CN110721744B - Solid acid catalyst with high reaction activity and preparation method and application thereof - Google Patents
Solid acid catalyst with high reaction activity and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a solid acid catalyst with high reaction activity and a preparation method and application thereof, wherein the catalyst comprises 100 parts of a carrier, 18-36 parts of sulfonic acid group, 8-16 parts of zinc group with active zinc content, 10-20 parts of zirconium group with active zirconium content and 7-14 parts of aluminum group with active aluminum content, the sulfonic acid group is chemically connected on the carrier, and the zinc group, the zirconium group and the aluminum group are chemically connected and/or physically attached on the carrier; the porous structure of the organic carbon skeleton of the carrier 1 has a unit structure with a chemical formula as follows: 1, 4-bis [ di (3-carbazolyl) -methyl) ] benzene, through carbon-based skeleton load acid and active site catalytic reaction, have high catalytic activity in the HDI synthetic process, have the advantages of easy recovery, low cost simultaneously, can not corrode chemical industry equipment.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a solid acid catalyst with high reaction activity and a preparation method and application thereof.
Background
The ester chemical products are more and more widely applied in various aspects in life, for example, citric acid esters are important active ingredients in high-end products such as environment-friendly plasticizers, food packaging materials, surfactants, cosmetics and the like, 1, 6-hexamethylene isocyanate (HDI) is a necessary component of various coatings and additives, and the phthalate plasticizer has wide application prospect in PVC manufacturing industry. In the industrial esterification reaction, the conventional homogeneous catalyst or toluenesulfonic acid is still used for synthesizing HDI, which has the defects of more side reactions, high corrosion on equipment, high cost due to difficult recycling and the like, so that the exploration and the search of an environment-friendly high-efficiency catalyst for replacing the conventional catalyst are urgent.
In the field of organic chemistry, there are the Bronsted acid-base theory and the Lewis acid-base theory, given or accepted as a distinction in proton/electron pairs, respectively. Under the definition, almost all organic reactions belong to acid-base reactions, so that the acid catalysis has high catalytic activity on various reactions such as esterification, amination and the like, and simultaneously overcomes the defects that liquid acid cannot be repeatedly used and equipment is corroded, and then the reaction activity still needs to be further improved. The solid acid catalyst used in industrial production is silicon-aluminum gel, and a large number of protons are attached to the inner wall of micropores of the silicon-aluminum gel and serve as active sites in the catalytic process, however, the silicon-aluminum gel does not have a regular structure, the distribution of the protons on the silicon-aluminum gel is irregular, and polymers can be formed in the catalytic process to block the micropores, so that the catalyst is inactivated, and the defects reduce the further development of the silicon-aluminum gel; later, scientists developed solid acid catalysts with various carriers such as zeolite molecular sieves, heteropolyacids, clays, cation exchange resins, etc., but still have various drawbacks.
Chinese patent CN 101337189B discloses a solid acid catalyst and its application in the synthesis of 1, 6-Hexamethylene Diisocyanate (HDI), which is characterized in that the solid acid catalyst is composed of titanate with mole fraction of 8-45%, water-soluble zinc salt 30-60%, water-soluble aluminum salt 3-10%, water-soluble zirconium salt 8-20%, H6-18%2SO4Reacting to obtain a composition SO4 2-/TiO2-ZnO-ZrO2-Al2O3The catalyst is used for preparing 1, 6-hexamethylene diisocyanate, has high reaction activity and selectivity, can adopt dimethyl carbonate with low price as a raw material, has aminolysis yield of 95 percent and pyrolysis yield of 88 percent, particularly has low catalytic pyrolysis temperature, can be reduced to the maximum value of not more than 230 ℃, obviously reduces the occurrence of side reactions, improves the product yield, and has total product yield of 83.6 percent; the catalyst uses a plurality of metal elements, has high cost, is easy to cause product pollution, and has insufficient framework stability, so that further improvement is needed. Lexintao et al propose a new process for synthesizing HDI from Hexamethylenediamine (HDA) via hexamethylenedicarbamate, i.e. hexamethylenediamine and phenylaminomethylMethyl formate (MPC) is subjected to ester exchange reaction to synthesize Hexamethylene Dicarbamate (HDC), and then subjected to pyrolysis to prepare 1, 6-hexamethylene diisocyanate, however, the overall side reaction is still excessive, and the final reaction efficiency is not high.
