized at 130 ° C for 60 hours, taken out, centrifuged, washed, and dried to obtain a nickel-based material. A nickel-based catalyst is used as a catalyst for the esterification reaction. 60 g of the above catalyst was placed in a reaction flask together with 2 mol of acetic acid, 80 mol of n-hexanol and 1 L of cyclohexane, stirred, and heated at 90 ° C for 8 h, centrifuged, and chromatographically detected. The chromatographic detection conversion rate reached 94% with a selectivity of 96%.

 Example 33

 96 g of nickel acetate tetrahydrate and 23.9 g of 2,5-furandic acid were separately dispersed in 2.5 L and 2 L of N,N-dimethylformamide to prepare a mother liquor. The above mother liquor was mixed at 25 ° C under stirring, and after reacting for 2.5 h, it was transferred to a reaction vessel and crystallized at 140 ° C for 48 h. The nickel-based catalyst was obtained by separating, washing and drying the precipitate. A microporous nickel-based material is used as a catalyst for the esterification reaction. 100 g of the above catalyst was placed in a reaction flask together with 1.8 mol of acetic acid and 80.4 mol of n-hexanol and 1 L of cyclohexane, stirred, and heated at 85 ° C for 10 h, centrifuged, and chromatographed. Chromatographic detection of conversion rate of 99%, selectivity of 96%.

 Example 34

 14.5 g of nickel sulfate hexahydrate and 18 g of terephthalic acid were respectively added to an organic solvent of 400 mL of N,N-diethylformamide and 5 LN,N-diethylformamide, and dissolved; The above two solutions were mixed at 100 ° C and stirred for 8.5 h to prepare a mother liquor. The above mother liquid was placed in a reaction vessel, sealed, and crystallized at 140 ° C for 72 hours, taken out, centrifuged, washed, and dried to obtain a nickel-based material. A nickel-based catalyst is used as a catalyst for the esterification reaction. 60 g of the above catalyst was placed in a reaction flask together with 2 mol of acetic acid and 70 mol of n-butanol and 10 mL of cyclohexane, stirred, and heated at 85 ° C for 10 h, centrifuged, and chromatographically detected. Chromatographic detection of conversion rate of 99%, selectivity of 99%.

 Example 35

28.6 g of nickel chloride hexahydrate and 9.96 g of isophthalic acid were separately added to 240 mL of N-ethylformamide and 60 mL of N-ethylformamide in an organic solvent to dissolve; after dissolution, at 40 °C Next, the above two solutions were mixed and stirred for 8 hours to prepare a mother liquor. The above mother liquid was placed in a reaction vessel, sealed, and crystallized at 150 ° C for 48 hours, taken out, centrifuged, washed, and dried to obtain a nickel-based material. A nickel-based catalyst is used as a catalyst for the esterification reaction. 160 g of the above catalyst was placed in a reaction flask together with 5 mol of acetic acid and 50 mol of n-butanol and 500 mL of cyclohexane, stirred, and heated at 70 ° C for 9 h, centrifuged, and chromatographed. Measurement. Chromatographic detection of conversion rate of 99%, selectivity of 99%.

 Example 36

 62.6 g of nickel stearate and 4.5 g of 2,5-furandic acid were respectively added to 10 LN, N-diethylformamide and 400 mL of N,N-diethylformamide in an organic solvent, and dissolved; After dissolving, the above two solutions were mixed at 55 ° C and stirred for 3 h to prepare a mother liquor. The above mother liquid was placed in a reaction vessel, sealed, and crystallized at 120 ° C for 72 hours, taken out, centrifuged, washed, and dried to obtain a nickel-based material. A nickel-based catalyst is used as a catalyst for the esterification reaction. 60 g of the above catalyst was placed in a reaction flask together with 5 mol of propionic acid and 10 mol of ethanol and 600 mL of cyclohexane, stirred, and heated at 65 ° C for 15 h, centrifuged, and chromatographically detected. The chromatographic detection conversion rate reached 100% with a selectivity of 97%.

 Example 37

 41.2 g of nickel oxalate dihydrate and 48.0 g of benzoic acid were separately added to an organic solvent of 1 LN-ethylformamide and 2 LN-ethylformamide, and dissolved; after being dissolved, the above two were mixed at 40 ° C The solution was stirred for 4 h to prepare a mother liquor. The above mother liquid was placed in a reaction vessel, sealed, and crystallized at 130 ° C for 60 hours, taken out, centrifuged, washed, and dried to obtain a nickel-based material. A nickel-based catalyst is used as a catalyst for the esterification reaction. 70 g of the above catalyst was placed in a reaction flask together with 5 mol of stearic acid and 50 mol of n-butanol and 1 L of cyclohexane, stirred, and heated at 85 ° C for 20 h, centrifuged, and chromatographed. . Chromatographic detection conversion rate reached 100% with a selectivity of 96%.

 Example 38

 96 g of nickel acetate tetrahydrate and 23.9 g of 2,5-furandic acid were separately dispersed in 2.5 L and 2 L of N,N-dimethylformamide to prepare a mother liquor. The above mother liquor was mixed at 25 ° C under stirring, and after reacting for 2.5 h, it was transferred to a reaction vessel and crystallized at 140 ° C for 48 h. The nickel-based catalyst was obtained by separating, washing and drying the precipitate. A nickel-based catalyst is used as a catalyst for the esterification reaction. 100 g of the above catalyst was placed in a reaction flask together with 1.8 mol of lactic acid and 80.4 mol of n-octanol and 1 L of cyclohexane, stirred, and heated at 110 ° C for 24 h, centrifuged, and chromatographically detected. Chromatographic detection of 96% conversion with a selectivity of 95%.

