CN101259419B - Method for preparing solid acid catalyst - Google Patents
Method for preparing solid acid catalyst Download PDFInfo
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- CN101259419B CN101259419B CN2008100642629A CN200810064262A CN101259419B CN 101259419 B CN101259419 B CN 101259419B CN 2008100642629 A CN2008100642629 A CN 2008100642629A CN 200810064262 A CN200810064262 A CN 200810064262A CN 101259419 B CN101259419 B CN 101259419B
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Abstract
A preparation method for a solid acid catalyst relates to a preparation method for a catalyst. The invention solves the problems of large sewage quantity generated in the existing process for manufacturing DDM and high manufacture cost. The solid acid catalyst of the invention takes a molecular sieve as a carrier, the carrier is subject to ammoniation, baking, re-dealuminzation or ammoniation, damp absorption and re-chemical liquid phase deposition, then is dipped in phosphor and boron for modifying, and finally undergoes hydro-thermal treatment. The solid acid catalyst of the invention can be repeatedly used and has good selectivity to DDM. The sewage quantity generated is greatly reduced when the product of the invention is used for catalyzing the reaction that aniline reacts with formaldehyde to generate 4,4'-diaminodiphenyl methane. As the chemical raw materials like muriatic acid and sodium hydroxide are not added in the reaction process, the manufacture cost is reduced and the yield of DDM reaches over 70 percent.
Description
Technical field
The present invention relates to a kind of Preparation of catalysts method, be specifically related to a kind ofly be used to produce 4, the preparation method of the solid acid catalyst of 4 '-diaminodiphenyl-methane.
Background technology
4,4 '-diaminodiphenyl-methane (DDM) is widely used intermediate temperature setting agent, especially is applied to the curing of epoxy resin.The polyimide resin of use diaminodiphenyl-methane preparation, insulated paint, polyimide resin, bismaleimide resin etc. have good mechanical property, insulating properties, resistance to elevated temperatures, radiation resistance and abrasion resistance.At present, mostly adopt on the commercial plant both at home and abroad to be raw material by aniline and formaldehyde, the synthetic route of hydrochloric acid catalysis just can obtain the DDM crude product through alkali cleaning, washing after the reaction.Producing 4, during 4 '-DDM, can produce and contain the amine brine waste greater than 10 times of product volumes.Simultaneously, the NaOH that a large amount of hydrochloric acid and neutralization are used can make the norm quota of consumption increase, and has increased production cost.
Summary of the invention
The objective of the invention is to produce sewage quantity in 4 '-diaminodiphenyl-methane process and reach the high problem of production cost greatly, and a kind of preparation method of solid acid catalyst is provided in order to solve existing production 4.
Scheme one: the preparation method of solid acid catalyst is realized by following step in this programme: one, the ammoniumization of molecular sieve: under 120～200 ℃ of conditions with molecular sieve drying 1～5h, again dried molecular sieve is put into the ammonium chloride solution that concentration is 0.5～2mol/L, under 80～100 ℃ of conditions, react 1.5～3h, thereafter with 60～100 ℃ water washing to there not being chlorion, dry 12～24h under 100～150 ℃ of conditions obtains ammonium type molecular sieve then; Two, roasting:, obtain hydrogen type molecular sieve with ammonium type molecular sieve roasting 2～4h under 400～600 ℃ of conditions; Three, dealuminzation: use hydrochloric acid room temperature dealuminzation method or oxalic acid dealuminzation method with the hydrogen type molecular sieve dealuminzation, wherein the dealuminzation degree reaches 2～80%, obtains the dealuminzation molecular sieve; Four, dipping: adopt equi-volume impregnating or vacuum impregnation technology in maceration extract, to flood 0.1～4h in the dealuminzation