In the process of searching for a HDI synthesis reaction catalyst, scientists find that the carbon-based solid acid catalyst has good thermal stability and catalytic activity, the overall strength of the carbon-based solid acid catalyst is high when the carbon-based solid acid catalyst is used as a framework of the solid acid catalyst, and meanwhile, various raw materials with complex components and low cost in the nature and even industrial waste are expected to be used as a carbon source of biomass, so that the carbon-based solid acid catalyst has good environmental friendliness and recyclability. Due to the high stability of the carbon base, high acid content and more active sites can be loaded, high catalytic activity is guaranteed, and the method has a good development prospect in the synthesis of HDI.
Disclosure of Invention
The present invention is directed to overcoming the above-mentioned disadvantages of the prior art and providing a solid acid catalyst with high reactivity and a method for preparing the same, and to provide a solid acid catalyst structure and a method for preparing the same with high reactivity and at the same time, which has high catalytic activity in catalyzing the HDI synthesis process.
In order to achieve the purpose, the invention provides the following technical scheme:
a solid acid catalyst with high reaction activity comprises, by weight, 100 parts of a carrier, 18-36 parts of sulfonic acid groups, 8-16 parts of zinc groups with active zinc content, 10-20 parts of zirconium groups with active zirconium content, and 7-14 parts of aluminum groups with active aluminum content, wherein the sulfonic acid groups are chemically connected to the carrier, and the zinc groups, the zirconium groups and the aluminum groups are chemically connected and/or physically attached to the carrier; the carrier unit structure has the chemical formula: 1, 4-bis [ di (3-carbazolyl) -methyl)]The benzene, this carrier is an organic carbon skeleton that is copolymerized and got to terephthalaldehyde and carbazole, have micron-scale cavity, the specific surface area is large, the sulfonic acid group is supported on skeleton through the chemical bond high strength, can still keep the high acidity value in using many times, the catalyst life is high; the active zinc, the active zirconium and the active aluminum can establish C-M (M represents a metal group) with carbazole in partial framework and can also adsorb through physical adhesionOn a carrier; simultaneously, the existence of sulfonic group and-COOM causes the solid acid to have Lewis site, and SO4 -2The polarization between S ═ O bonds and metal groups in the structural units, which are not bonded, generates Bronsted acid sites, so that the solid acid catalyst prepared is a double-acid-site solid acid catalyst.
Preferably, the sulfonic acid group content is 36 parts, and the active zinc content is 12 parts; the active zirconium content is 15 parts; the content of active aluminum is 10 parts.
Preferably, the zinc group, the zirconium group and the aluminum group are respectively zinc, zirconium and aluminum in single forms by weight parts, and the groups can be combined with a carrier framework through a C-Metal bond generated by the carrier framework and play a catalytic role.
More preferably, the silane coupling agent is also included by 5-10 parts, and the coupling agent can more effectively realize the combination of the metal group and the carrier backbone.