 Example 39

 14.5 g of nickel sulfate hexahydrate and 18 g of terephthalic acid were respectively added to an organic solvent of 400 mL of N,N-diethylformamide and 5 LN,N-diethylformamide, and dissolved; The above two solutions were mixed at 100 ° C and stirred for 8.5 h to prepare a mother liquor. The above mother liquid was placed in a reaction vessel, sealed, and crystallized at 140 ° C for 72 hours, taken out, centrifuged, washed, and dried to obtain a nickel-based material. A nickel-based catalyst is used as a catalyst for the esterification reaction. 100 g of the above catalyst was placed in a reaction flask together with 2 mol of benzoic acid and 10 mol of propanol and 500 mL of cyclohexane, stirred, and heated at 100 ° C for 10 h, centrifuged, and chromatographically detected. The chromatographic conversion was 98% and the selectivity was 99%.

 Example 40

28.6 g of nickel chloride hexahydrate and 9.96 g of isophthalic acid were separately added to 240 mL of N-ethylformamide and 60 mL of N-ethylformamide in an organic solvent to dissolve; after dissolution, at 40 °C Next, the above two solutions were mixed and stirred for 8 hours to prepare a mother liquor. The above mother liquid was placed in a reaction vessel, sealed, and crystallized at 150 ° C for 48 hours, taken out, centrifuged, washed, and dried to obtain a nickel-based material. A nickel-based catalyst is used as a catalyst for the esterification reaction. 50 g of the above catalyst was placed in a reaction flask together with 5 mol of propionic acid and 50 mol of ethanol and 500 mL of cyclohexane, stirred, and heated at 50 ° C for 11 h, centrifuged, and chromatographically detected. Chromatographic detection of conversion rate of 99%, selectivity of 100%.

 Example 41

62.6 g of nickel stearate and 4.5 g of 2,5-furandic acid were respectively added to 10 LN, N-diethylformamide and 400 mL of N,N-diethylformamide in an organic solvent, and dissolved; After dissolution, the above two solutions were mixed at 55 ° ^G and stirred for 3 hours to prepare a mother liquor. The above mother liquid was placed in a reaction vessel, sealed, and crystallized at 120 ° C for 72 hours, taken out, centrifuged, washed, and dried to obtain a nickel-based material. A nickel-based catalyst is used as a catalyst for the esterification reaction. 60 g of the above catalyst was placed in a reaction flask together with 4 mol of stearic acid and 80 mol of n-butanol and 1 L of cyclohexane, stirred, and heated at 80 ° C for 13 h, centrifuged, and chromatographed. . Chromatographic detection of conversion rate of 95%, selectivity of 100%.

 Example 42

 41.2 g of nickel oxalate dihydrate and 48.0 g of benzoic acid were separately added to an organic solvent of 1 LN-ethylformamide and 2 LN-ethylformamide, and dissolved; after being dissolved, the above two were mixed at 40 ° C The solution was stirred for 4 h to prepare a mother liquor. The above mother liquid was placed in a reaction vessel, sealed, and crystallized at 130 ° C for 60 hours, taken out, centrifuged, washed, and dried to obtain a nickel-based material. A nickel-based catalyst is used as a catalyst for the esterification reaction. 100 g of the above catalyst was placed in a reaction flask together with 7 mol of propionic acid and 10 mol of ethanol and 500 mL of cyclohexane, stirred, and heated at 160 ° C for 12 h, centrifuged, and chromatographed. The chromatographic detection conversion rate was 93% with a selectivity of 98%.

 Example 43

 96 g of nickel acetate tetrahydrate and 23.9 g of 2,5-furandic acid were separately dispersed in 2.5 L and 2 L of N,N-dimethylformamide to prepare a mother liquor. The above mother liquor was mixed at 25 ° C under stirring, and after reacting for 2.5 h, it was transferred to a reaction vessel and crystallized at 140 ° C for 48 h. The nickel-based catalyst was obtained by separating, washing and drying the precipitate. A nickel-based catalyst is used as a catalyst for the esterification reaction. 30 g of the above catalyst was placed in a reaction flask together with 1.8 mmol of stearic acid and 80.4 mmol of n-butanol and 10 mL of cyclohexane, stirred, and heated at 110 ° C for 6 h, centrifuged, and chromatographed. . The chromatographic conversion was 95% and the selectivity was 99%.

 Example 44

 14.5 g of nickel sulfate hexahydrate and 18 g of terephthalic acid were respectively added to an organic solvent of 400 mL of N,N-diethylformamide and 5 LN,N-diethylformamide, and dissolved; The above two solutions were mixed at 100 ° C and stirred for 8.5 h to prepare a mother liquor. The above mother liquid was placed in a reaction vessel, sealed, and crystallized at 140 ° C for 72 hours, taken out, centrifuged, washed, and dried to obtain a nickel-based material. A nickel-based catalyst is used as a catalyst for the esterification reaction. 40 g of the above catalyst was placed in a reaction flask together with 2 mol of lactic acid and 80 mol of n-octanol and 800 mL of cyclohexane, stirred, and heated at 100 ° C for 10 h, centrifuged, and chromatographically detected. Chromatographic detection of 96% conversion with a selectivity of 100%.