molecular sieve; Five, hydrothermal treatment consists: the molecular sieve after will flooding carries out hydrothermal treatment consists; Promptly obtain solid acid catalyst; Wherein molecular sieve described in the step 1 is the molecular sieve that window is made up of 10～12 atoms; The step of the hydrochloric acid room temperature dealuminzation method described in the step 3 is as follows: hydrogen type molecular sieve is added in 0.1～1mol/L hydrochloric acid, wherein the consumption of hydrochloric acid is 8～12 times of hydrogen type molecular sieve quality, stir 12～20h at ambient temperature, hot wash is to there not being chlorion behind the vacuum filtration, at 110 ℃ of drying 12～24h, thereafter at 450～600 ℃ of roasting 4～12h, promptly obtain the dealuminzation molecular sieve.The step of described oxalic acid dealuminzation method is as follows: hydrogen type molecular sieve is added in the distilled water, wherein the consumption of distilled water is 8～12 times of hydrogen type molecular sieve quality, stir with 300～600r/min rotating speed, add oxalic acid dihydrate, be heated to 90～100 ℃ then, insulation reaction 0.5～4h, hot wash is three to five times behind the vacuum filtration, at 110 ℃ of drying 12～24h, at 450～600 ℃ of roasting 4～12h, promptly obtain the dealuminzation molecular sieve thereafter; The aluminium of wherein taking off is 1: 4 with adding the oxalic acid dihydrate molal quantity.
Scheme two: the preparation method of solid acid catalyst is realized by following step in this programme: the ammoniumization of a, molecular sieve: under 120～200 ℃ of conditions with molecular sieve drying 1～5h, dried molecular sieve is put into 0.5～2mol/L ammonium chloride solution, react 1.5～3h down at 80～100 ℃, 60～100 ℃ water washing is to there not being chlorion, dry 12～24h under 100～150 ℃ of conditions obtains ammonium type molecular sieve then; B, the moisture absorption: is the moisture absorption 10～20 days under 40～80% conditions with ammonium type molecular sieve in air humidity; C, chemical liquid deposition: add in the non-polar organic solvent solution of positive esters of silicon acis, stirring at room 3～8h is dried under 50～100 ℃ of conditions, puts into Muffle furnace again, at the uniform velocity is warmed up to 450～550 ℃ in 2～3h, roasting 2～6h again; D, repetitive operation step c one to three time; E, dipping: adopt equi-volume impregnating or vacuum impregnation technology in maceration extract, to flood in the molecular sieve after steps d is handled; F, hydrothermal treatment consists: the molecular sieve after will flooding carries out hydrothermal treatment consists; Promptly obtain solid acid catalyst; Wherein molecular sieve is the molecular sieve that window is made up of 10～12 atoms among the step a.
Described molecular sieve is the molecular sieve that window is made up of 10～12 atoms.Described maceration extract is PO
4 3-Mixed solution with boric acid; PO wherein
4 3-Mass concentration be 0.01～10%, PO
4 3-The excellent mass concentration of selecting is 2～5%; The boric acid mass concentration is 0.01～10%, and boric acid preferred mass concentration is 1～4%.PO
4 3-Be to provide by phosphoric acid, ammonium dihydrogen phosphate (ADP) or diammonium hydrogen phosphate.
Described hydrothermal treatment consists method is steam treated method or crucible facture.Described steam treated is meant in roasting and feeds water vapour and Air mixing gas or water vapour in the molecular sieve process of impregnation process, and sintering temperature is 150～600 ℃, and the processing time is 2～10h; Water vapour in water vapour and the air Mixture accounts for 50～99% of cumulative volume.Described crucible facture is that the molecular sieve after impregnation process is put into crucible, compress behind the lid crucible cover, join in the Muffle furnace, evenly heat up, be warming up to 140～160 ℃ in the 1h, constant temperature 0.5～1.5h evenly heats up again, is warming up to 280～310 ℃ in the 1h, constant temperature 0.5～1.5h, evenly heat up again, be warming up to 550 ℃ in the 1h, constant temperature 3～6h.