A method for preparing a high-reactivity solid acid catalyst comprises the following steps:
the method comprises the following steps: adding terephthalaldehyde, carbazole and hydrochloric acid with standard concentration into a proper amount of 1, 4-dioxane solution, keeping the molar ratio of the terephthalaldehyde to the carbazole at 1:2, keeping the volume ratio of the hydrochloric acid solution to the 1, 4-dioxane solution at 5:1 to keep an acidic environment, keeping stirring and reacting at 90-100 ℃ for at least 24h, and cooling to room temperature to obtain liquid A; in the environment of 1, 4-dioxane solution and hydrochloric acid, benzene dicarbaldehyde and carbazole are primarily polymerized to form an organic porous carbon monomer, and the chemical formula is as follows: {1, 4-bis [ bis (3-carbazolyl) -methyl) ] benzene };
step two: dissolving soluble salt containing zinc group, aluminum group and zirconium group in deionized water and uniformly stirring to prepare liquid B, so that each metal group is in a free state to facilitate the attachment and combination with the framework in the next step; the volume of the deionized water is small, and the deionized water is preferably controlled to be 1/2 of hydrochloric acid solution so as to avoid over-dilution of the solution, and if the volume of the deionized water is large, the hydrochloric acid needs to be supplemented;
step three: heating the liquid A to 210-220 ℃, slowly dripping the liquid B into the liquid A while keeping stirring, controlling the dripping speed to be 1-2 drops/second so as to ensure that the metal group fully enters the oil phase and contacts with the framework of the preliminary reaction, and continuously reacting for at least 24 hours to obtain a solid-liquid mixture C;
step four: washing the solid-liquid mixture C to remove unreacted raw materials, repeatedly performing suction filtration to obtain a solid, and drying at 50 ℃ for 5-6h to obtain a solid D;
step five: 0.6g of solid D is dissolved in a defined amount of CH2Cl2Mixing, stirring at room temperature to dissolve completely, and adding ClSO dropwise in ice water bath3H, controlling the speed to be 1-2 drops/second, avoiding sputtering caused by excessively fast addition, simultaneously reacting insufficiently, and stirring for at least 4 hours at room temperature to obtain a solid-liquid mixture E;
step six: and washing the solid-liquid mixture E to be neutral, carrying out suction filtration to obtain a solid, and drying at 80 ℃ for at least 24h to obtain the solid acid catalyst.
Preferably, in the second step, the soluble salts containing zinc group, aluminum group and zirconium group are zinc sulfate, aluminum sulfate and zirconium sulfate, which are easily available, easily soluble in water, and easily released active group, and the sulfate group does not damage the skeleton.
Preferably, in the fourth step, the washing agent used for washing the unreacted raw materials by the solid-liquid mixture C is THF.
Preferably, in the sixth step, the detergents used for washing away the unreacted raw materials by the solid-liquid mixture E are deionized water and methanol, and the deionized water is firstly used for washing for multiple times, and then the pH of the solid-liquid mixture E is adjusted to be neutral by using methanol with the aid of a pH meter.
The application of a high-reactivity solid acid catalyst for preparing 1, 6-hexamethylene diisocyanate is characterized in that:
(1) mixing hexamethylenediamine, dimethyl carbonate and a solid acid catalyst, carrying out aminolysis reaction at 50-90 ℃ in a nitrogen atmosphere, and distilling, washing and separating to obtain hexamethylenediamine methyl formate;
(2) the hexamethylene diisocyanate is pyrolyzed at the temperature of 200-300 ℃ to prepare the 1, 6-hexamethylene diisocyanate.
Compared with the prior art, the invention has the beneficial effects that: (1) the carbon-based framework has good chemical and physical stability and can stably exist under the synthesis condition of HDI; (2) through the loading of sulfonic group and metal group, the acid amount can reach 2.75-3.24mmol/g, and the metal active site makes the solid acid catalyst simultaneously have Bronsted and Lewis acid sites, so that the whole solid acid catalyst has high reaction activity and selectivity, the reaction efficiency for preparing HDI is high, and the product is strong in unicity; (3) the whole reactant has good circulation stability, and after a certain circulation fails, the active site loading can be carried out on the framework again, so that the reusability is good; (4) the preparation method of the 1, 6-hexamethylene diisocyanate can obtain products with high purity and high yield, and does not corrode a reaction container.
Drawings
FIG. 1 is a chemical structural diagram of the present invention;
FIG. 2 is a chemical structural diagram of the vector of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
preparing raw materials: terephthalaldehyde is Meryer reagent; chlorosulfonic acid (ClSO3H) is Annaiji reagent, KH-550, carbazole, 1, 4-dioxane, Tetrahydrofuran (THF), dichloromethane (CH2Cl2), methanol, potassium hydroxide, hydrochloric acid (HCl), Zr (SO4)2, ZnSO4 and Al2(SO4)3 are all analytically pure, and are produced by national medicine group chemical reagent Limited; the above reagents are all analytically pure.