 Example 45

28.6 g of nickel chloride hexahydrate and 9.96 g of isophthalic acid were separately added to 240 mL of N-ethylformamide and 60 mL of N-ethylformamide in an organic solvent to dissolve; after dissolution, at 40 °C Next, the above two solutions were mixed and stirred for 8 hours to prepare a mother liquor. The above mother liquid was placed in a reaction vessel, sealed, and crystallized at 150 ° C for 48 hours, taken out, centrifuged, washed, and dried to obtain a nickel-based material. A nickel-based catalyst is used as a catalyst for the esterification reaction. 60 g of the above catalyst was placed in a reaction flask together with 1.8 mol of benzoic acid and 80.4 mol of propanol and 1 L of cyclohexane, stirred, and heated at 85 ° C for 15 h, centrifuged, and chromatographically detected. The chromatographic conversion was 92% with a selectivity of 99%.

 Example 46

 62.6 g of nickel stearate and 4.5 g of 2,5-furandic acid were respectively added to 10 LN, N-diethylformamide and 400 mL of N,N-diethylformamide in an organic solvent, and dissolved; After dissolving, the above two solutions were mixed at 55 ° C and stirred for 3 h to prepare a mother liquor. The above mother liquid was placed in a reaction vessel, sealed, and crystallized at 120 ° C for 72 hours, taken out, centrifuged, washed, and dried to obtain a nickel-based material. A nickel-based catalyst is used as a catalyst for the esterification reaction. 30 g of the above catalyst was placed in a reaction flask together with 2 mol of propionic acid and 70 mol of ethanol and 1 L of cyclohexane, stirred, and heated at 100 ° C for 10 h, centrifuged, and chromatographically detected. Chromatographic detection of conversion rate of 98%, selectivity of 100%.

 Example 47

 41.2 g of nickel oxalate dihydrate and 48.0 g of benzoic acid were separately added to an organic solvent of 1 LN-ethylformamide and 2 LN-ethylformamide, and dissolved; after being dissolved, the above two were mixed at 40 ° C The solution was stirred for 4 h to prepare a mother liquor. The above mother liquid was placed in a reaction vessel, sealed, and crystallized at 130 ° C for 60 hours, taken out, centrifuged, washed, and dried to obtain a nickel-based material. A base catalyst is used as a catalyst for the esterification reaction. 150 g of the above catalyst was placed in a reaction flask together with 10 mol of acetic acid and 100 mol of n-hexanol and 1.5 L of cyclohexane, stirred, and heated at 80 ° C for 10 h, centrifuged, and chromatographically detected. The chromatographic detection conversion rate reached 94% with a selectivity of 100%.

 Example 48

 96 g of nickel acetate tetrahydrate and 23.9 g of 2,5-furandic acid were separately dispersed in 2.5 L and 2 L of N,N-dimethylformamide to prepare a mother liquor. The above mother liquor was mixed at 25 ° C under stirring, and after reacting for 2.5 h, it was transferred to a reaction vessel and crystallized at 140 ° C for 48 h. The nickel-based catalyst was obtained by separating, washing and drying the precipitate. A nickel-based catalyst is used as a catalyst for the esterification reaction. 60 g of the above catalyst was placed in a reaction flask together with 4 mol of acetic acid and 80 mol of n-hexanol and 800 mL of cyclohexane, stirred, and heated at 85 ° C for 10 h, centrifuged, and chromatographically detected. Chromatographic detection of 96% conversion with a selectivity of 97%.

 Example 49

 62.6 g of nickel stearate and 4.5 g of 2,5-furandic acid were respectively added to 10 LN, N-diethylformamide and 400 mL of N,N-diethylformamide in an organic solvent, and dissolved; After dissolving, the above two solutions were mixed at 55 ° C and stirred for 3 h to prepare a mother liquor. The above mother liquid was placed in a reaction vessel, sealed, and crystallized at 120 ° C for 72 hours, taken out, centrifuged, washed, and dried to obtain a nickel-based material. A nickel-based catalyst is used as a catalyst for the esterification reaction. 70 g of the above catalyst was placed in a reaction flask together with 10 mol of oxalic acid and 10 mol of ethanol and 700 mL of cyclohexane, stirred, and heated at 80 ° C for 10 h, centrifuged, and chromatographically detected. The chromatographic conversion was 98% and the selectivity was 99%.

 Example 50

91.5 g of nickel oxalate dihydrate and 16.6 g of benzoic acid were separately added to 1.5 L of N, dimethylformamide and 500 mL of N,N-dimethylformamide in an organic solvent to dissolve; after dissolution, at 35 The above two solutions were mixed at ° C to prepare a mother liquor, which was stirred for 7 h. The reaction vessel containing the above mixture was sealed, and after crystallization at 160 ° C for 78 hours, it was taken out, centrifuged, washed, and dried to obtain an adsorbent having a specific surface of 306.5 m ² g and a pore diameter of 1 nm. The material is pressed into a sheet under a pressure of 15 MPa, ground, sieved to take 100 to 200 mesh particles, filled into an adsorption separation column, and a mixture of 99% by mass of ethanol and water is introduced into the packed column by horizontal injection. . After adsorption, the alcohol concentration increased to 99.96%. Example 51