Solid acid catalyst of the present invention can reuse, and is good to the DDM selectivity.Product of the present invention generates 4 at catalysis aniline and formolite reaction, in the reaction of 4 '-diaminodiphenyl-methane, produce sewage quantity and reduce greatly, because industrial chemicals such as not additional hydrochloric acid, NaOH have reduced production cost in the course of reaction, and the yield of DDM reaches more than 70%.
Description of drawings
Fig. 1 is the infrared spectrum of the solid acid catalyst of use in the specific embodiment six.Fig. 2 is the infrared spectrum of the solid acid catalyst of use in the specific embodiment seven.
The specific embodiment
The specific embodiment one: present embodiment solid acid catalyst preparation method's step is as follows: one, the ammoniumization of molecular sieve: under 120～200 ℃ of conditions with molecular sieve drying 1～5h, again dried molecular sieve is put into the ammonium chloride solution that concentration is 0.5～2mol/L, under 80～100 ℃ of conditions, react 1.5～3h, thereafter with 60～100 ℃ water washing to there not being chlorion, dry 12～24h under 100～150 ℃ of conditions obtains ammonium type molecular sieve then; Two, roasting:, obtain hydrogen type molecular sieve with ammonium type molecular sieve roasting 2～4h under 400～600 ℃ of conditions; Three, dealuminzation: use hydrochloric acid room temperature dealuminzation method or oxalic acid dealuminzation method with the hydrogen type molecular sieve dealuminzation, wherein the dealuminzation degree reaches 2～80% (weight), obtains the dealuminzation molecular sieve; Four, dipping: adopt equi-volume impregnating or vacuum impregnation technology in maceration extract, to flood 0.1～4h in the dealuminzation molecular sieve; Five, hydrothermal treatment consists: the molecular sieve after will flooding carries out hydrothermal treatment consists; Promptly obtain solid acid catalyst; Wherein molecular sieve is the molecular sieve that window is made up of 10～12 atoms in the step 1.
The quality of ammonium chloride solution is 5～20 times of molecular sieve.Produce in the DDM process, the aperture is greater than 6
Less than 8.0
Molecular sieve just may make 2 of aniline and generation, the free external diffusion in molecular sieve of 4 '-diaminodiphenyl-methane (MDA) is carried out the inner surface that is reflected at molecular sieve, suppresses accessory substance MDA and polyamine compounds simultaneously and produces.Therefore the solid catalyst carrier molecular sieve that should select window to form by 10～12 atoms.
Because in building-up process, can there be a certain amount of non-framework aluminum in molecular sieve, these materials can stop up the aperture of molecular sieve, influence the selectivity of solid catalyst to DDM.Remove a spot of framework aluminum the acidity of molecular sieve is increased, produce the hydroxyl hole, favourable reaction is carried out.
The vacuum impregnation technology step is as follows in the present embodiment step 4: the dealuminzation molecular sieve is joined in the maceration extract, flooded 0.1～4 hour, vacuum dehydration drying is then promptly finished the vacuum impregnation of dealuminzation molecular sieve.Maceration extract is PO
4 3-Mixed solution with boric acid; PO wherein
4 3-Mass concentration be 0.01～10%, preferred mass concentration is 2～5%; The boric acid mass concentration is 0.01～10%, and preferred mass concentration is 1～4%.PO43-is provided by phosphoric acid, ammonium dihydrogen phosphate (ADP) or diammonium hydrogen phosphate.Phosphoric acid, boric acid modified meeting descend molecular sieve strong acid center quantity, and the weak acid centric quantity increases.Simultaneously, phosphoric acid, boric acid modified meeting change molecular sieve window diameter, make the window diameter be suitable for reacting requirement.
It is 0.01～50% that the solid acid catalyst that present embodiment obtains contains the phosphorous oxides percent by weight, contains boron oxide compound 0.01～50%, aluminum oxide 0.01～20%, Si oxide 30～90%.