The solid acid catalyst was prepared as follows:
(1) adding 0.01mol of terephthalaldehyde, 0.02mol of carbazole and 10mL of hydrochloric acid standard solution into 50mL of 1, 4-dioxane solution, stirring for 24 hours in an oil bath kettle at 100 ℃, observing that the solution gradually changes from bright yellow to black to obtain liquid A, and preliminarily polymerizing the terephthalaldehyde and the carbazole to form an organic porous carbon monomer in the environment of the 1, 4-dioxane solution and hydrochloric acid, wherein the chemical formula is as follows: {1, 4-bis [ bis (3-carbazolyl) -methyl) ] benzene };
(2) taking 0.01mol of Zr (SO)4)2、ZnSO4、Al2(SO4)3Dissolving 0.02mol of KH-550 in 5ml of deionized water, and uniformly stirring to obtain liquid B;
(3) pouring the liquid A into a 100mL high-temperature reaction kettle, placing the liquid B into a constant-pressure separating funnel, adding the liquid B in the dropwise adding process, ensuring the uniformity of the dropping speed by adopting the constant-pressure separating funnel, preventing backflow and suck-back, controlling the adding speed to be 1-2 drops/second, and reacting for 24 hours in a closed high-temperature reaction kettle at 220 ℃ after the adding by utilizing the constant-pressure separating funnel is finished to obtain a mixture C;
(4) washing the mixture C for multiple times by THF (tetrahydrofuran), removing residual raw materials, and drying for 12 hours at 50 ℃ by using an oven to obtain a solid D;
(5) 0.8g of solid D and 50mL of CH2Cl2Mixing the mixture in a 250mL flask, stirring the mixture for 1h at room temperature, dropwise adding 5mL of ClSO3H in an ice-water bath, and stirring the mixture for 4h at room temperature to obtain a solid-liquid mixture E;
(6) and (3) gradually washing the lower-layer solid to be neutral by deionized water and methanol, performing suction filtration for multiple times to obtain a solid, and drying for 24 hours at 80 ℃ by using an oven to obtain the solid acid catalyst.
The catalyst structure is as follows:
the obtained solid acid catalyst is subjected to microstructure and component analysis, and the components of the solid acid catalyst comprise 100 parts of carrier, 25 parts of sulfonic acid group, 10 parts of active zinc, 15 parts of active zirconium and 10 parts of active aluminum; the carrier unit structure has the chemical formula: 1, 4-bis [ di (3-carbazolyl) -methyl) ] benzene, the molecular structure is shown in figure 2;
the specific surface area of the support was 621m2·g-1The aperture is 3.2-5.3 nm; the specific surface area of the finally prepared carrier is reduced to 132.5m2·g-1The pore diameter is 2.85nm, which proves that sulfonic acid group and metal group are successfully loaded on the surface of the carrier as active sites, and the total acid amount is 2.75mmol/g；
In infrared analysis, 3424cm can be observed obviously-1The absorption peak is-NH-stretching vibration peak, 1592cm-1The absorption peak is a C ═ C skeleton stretching vibration peak on a benzene ring, and the structural general formula of the carrier unit is met; compared with the carrier TC, the carbon-based solid acid catalyst has 3 new absorption peaks at 701.9cm-1、1164cm-1And 1030cm-1The absorption peak is C-S stretching vibration peak and-SO3H and S ═ O, indicating-SO3H is successfully supported and part of the metal is also in-SO3The form of M binds to the stem; since the infrared is not sensitive to the detection of metals, the components of zinc, zirconium, aluminum, etc. are observed by EDS elemental analysis, and the approximate structure is shown in FIG. 1.