96 g of nickel acetate tetrahydrate and 23.9 g of 2,5-furandic acid were separately dispersed in 2.5 L and 2 LN,N-dimethylformamide to prepare a mother liquid. The mother liquid was mixed at 25 ° C under stirring, and after reacting for 2.5 h, it was transferred to a reaction kettle, and the precipitate was separated, washed and dried at a temperature of 140 ° C for 48 ho. The adsorbent material has a specific surface area of 252.8 m ² g and a pore diameter of 0.48 nm. The material is pressed into a sheet at a pressure of 25 MPa, ground, sieved to take 100 to 200 mesh particles, and filled into an adsorption-separated column to form a mixture of ethanol and water having a mass concentration of 94.9% from top to bottom. Introduced into the packed column. After adsorption, the alcohol concentration increased to 98.9 %.

 Example 52

 197.3 g of nickel sulfate hexahydrate and 16.5 g of 2-pyridinedicarboxylic acid were respectively added to an organic solvent of 15 L of formamide and 500 mL of formamide, and dissolved; after being dissolved, the above two solutions were mixed at 40 ° C to prepare Mother liquor, stir for 5 h. The reaction vessel containing the above mixture was sealed, and after crystallization for 48 hours at 180 ° C, it was taken out, centrifuged, washed, and dried to obtain an adsorbent material having a specific surface of 307.5 !^^, a pore diameter of 0.6 nm. . The adsorbed material is pressed into a sheet under a pressure of 30 MPa, ground, sieved to take 200 to 400 mesh particles, filled into an adsorption separation column, and a mass concentration of 90.0% of propanol and water is injected in a horizontal injection manner. The mixture was introduced into a packed column, and after adsorption, the alcohol concentration was increased to 96.5 %.

 Example 53

 125 g of nickel chloride hexahydrate and 51.1 g of oxalic acid were separately added to an organic solvent of 2.1 L of N-methylformamide and 500 mL of N-methylformamide, and dissolved; after being dissolved, at 50 ° C The above two solutions were mixed to prepare a mother liquor and stirred for 4 hours. The reaction vessel containing the above mixture was sealed, and after crystallization at 150 ° C for 24 hours, it was taken out, centrifuged, washed, and dried to obtain an adsorbent material having a specific surface area of 217.6 ?^^ and a pore diameter of 0.4 nm. The material is pressed into a sheet under a pressure of 10 MPa, ground, sieved to 50 to 100 mesh particles, filled into an adsorption separation column, and a mixture of butanol and water having a mass concentration of 89.5 % is introduced into the packed column by pressure injection. in. After adsorption, the alcohol concentration increased to 94.6%.

 Example 54

 96 g of nickel acetate tetrahydrate and 23.9 g of 2,5-furandic acid were separately dispersed in 2.5 L and 2 L of N,N-dimethylformamide to prepare a mother liquor. The above mother liquor was mixed at 25 ° C under stirring, and after reacting for 2.5 h, it was transferred to a reaction kettle, and the precipitate was separated, washed and dried at a temperature of 140 ° C for 48 ho. The adsorbent material has a specific surface area of 252.81^ and a pore diameter of 0.48 nm. The material was pressed into a sheet under a pressure of 35 MPa, ground, sieved to take 100 to 200 mesh particles, and filled into an adsorption-separated column to mass-concentrate 85.1% of isopropanol and water from top to bottom. The mixture is introduced into a packed column. After adsorption, the alcohol concentration increased to 95.9 %.

 Example 55

91.5 g of nickel oxalate dihydrate and 16.6 g of benzoic acid were separately added to 1.5 L of N, dimethylformamide and 500 mL of N,N-dimethylformamide in an organic solvent to dissolve; after dissolution, at 35 The above two solutions were mixed at ° C to prepare a mother liquor, which was stirred for 7 h. The reaction vessel containing the above mixture was sealed, and after crystallization at 160 ° C for 78 hours, it was taken out, centrifuged, washed, and dried to obtain an adsorbent having a specific surface of 306.5 m ² g and a pore diameter of 1 nm. The material was pressed into a sheet under a pressure of 25 MPa, ground, and sieved to take 200-540 mesh particles, and filled into an adsorption-separated column, and a mass concentration of 96.5 % isobutanol and water was injected from bottom to top. The mixture is introduced into a packed column. After adsorption, the alcohol concentration increased to 99.3%. Example 56

 96 g of nickel acetate tetrahydrate and 23.9 g of 2,5-furandic acid were separately dispersed in 2.5 L and 2 L of N,N-dimethylformamide to prepare a mother liquor. The above mother liquor was mixed at 25 ° C under stirring, and after reacting for 2.5 h, it was transferred to a reaction vessel, and at a temperature of 140 ° C, crystallization 48 was separated, washed, and dried to obtain the adsorption. The material has a specific surface area of 252.81^^ and a pore size of 0.48 nm. The material is pressed into a sheet under a pressure of 15 MPa, ground, sieved to take 100 to 200 mesh particles, filled into an adsorption separation column, and a mixture of cyclohexanol and water having a mass concentration of 99.3% is injected by pressure injection. Introduced into the packed column. After adsorption, the alcohol concentration increased to 99.5 %.