The specific embodiment two: what present embodiment and the specific embodiment one were different is that molecular sieve is X type molecular sieve, Y zeolite, ZSM-12 molecular sieve or beta molecular sieve in the step 1.Other is identical with the specific embodiment one.
The specific embodiment three: what present embodiment and the specific embodiment one were different is that sintering temperature is 550 ℃ in the step 2.Other is identical with the specific embodiment one.
The specific embodiment four: what present embodiment and the specific embodiment one were different is: the step of hydrochloric acid room temperature dealuminzation method is as follows in the step 3: hydrogen type molecular sieve is added in 0.1～1mol/L hydrochloric acid, wherein the consumption of hydrochloric acid is 8～12 times of hydrogen type molecular sieve quality, stir 12～20h at ambient temperature, hot wash is to there not being chlorion behind the vacuum filtration, at 110 ℃ of drying 12～24h, thereafter at 450～600 ℃ of roasting 4～12h, promptly obtain the dealuminzation molecular sieve.Other is identical with the specific embodiment one.
Hydrochloric acid room temperature dealuminzation method mainly is the non-framework aluminum that removes the molecular sieve surface in the present embodiment.
The specific embodiment five: what present embodiment and the specific embodiment one were different is: the step of step 3 mesoxalic acid dealuminzation method is as follows: hydrogen type molecular sieve is added in the distilled water, wherein the consumption of distilled water is 8～12 times of hydrogen type molecular sieve quality, stir with 300～600r/min rotating speed, add oxalic acid dihydrate, be heated to 90～100 ℃ then, insulation reaction 0.5～4h, hot wash is three to five times behind the vacuum filtration, at 110 ℃ of drying 12～24h, thereafter at 450～600 ℃ of roasting 4～12h, promptly obtain the dealuminzation molecular sieve; Other is identical with the specific embodiment one.
The aluminium that present embodiment is taken off is 1: 4 with adding the oxalic acid dihydrate molal quantity.
The specific embodiment six: what present embodiment and the specific embodiment one were different is that the dealuminzation degree reaches 20～40% (weight) in the step 3.Other is identical with the specific embodiment one.
The specific embodiment seven: what present embodiment and the specific embodiment one were different is that the hydrothermal treatment consists method is steam treated method or crucible facture in the step 4.Other is identical with the specific embodiment one.
The present embodiment steam treated is meant in roasting and feeds water vapour and Air mixing gas or water vapour in the molecular sieve process of impregnation process, divides one-step baking, and temperature is 150～600 ℃, and the processing time is 2～10h; Water vapour and air Mixture steam account for 50～99% of cumulative volume.
The crucible facture is that the molecular sieve after impregnation process is put into crucible, compress behind the lid crucible cover, join in the Muffle furnace, evenly heat up, be warming up to 140～160 ℃ in the 1h, constant temperature 0.5～1.5h evenly heats up again, is warming up to 280～310 ℃ in the 1h, constant temperature 0.5～1.5h, evenly heat up again, be warming up to 550 ℃ in the 1h, constant temperature 3～6h.