Finally, the carrier is an organic carbon skeleton obtained by copolymerizing terephthalaldehyde and carbazole, has a nanoscale pore diameter, is loaded on the skeleton through a chemical bond with high strength and large specific surface area of a sulfonic group, can still keep a high acidity value in multiple uses, and has a long service life; the active zinc, the active zirconium and the active aluminum can establish C-M (M represents a metal group) with carbazole in a part of the framework, and can be adsorbed on a carrier through physical adhesion.
Catalyst application and activity test:
the solid acid catalyst can be used for catalyzing the reaction for synthesizing 1, 6-hexamethylene diisocyanate (HDI for short) by using hexamethylene diamine and dimethyl carbonate as raw materials, and the specific reaction process is as follows:
(1) taking a 1000mL reaction bottle, adding 100g of hexamethylene diamine, 400g of dimethyl carbonate and 8g of solid acid catalyst into the reaction bottle, replacing air in the bottle by using nitrogen, keeping the reaction bottle in a nitrogen atmosphere, slowly stirring and heating to 90 ℃, and reacting for at least 5 hours;
(2) rectifying the solution obtained in the step one, wherein distillate can be used for recovering dimethyl carbonate and methanol; reducing the pressure in the bottle to about 3KPa by using a vacuum pump, raising the temperature to 120 ℃, and distilling to remove low fraction;
(3) and (3) filling nitrogen into the reaction bottle in the second step to normal pressure, adding 400g of naphthenic oil, reducing the pressure in the bottle to 4KPa again after the addition is finished, heating to 220 ℃, and then carrying out pyrolysis under stirring. In the final product, 132.6g of a total product was collected, wherein the pure HDI was 129.6g and the purity was 97.73%; the reaction ratio of the hexamethylene diamine as the raw material is 89.40 percent, and the overall reaction can be considered to be more sufficient;
(4) removing the solid acid catalyst, washing with ethanol and deionized water, drying, and recycling; after the circulation is carried out for 20 times, the reaction proportion of the raw material hexamethylene diamine is reduced to 85.32 percent, and the yield is still high; after 50 cycles, the reaction rate of the hexamethylenediamine raw material is reduced to below 80%, and the active sites need to be replenished again.
Example 2:
keeping the raw materials and the method in example 1 inconvenient, adjusting the dosage of the raw materials, and preparing solid acid catalysts with different compositions;
the obtained solid acid catalyst is subjected to microstructure and component analysis, and the components of the solid acid catalyst comprise 100 parts of carrier, 18 parts of sulfonic acid group, 8 parts of active zinc, 10 parts of active zirconium and 7 parts of active aluminum; the carrier unit structure has the chemical formula: 1, 4-bis [ di (3-carbazolyl) -methyl) ] benzene;
the specific surface area of the support was 621m2·g-1The aperture is 3.2-5.3 nm; the specific surface area of the finally prepared carrier is reduced to 179.6m2·g-1The pore diameter is 3.25nm, which proves that the sulfonic group and the metal group are successfully loaded on the surface of the carrier as active sites, the total acid amount is 2.15mmol/g, and the whole active sites are less than that of the embodiment 1;
the major peak observed in the infrared analysis was the same as in example 1, indicating-SO3H is successfully loaded; by EDS elemental analysis, components such as zinc, zirconium, aluminum and the like are observed, and the successful loading of the metal group is proved.
Finally, the carrier is an organic carbon skeleton obtained by copolymerizing terephthalaldehyde and carbazole, has a nanoscale pore diameter, is loaded on the skeleton through a chemical bond with high strength and large specific surface area of a sulfonic group, can still keep a high acidity value in multiple uses, and has a long service life; the active zinc, the active zirconium and the active aluminum can establish C-M (M represents a metal group) with carbazole in a part of the framework, and can be adsorbed on a carrier through physical adhesion.
The solid acid catalyst was used for the examination of catalytic activity: the proportion of pure HDI in the final product was 95.25%; the reaction ratio of the raw material hexamethylene diamine is 89.67 percent, and the effect is lower than that of the example 1;
(4) removing the solid acid catalyst, washing with ethanol and deionized water, drying, and recycling; after 20 cycles, the reaction rate of the hexamethylenediamine raw material is reduced to below 80%, and the active sites need to be replenished again.