 Example 57

 96 g of nickel acetate tetrahydrate and 23.9 g of 2,5-furandic acid were separately dispersed in 2.5 L and 2 L of N,N-dimethylformamide to prepare a mother liquor. The above mother liquor was mixed at 25 ° C under stirring, and after reacting for 2.5 h, it was transferred to a reaction vessel, and at a temperature of 140 ° C, crystallization 48 was separated, washed, and dried to obtain the adsorption. The material has a specific surface area of 252.81^^ and a pore size of 0.48 nm. The material was pressed into a sheet at a pressure of 30 MPa, ground, and 50 to 100 mesh particles were sieved, and packed into an adsorption-separated column to mass-concentrate 85.4% of tert-butanol and water from top to bottom. The mixture is introduced into a packed column. After adsorption, the alcohol concentration increased to 93.7%.

 Example 58

 125 g of nickel chloride hexahydrate and 51.1 g of oxalic acid were separately added to an organic solvent of 2.1 L of N-methylformamide and 500 mL of N-methylformamide, and dissolved; after being dissolved, mixed at 50 ° C The above two solutions were prepared into a mother liquor and stirred for 4 h. The reaction vessel containing the above mixture was sealed, and after crystallization at 150 ° C for 24 hours, it was taken out, centrifuged, washed, and dried to obtain an adsorbent material having a specific surface area of 217.6 ?^^ and a pore diameter of 0.4 nm. The material is pressed into a sheet under a pressure of 10 MPa, ground, sieved to take 100 to 200 mesh particles, filled into an adsorption separation column, and a mixture of butanol and water having a mass concentration of 99% is injected from bottom to top. Introduced into the packed column. After adsorption, the alcohol concentration increased to 99.9%.

 Example 59

 197.3 g of nickel sulfate hexahydrate and 16.5 g of 2-pyridinedicarboxylic acid were respectively added to an organic solvent of 15 L of formamide and 500 mL of formamide, and dissolved; after being dissolved, the above two solutions were mixed at 40 ° C to prepare Mother liquor, stir for 5 h. The reaction vessel containing the above mixture was sealed, and after crystallization for 48 hours at 180 ° C, it was taken out, centrifuged, washed, and dried to obtain an adsorbent material having a specific surface of 307.5 !^^, a pore diameter of 0.6 nm. . The material is pressed into a sheet at a pressure of 45 MPa, ground, sieved to take 200 to 400 mesh particles, filled into an adsorption-separated column, and a mixture of 99% by mass of isopropanol and water is introduced by horizontal injection. Fill the column. After adsorption, the alcohol concentration increased to 99.5 %.

 Example 60

125 g of nickel chloride hexahydrate and 51.1 g of oxalic acid were separately added to an organic solvent of 2.1 L of N-methylformamide and 500 mL of N-methylformamide, and dissolved; after being dissolved, mixed at 50 ° C The above two solutions were prepared into a mother liquor and stirred for 4 h. The reaction vessel containing the above mixture was sealed, and after crystallization at 150 ° C for 24 hours, it was taken out, centrifuged, washed, and dried to obtain an adsorbent material having a specific surface area of 217.6 ?^^ and a pore diameter of 0.4 nm. The material is pressed into a sheet under a pressure of 30 MPa, ground, sieved to take 100 to 200 mesh particles, filled into an adsorption separation column, and a mixture of isobutanol and water having a mass concentration of 90% by a pressure injection method. Introduced into the packed column. After adsorption, the alcohol concentration increased to 92.6%. Example 61

 109.8 g of nickel oxalate dihydrate and 71.8 g of 2,5-furandicarboxylic acid were separately added to 2 LN,N-dimethylformamide and 2.3 LN,N-dimethylformamide in an organic solvent to dissolve; Mixing the above two solutions at 30 ° C to prepare a mother liquor, stirring 72 to seal the reaction vessel containing the above mixture, crystallization at 180 ° C for 72 hours, taking out, centrifuging, washing, drying, and making A nickel-based material having a specific surface area of 251.7!^^ and a pore diameter of 2 nm was obtained. The material is pressed into a sheet under a pressure of 15 MPa, ground, sieved to take 100 to 200 mesh particles, and filled into an adsorption-separated column, and a mass concentration of 97% cyclohexanol and water is injected from top to bottom. The mixture is introduced into a packed column. After adsorption, the alcohol concentration increased to 99.9%.

 Example 62

91.5 g of nickel oxalate dihydrate and 16.6 g of benzoic acid were separately added to 1.5 L of N, dimethylformamide and 500 mL of N,N-dimethylformamide in an organic solvent to dissolve; after dissolution, at 35 ° C The above two solutions were mixed underneath to prepare a mother liquor, which was stirred for 7 hours. The reaction vessel containing the above mixture was sealed, and after crystallization at 160 ° C for 78 hours, it was taken out, centrifuged, washed, and dried to obtain an adsorbent having a specific surface of 306.5 m ² g and a pore diameter of 1 nm. The material is pressed into a sheet at a pressure of 30 MPa, ground, sieved to 50 to 100 mesh particles, filled into an adsorption-separated column, and a mass concentration of 89.5% of tert-butanol and water is injected from bottom to top. The mixture is introduced into a packed column. After adsorption, the alcohol concentration increased to 94.6%.