Example 3:
in this example, the silane coupling agent KH-550 was used to increase the carrier's attachment properties to the metal groups.
Preparing raw materials: terephthalaldehyde is Meryer reagent; chlorosulfonic acid (ClSO3H) is Annage reagent, and is prepared from carbazole, 1, 4-dioxane, Tetrahydrofuran (THF), and dichloromethane (CH)2Cl2) Methanol, potassium hydroxide, hydrochloric acid (HCl), Zr (SO)4)2、ZnSO4、Al2(SO4)3All are analytically pure, produced by chemical reagents of national drug group limited; the above reagents are all analytically pure.
The solid acid catalyst was prepared as follows:
(1) adding 0.01mol of terephthalaldehyde, 0.02mol of carbazole and 10mL of hydrochloric acid standard solution into 50mL of 1, 4-dioxane solution, stirring for 24 hours in an oil bath kettle at 100 ℃, observing that the solution gradually changes from bright yellow to black to obtain liquid A, and preliminarily polymerizing the terephthalaldehyde and the carbazole to form an organic porous carbon monomer in the environment of the 1, 4-dioxane solution and hydrochloric acid, wherein the chemical formula is as follows: {1, 4-bis [ bis (3-carbazolyl) -methyl) ] benzene };
(2) taking 0.02mol of Zr (SO)4)2、ZnSO4、Al2(SO4)3Dissolving in 5ml deionized water, performing ultrasonic treatment at 30KHz frequency for 1h, adding 0.05mol KH550, and stirring to obtain liquid B;
(3) pouring the liquid A into a 100mL high-temperature reaction kettle, placing the liquid B into a constant-pressure separating funnel, adding the liquid B in the dropwise adding process, ensuring the uniformity of the dropping speed by adopting the constant-pressure separating funnel, preventing backflow and suck-back, controlling the adding speed to be 1-2 drops/second, and reacting for 24 hours in a closed high-temperature reaction kettle at 220 ℃ after the adding by utilizing the constant-pressure separating funnel is finished to obtain a mixture C;
(4) washing the mixture C for multiple times by THF (tetrahydrofuran), removing residual raw materials, and drying for 12 hours at 50 ℃ by using an oven to obtain a solid D;
(5) 0.6g of solid D and 50mL of CH2Cl2Mixing in a 250mL flask, stirring at room temperature for 1h, and adding 10mL ClSO dropwise under ice-water bath3H, stirring for 4 hours at room temperature to obtain a solid-liquid mixture E;
(6) and (3) gradually washing the lower-layer solid to be neutral by deionized water and methanol, performing suction filtration for multiple times to obtain a solid, and drying for 24 hours at 80 ℃ by using an oven to obtain the solid acid catalyst.
The catalyst structure is as follows:
the obtained solid acid catalyst is subjected to microstructure and component analysis, and the components of the solid acid catalyst comprise 100 parts of carrier, 36 parts of sulfonic acid group, 16 parts of active zinc, 20 parts of active zirconium, 14 parts of active aluminum and 10 parts of silane coupling agent; the carrier unit structure has the chemical formula: 1, 4-bis [ di (3-carbazolyl) -methyl) ] benzene;
the specific surface area of the support was 621m2G-1, pore size 3.2-5.3 nm; the specific surface area of the finally prepared carrier is reduced to 116.5m2·g-1The pore diameter is 1.32nm, which proves that sulfonic acid group and metal group are successfully loaded on the surface of the carrier as active sites, and the total acid amount is 3.24 mmol/g; due to the addition of the silane coupling agent, the loading capacity of the metal group is improved, the overall aperture is reduced, and compared with the embodiment 1, the acid amount and the metal loading capacity are both increased;
in infrared analysis, 3424cm can be observed obviously-1The absorption peak is-NH-stretching vibration peak, 1592cm-1The absorption peak is a C ═ C skeleton stretching vibration peak on a benzene ring, and the structural general formula of the carrier unit is met; compared with the carrier framework, the carbon-based solid acid catalyst has 3 new absorption peaks at 702.8cm-1、1168cm-1And 1032cm-1Absorption peaks are respectively C-S stretching vibration peak and-SO3H and S ═ O, indicating-SO3H is successfully loaded; because the infrared is not sensitive to the detection of metals, the components such as zinc, zirconium, aluminum and the like are observed by further detecting and analyzing by using EDS elements.
Finally, the carrier is an organic carbon skeleton obtained by copolymerizing terephthalaldehyde and carbazole, and the organic carbon skeleton has a nanoscale pore diameter, in the embodiment, a coupling agent is used, so that a metal group is more easily attached to the carrier skeleton, a sulfonic group with a large specific surface area is loaded on the skeleton through a chemical bond and high strength, a high acidity value can be still kept in multiple uses, and the service life of the catalyst is long; the active zinc, the active zirconium and the active aluminum can establish C-M (M represents a metal group) with carbazole in a part of the framework and can be adsorbed on a carrier through physical adhesion.
Catalyst application and activity testing:
the solid acid catalyst can be used for catalyzing the reaction for synthesizing 1, 6-hexamethylene diisocyanate (HDI for short) by using hexamethylene diamine and dimethyl carbonate as raw materials, and the specific reaction process is as follows:
(1) taking a 1000mL reaction bottle, adding 100g of hexamethylene diamine, 400g of dimethyl carbonate and 8g of solid acid catalyst into the reaction bottle, replacing air in the bottle by using nitrogen, keeping the reaction bottle in a nitrogen atmosphere, slowly stirring and heating to 90 ℃, and reacting for at least 5 hours;
(2) rectifying the solution obtained in the step one, wherein distillate can be used for recovering dimethyl carbonate and methanol; reducing the pressure in the bottle to about 3KPa by using a vacuum pump, raising the temperature to 120 ℃, and distilling to remove low fraction;
(3) and (3) filling nitrogen into the reaction bottle in the second step to normal pressure, adding 400g of naphthenic oil, reducing the pressure in the bottle to 4KPa again after the addition is finished, heating to 220 ℃, and then carrying out pyrolysis under stirring. In the final product, 141.72g of pure HDI was collected, wherein 138.25g of pure HDI had a purity of 98.65%; the reaction ratio of the raw material hexamethylene diamine is 94.36%, and the effect is better compared with that of the example I;
(4) removing the solid acid catalyst, washing with ethanol and deionized water, drying, and recycling; after 30 times of circulation, the reaction proportion of the raw material hexamethylene diamine is reduced to 85.32 percent, and the yield is still high; after 80 cycles, the reaction rate of the raw material hexamethylenediamine is reduced to below 80%, and the active sites need to be replenished again.
Example 4:
keeping the raw materials and the method in example 3 inconvenient, adjusting the dosage of the raw materials, and preparing solid acid catalysts with different compositions;
the obtained solid acid catalyst is subjected to microstructure and component analysis, and the components of the solid acid catalyst comprise 100 parts of carrier, 18 parts of sulfonic acid group, 8 parts of active zinc, 10 parts of active zirconium, 7 parts of active aluminum and 5 parts of KH-550; the carrier unit structure has the chemical formula: 1, 4-bis [ di (3-carbazolyl) -methyl) ] benzene;
the specific surface area of the support was 621m2G-1, pore size 3.2-5.3 nm; the specific surface area of the finally prepared carrier is reduced to 153.58.6m2G-1, pore diameter 3.08nm, which proves that sulfonic acid group and metal group are successfully loaded on the surface of the carrier as active sites, total acid amount is 2.18mmol/g, and the total active sites are less than that of example 3; the major peak observed in the infrared analysis was the same as in example 3, indicating-SO3H is successfully loaded; by EDS elemental analysis, components such as zinc, zirconium, aluminum and the like are observed, and the successful loading of the metal group is proved.