 Example 63

 109.8 g of nickel oxalate dihydrate and 71.8 g of 2,5-furandicarboxylic acid were separately added to 2 LN,N-dimethylformamide and 2.3 LN,N-dimethylformamide in an organic solvent to dissolve; Mixing the above two solutions at 30 ° C to prepare a mother liquor, stirring 72 to seal the reaction vessel containing the above mixture, crystallization at 180 ° C for 72 hours, taking out, centrifuging, washing, drying, and making A nickel-based material having a specific surface area of 251.7!^^ and a pore diameter of 2 nm was obtained. The material is pressed into a sheet under a pressure of 40 MPa, ground, sieved to take 100 to 200 mesh particles, filled into an adsorption separation column, and a mixture of 99% by mass of ethanol and water is introduced by pressure injection. Fill the column. After adsorption, the alcohol concentration increased to 99.8%.

 Example 64

 197.3 g of nickel sulfate hexahydrate and 16.5 g of 2-pyridinedicarboxylic acid were respectively added to an organic solvent of 15 L of formamide and 500 mL of formamide, and dissolved; after being dissolved, the above two solutions were mixed at 40 ° C to prepare Mother liquor, stir for 5 h. The reaction vessel containing the above mixture was sealed, and after crystallization for 48 hours at 180 ° C, it was taken out, centrifuged, washed, and dried to obtain an adsorbent material having a specific surface of 307.5 !^^, a pore diameter of 0.6 nm. . The material is pressed into a sheet under a pressure of 20 MPa, ground, and 50 to 100 mesh particles are sieved, and packed into an adsorption separation column to introduce a mixture of ethanol and water having a mass concentration of 97.5 % from the top to the bottom. Fill the column. After adsorption, the alcohol concentration increased to 98.9%.

 Example 65

109.8 g of nickel oxalate dihydrate and 71.8 g of 2,5-furandicarboxylic acid were separately added to 2 LN,N-dimethylformamide and 2.3 LN,N-dimethylformamide in an organic solvent to dissolve; Mixing the above two solutions at 30 ° C to prepare a mother liquor, stirring 72 to seal the reaction vessel containing the above mixture, crystallization at 180 ° C for 72 hours, taking out, centrifuging, washing, drying, and making A nickel-based material having a specific surface area of 251.7!^^ and a pore diameter of 2 nm was obtained. The material is pressed into a sheet under a pressure of 40 MPa, ground, sieved to take 200 to 400 mesh particles, filled into an adsorption separation column, and a mass concentration of 88.9 % of a mixture of propanol and water is introduced by a pressure injection method. Fill the column. After adsorption, the alcohol concentration increased to 98.6%. Example 66

91.5 g of nickel oxalate dihydrate and 16.6 g of benzoic acid were separately added to 1.5 L of N, dimethylformamide and 500 mL of N,N-dimethylformamide in an organic solvent to dissolve; after dissolution, at 35 The above two solutions were mixed at ° C to prepare a mother liquor, which was stirred for 7 h. The reaction vessel containing the above mixture was sealed, and after crystallization at 160 ° C for 78 hours, it was taken out, centrifuged, washed, and dried to obtain an adsorbent having a specific surface of 306.5 m ² g and a pore diameter of 1 nm. The material is pressed into a sheet under a pressure of 15 MPa, ground, sieved to take 100 to 200 mesh particles, and filled into an adsorption-separated column, and a mass concentration of 99.5% of tert-butanol and water is injected from top to bottom. The mixture is introduced into a packed column. After adsorption, the alcohol concentration increased to 99.8%.

 Example 67

 96 g of nickel acetate tetrahydrate and 23.9 g of 2,5-furandic acid were separately dispersed in 2.5 L and 2 L of N,N-dimethylformamide to prepare a mother liquor. The above mother liquor was mixed at 25 ° C under stirring, and after reacting for 2.5 h, it was transferred to a reaction kettle, and the precipitate was separated, washed and dried at a temperature of 140 ° C for 48 ho. The adsorbent material has a specific surface area of 252.81^ and a pore diameter of 0.48 nm. The material is pressed into a sheet at a pressure of 30 MPa, ground, sieved to take 100 to 200 mesh particles, and filled into an adsorption-separated column to convert a mass concentration of 92.3% of butanol and water from bottom to top. The mixture is introduced into a packed column. After adsorption, the alcohol concentration increased to 95.2%.

 Example 68

 197.3 g of nickel sulfate hexahydrate and 16.5 g of 2-pyridinedicarboxylic acid were respectively added to an organic solvent of 15 L of formamide and 500 mL of formamide, and dissolved; after being dissolved, the above two solutions were mixed at 40 ° C to prepare Mother liquor, stir for 5 h. The reaction vessel containing the above mixture was sealed, and after crystallization for 48 hours at 180 ° C, it was taken out, centrifuged, washed, and dried to obtain an adsorbent material having a specific surface of 307.5 !^^, a pore diameter of 0.6 nm. . The material is pressed into a sheet under a pressure of 40 MPa, ground, sieved to take 100 to 200 mesh particles, filled into an adsorption separation column, and a mixture of 99% by mass of isopropanol and water is introduced by horizontal injection. Fill the column. After adsorption, the alcohol concentration increased to 99.98 %.