Finally, the carrier is an organic carbon skeleton obtained by copolymerizing terephthalaldehyde and carbazole, has a nanoscale pore diameter, is loaded on the skeleton through a chemical bond with high strength and large specific surface area of a sulfonic group, can still keep a high acidity value in multiple uses, and has a long service life; the active zinc, the active zirconium and the active aluminum can establish C-M (M represents a metal group) with carbazole in a part of the framework and can be adsorbed on a carrier through physical adhesion.
The solid acid catalyst was used for the examination of catalytic activity: the proportion of pure HDI in the final product was 95.89%; the reaction ratio of the hexamethylenediamine as a raw material was 91.32%, and the effect was lower than that in example 3.
Claims (7)
1. A solid acid catalyst having high reactivity, characterized in that: the material comprises, by weight, 100 parts of a carrier, 18-36 parts of sulfonic acid groups, 8-16 parts of active zinc, 10-20 parts of active zirconium and 7-14 parts of active aluminum, wherein the sulfonic acid groups are chemically connected to the carrier, and the zinc, the zirconium and the aluminum are chemically connected and/or physically attached to the carrier;
the carrier is a porous structure with an organic carbon skeleton, and the chemical formula of the unit structure is as follows: 1, 4-bis [ bis (3-carbazolyl) -methyl ] benzene;
the preparation method of the solid acid catalyst comprises the following steps:
the method comprises the following steps: adding terephthalaldehyde, carbazole and hydrochloric acid with standard concentration into a proper amount of 1, 4-dioxane solution, keeping stirring at 90-100 ℃ for reaction for at least 24 hours, and cooling to room temperature to obtain liquid A, wherein the molar ratio of the terephthalaldehyde to the carbazole is 1: 2;
step two: dissolving soluble salt containing zinc, aluminum and zirconium in deionized water and uniformly stirring to prepare liquid B;
step three: heating the liquid A to between 210 ℃ and 220 ℃, slowly dripping the liquid B into the liquid A while keeping stirring, and continuously reacting for at least 24 hours to obtain a solid-liquid mixture C;
step four: washing the solid-liquid mixture C with a detergent to remove unreacted raw materials, and drying at 50 ℃ for 5-6h to obtain a solid D;
step five: dissolving solid D in a certain amount of CH2Cl2Stirring at room temperature until the mixture is fully dissolved, and dropwise adding ClSO in ice water bath3H, stirring for at least 4 hours at room temperature to obtain a solid-liquid mixture E;
step six: and washing the solid-liquid mixture E to be neutral, and drying the solid-liquid mixture E for at least 24h at 80 ℃ to obtain the solid acid catalyst.
2. The solid acid catalyst with high reactivity according to claim 1, characterized in that: the sulfonic acid group content is 36 parts, and the active zinc content is 12 parts; the active zirconium content is 15 parts; the content of active aluminum is 10 parts.
3. The solid acid catalyst of claim 1, wherein: in the second step, the soluble salts containing zinc, aluminum and zirconium are respectively zinc sulfate, aluminum sulfate and zirconium sulfate.
4. The solid acid catalyst of claim 1, wherein: and step two, adding a silane coupling agent, carrying out ultrasonic treatment on the liquid B for 1h at the frequency of 30KHz, then adding the silane coupling agent, and uniformly dissolving.
5. The solid acid catalyst of claim 1, wherein: in the fourth step, the washing agent used for washing the unreacted raw materials from the solid-liquid mixture C is THF.
6. The solid acid catalyst of claim 1, wherein: in the sixth step, the detergents used for washing the solid-liquid mixture E to be neutral are deionized water and methanol.
7. The use of the solid acid catalyst of claim 1, wherein: the solid acid catalyst is used for preparing 1, 6-hexamethylene diisocyanate and has the use method that:
(1) mixing hexamethylenediamine, dimethyl carbonate and a solid acid catalyst, carrying out aminolysis reaction at 50-90 ℃ in a nitrogen atmosphere, and distilling, washing and separating to obtain hexamethylenediamine methyl formate;
(2) the hexamethylene diisocyanate is pyrolyzed at the temperature of 200-300 ℃ to prepare the 1, 6-hexamethylene diisocyanate.
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