 Example 69

 96 g of nickel acetate tetrahydrate and 23.9 g of 2,5-furandic acid were separately dispersed in 2.5 L and 2 L of N,N-dimethylformamide to prepare a mother liquor. The above mother liquor was mixed at 25 ° C under stirring, and after reacting for 2.5 h, it was transferred to a reaction kettle, and the precipitate was separated, washed and dried at a temperature of 140 ° C for 48 ho. The adsorbent material has a specific surface area of 252.8 m 2 g-l and a pore diameter of 0.48 nm. The material is pressed into a sheet under a pressure of 5 MPa, ground, sieved to take 100 to 200 mesh particles, filled into an adsorption separation column, and a mass concentration of 90.6 % cyclohexanol and water is injected by pressure injection. The mixture is introduced into a packed column. After adsorption, the alcohol concentration increased to 90.6 %.

 Example 70

109.8 g of nickel oxalate dihydrate and 71.8 g of 2,5-furandicarboxylic acid were separately added to 2 LN,N-dimethylformamide and 2.3 LN,N-dimethylformamide in an organic solvent, dissolved; to be dissolved Thereafter, the above two solutions were mixed at 30 ° C to prepare a mother liquid, which was stirred for 72 hours. The reaction vessel containing the above mixture was sealed, and after the reaction temperature was 180 ° C, the reaction was taken for 72 hours, taken out, centrifuged, washed, and dried to obtain a nickel-based material having a specific surface area of 251.7 m ² ^ and a pore diameter of 2 nm. This material was directly adsorbed in a beaker containing a mixture of cyclohexanol and water at a mass concentration of 87.5 %. After adsorption, it was filtered, and a clear solution was detected, and the alcohol concentration was increased to 90.6 %.

Comparative Example 1: Concentrated sulfuric acid as a catalyst for esterification 100 g of concentrated sulfuric acid was placed in a reaction flask together with 1.8 mol of acetic acid and 80.4 mol of n-hexanol and 1 L of cyclohexane, stirred, and heated at 85 ° C for 10 h, centrifuged, and chromatographically detected. The chromatographic conversion was 99% and the selectivity was 99%.

 Comparative Example 2: Amberlyst-15 as an esterification catalyst

 100 g of Amberlyst-15 was placed in a reaction flask with 1.8 mol of acetic acid, 80.4 mol of n-hexanol and 1 L of cyclohexane, stirred, and heated at 85 ° C for 10 h, centrifuged, and chromatographically detected. Chromatography detected a conversion of 95% with a selectivity of 100%.

 Comparative Example 3: Phosphotungstic heteropoly acid as esterification catalyst

 100 g of phosphotungstic heteropoly acid was placed in a reaction flask together with 1.8 mol of acetic acid and 80.4 mol of n-hexanol and 1 L of cyclohexane, stirred, and heated at 85 ° C for 10 h, centrifuged, and chromatographed. . The chromatographic detection conversion rate reached 96% with a selectivity of 99%.

Comparative Example 4: a load S0 ₄ ² - of Ti0 ₂ as an esterification catalyst

100 g of S0 ₄ ² -containing Ti0 ₂ was placed in a reaction flask together with 1.8 mol of acetic acid and 80.4 mol of n-hexanol and 1 L of cyclohexane, stirred, and heated at 85 ° C for 10 h, centrifuged. , chromatographic detection. Chromatographic detection of conversion rate of 98%, selectivity of 98%.

 Comparative Example 5: Using nickel formate inorganic salt as a catalyst for esterification

 100 g of nickel formate inorganic salt was placed in a reaction flask together with 1.8 mol of acetic acid, 80.4 mol of n-hexanol and 1 L of cyclohexane, stirred, and heated at 85 ° C for 10 h, centrifuged and chromatographed. Chromatography detected a conversion of 90% with a selectivity of 82%.

Claims

Claim

A nickel-based microporous material, characterized in that: a nickel-containing precursor compound and a mono- or poly-organic acid are separately dispersed in an organic solvent to prepare a mother liquor of a certain concentration;

The concentration of Ni ions in the mother liquor of the nickel-containing precursor compound is Ni ²⁺ : 0.01 ～ 2.5 mol-L ¹ ,

The concentration of organic acid ions in the monobasic or polybasic organic acid mother liquor is: -COOH is 0.01 ~ S mol - ¹ ; at a synthesis temperature of 0 °C to 150 °C, under stirring, Ni ²⁺ / -COOH is 20 : 1 ~ 1 : 10 molar ratio, the above mother liquid is mixed, the reaction is 0.1 h ~ 72 h, transferred to the reaction kettle, at 0 ° C ~ 200 ° C temperature, crystallization 1 1! ~ 360 h; The nickel-based material is obtained by separating, washing and drying the precipitate.

2. A method for preparing a nickel-based microporous material according to claim 1, wherein: the nickel-containing precursor compound and the mono- or polybasic organic acid are separately dispersed in an organic solvent to prepare a mother liquor having a certain concentration; The concentration of Ni ions in the mother liquid of the nickel precursor compound is Ni ²⁺ : 0.01 ～ 2.5 mol-L ¹ ,

The concentration of organic acid ion (-COOH) in the monobasic or polybasic organic acid mother liquor is: 0.01 ~ 2.5 mol-L ¹ ; at a synthesis temperature of 0 ° C to 150 ° C, under stirring, according to Ni ²⁺ / -COOH For the molar ratio of 20:1 to 1:10, the above mother liquor is mixed and reacted 0.1 1! After ~ 72 h, transfer to the reaction kettle, at a temperature of 0 °C ~ 200 °C, crystallize 1 1! ~ 360 h; The nickel-based material is obtained by separating, washing and drying the precipitate.

 3. The method according to claim 2, wherein the nickel-containing precursor compound is nickel nitrate, nickel chloride, nickel acetate, nickel sulfate, nickel oxalate, nickel acetylacetonate, nickel sulfamate, One or more of nickel stearate;

 The monobasic or polybasic organic acid is: formic acid, acetic acid, propionic acid, 2-furancarboxylic acid, 2-picolinic acid, benzoic acid, p-methylbenzoic acid, oxalic acid, malonic acid, succinic acid, suberic acid And one or more of 2-furanic acid, 2, 5-pyridinedicarboxylic acid, terephthalic acid, and phthalic acid;

 The organic solvent is one or more of formamide, N-methylformamide, N-ethylformamide, N,N-dimethylformamide, and N,N-diethylformamide.

 4. The preparation method according to claim 2 or 3, wherein the mother liquor synthesis temperature is from 10 ° C to 130 ° C, and the synthesis time is: 0.5 1! ~ 30 h;

 The crystallization temperature is: 20 ° C ~ 150 ° C, and the crystallization time is: 10 h to 240 h.

 5. The preparation method according to claim 2 or 3, characterized in that:

The concentration of Ni ²⁺ ions in the mother liquor of the nickel-containing precursor compound is: 0.1 to 1.0 mol-L ¹ ;

The concentration of the organic acid ion (-COOH) in the monobasic or polybasic organic acid mother liquor is: 0.1 to 1.0 mol'L - the molar ratio of the Ni ²⁺ / -COOH is: 10:1 to 1:5.

 6. Use of a nickel-based material according to claim 1 in an esterification reaction, characterized in that: the nickel-based material according to claim 1 is used as a catalyst for the esterification reaction, the reaction process is: adding the catalyst to the organic A mixed system of an acid and an alcohol is reacted under stirring for a certain period of time to form a corresponding ester.

 7. The application of claim 6 wherein:

 The organic acid is formic acid, acetic acid, propionic acid, stearic acid, palmitic acid, lactic acid, n-butyric acid, isobutyric acid, malonic acid, succinic acid, adipic acid, pimelic acid, salicylic acid, cinnamon One or more of acid, syringic acid, vanillic acid, benzoic acid, p-hydroxybenzoic acid, o-toluic acid, m-toluic acid, terephthalic acid, 2, 5-furan dicarboxylic acid;

The alcohol is methanol, ethanol, propanol, butanol, pentanol, butanol, n-hexanol, heptanol, octanol, benzyl alcohol, Ethylene glycol, glycerol, isopropanol, tert-butanol, sec-butanol, isoamyl alcohol, octanol, 2-methyl-1-pentanol, 2-methoxybenzyl alcohol or A variety.

 8. The application of claim 6 wherein:

In the liquid phase, when a nickel-based material having a concentration of SO g'mor^SOO g'mor ¹ (-COOH) is used as a catalyst, the molar ratio of alcohol (-OH) to acid (-COOH) is 1 to 100, and stirring is carried out. After the reaction for a certain period of time, the catalyst was separated by centrifugation to obtain an esterified product.

 9. Use according to claim 6 or 8, characterized in that the reaction temperature is from 50 ° C to 200 °. C, the reaction time is 2 1! ~ 40 h;

 The preferred reaction temperature is from 60 ° C to 180 ° C, and the preferred reaction time is 2 1! ~ 20 h;

 The optimum reaction temperature is 75 °C ~ 150 °C, and the optimum reaction time is 2 1! ~ 12 h.

 10. Use of a nickel-based material according to claim 1 for alcohol-water separation, characterized in that: the nickel-based material according to claim 1 is mixed with an alcohol and water, and then separated from the alcohol-water mixture. The water in the alcohol-water mixture is adsorbed by the material for the purpose of alcohol-water separation.

 11. The use according to claim 10, characterized in that:

 The nickel-based material is formed by grinding at a pressure of 5 MPa to 30 MPa, and then granules of 30 to 540 mesh are sieved, and the alcohol-water mixture to be separated is contacted with the material, and the two are separated to obtain a high concentration of alcohol. - water mixture.

 12. The use according to claim 11, characterized in that:

 The nickel-based material is pressed into a sheet under a pressure of 5 MPa to 30 MPa, ground, sieved to take 30 to 540 mesh particles, filled into an adsorption-separated column, and an alcohol-water mixture is introduced into the column to make the alcohol- The water mixture flows through the column and is an alcohol-water mixture with an increased alcohol concentration.

 13. Use according to claim 11 or 12, characterized in that:

 The preferred pressure is: 5 MPa~20 MPa; the optimum pressure is: 5 MPa~10 MPa;

 The preferred nickel-based material has a mesh number of 100 to 400; the optimum nickel-based material has a mesh number of 100-200;

 The alcohol-water mixture is introduced by means of pressure injection, up, down, down, or horizontal injection.

14. Use according to claim 10, 11 or 12, characterized in that:

 The lower alcohol is one or more of ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, cyclohexanol;

 The composition of the alcohol-water mixture is: the mass concentration of the alcohol is 80 to 99%;

 The mass concentration of the alcohol in the alcohol-water mixture after the water is adsorbed by the material is 99 to 99.99%.