The specific embodiment eight: present embodiment solid acid catalyst preparation method's step is as follows: one, the ammoniumization of molecular sieve: under 200 ℃ of conditions with 200g molecular sieve drying 2h, dried molecular sieve being put b, to go into 2000ml concentration be in the 1mol/L ammonium chloride solution again, under 90 ℃ of conditions, react 2h, thereafter with 60～100 ℃ water washing to there not being chlorion, dry 12～24h under 110 ℃ of conditions obtains ammonium type molecular sieve then; Molecular sieve is the molecular sieve that window is made up of 10～12 atoms; Two, roasting:, obtain hydrogen type molecular sieve with ammonium type molecular sieve roasting 2～4h under 550 ℃ of conditions; Three, dealuminzation: the 100g hydrogen type molecular sieve is added in the 200ml distilled water, stir with 300～600r/min rotating speed, add the 52.5g oxalic acid dihydrate, be heated to 90～100 ℃ then, insulation reaction 1～2h, hot wash is three to five times behind the vacuum filtration, at 110 ℃ of drying 12～24h, thereafter at 450～600 ℃ of roasting 4～12h, promptly obtain the dealuminzation molecular sieve; Four, flood, 20g dealuminzation molecular sieve is joined 200ml NH
4H
2PO
4And H
3BO
3In the mixed liquor, react 1～2h under 90-100 ℃ of condition, vacuum is steamed water, NH
4H
2PO
4Mass concentration be 3%, H
3BO
3Mass concentration be 1%; Five, hydrothermal treatment consists: the molecular sieve after impregnation process is put into crucible, compress behind the lid crucible cover, join in the Muffle furnace, evenly heat up, be warming up to 150 ℃ in the 1h, constant temperature 1h evenly heats up again, is warming up to 300 ℃ in the 1h, constant temperature 1h evenly heats up again, is warming up to 550 ℃ in the 1h, constant temperature 4h; Obtain the 24.5g solid acid catalyst.Present embodiment makes consisting of of solid acid catalyst: H
2OAl
2O
36.88SiO
20.69P
2O
50.43B
2O
3
The solid acid catalyst preparation 4 that utilizes present embodiment to obtain, 4 '-diaminodiphenyl-methane is verified effect of the present invention, preparation 4, the step of 4 '-diaminodiphenyl-methane is as follows: aniline is joined in the reactor, drip the formalin of 1/7 aniline molal quantity under the room temperature, the control reaction temperature is lower than 5O ℃, after adding, and stirred overnight at room temperature.The reaction product that obtains divides water through separatory funnel, and decompression steams 1/7 of about aniline addition again, to remove whole water; Measure etc. and to steam aniline amount dehydration aniline, join in the distillation still substrate; Obtain benzene feedstock amine formaldehyde ratio and be 7: 1 translocation reaction raw material; The solid acid catalyst that the present embodiment of adding 5g obtains in 150ml acetal solution, reaction temperature is 150 ℃, reaction time 4h.After finishing reaction, steam aniline, liquid-phase chromatographic analysis, formaldehyde conversion ratio: 100%; 4, the yield of 4 '-diaminodiphenyl-methane: 53.5%; 2, the yield of 4 '-diaminodiphenyl-methane: 15.6%, the yield of triamine and polyamines: 30.9%.
The specific embodiment eight: the present embodiment and the specific embodiment seven are not both: add 18.7g two pasture and water in the step 3; Finally obtain the 24.5g solid acid catalyst.Other is identical with the specific embodiment seven.Present embodiment makes the H that consists of of solid acid catalyst
2OAl
2O
335.4SiO
22.9P
2O
51.8B
2O
3
By the preparation of the method in the specific embodiment seven 4,4 '-diaminodiphenyl-methane.The conversion ratio of formaldehyde: 100%; 4, the yield of 4 '-diaminodiphenyl-methane: 71.2%; 2, the yield of 4 '-diaminodiphenyl-methane: 13.2%, the yield of triamine and polyamines: 15.6%.
The specific embodiment nine: the preparation process of present embodiment solid acid catalyst is as follows: the ammoniumization of a, molecular sieve: under 120～200 ℃ of conditions with molecular sieve drying 1～5h, dried molecular sieve is put into 0.5～2mol/L ammonium chloride solution, react 1.5～3h down at 80～100 ℃, 60～100 ℃ water washing is to there not being chlorion, dry 12～24h under 100～150 ℃ of conditions obtains ammonium type molecular sieve then; B, the moisture absorption: is the moisture absorption 10～20 days under 40～80% conditions with ammonium type molecular sieve in air humidity; C, chemical liquid deposition: add in the non-polar organic solvent solution of positive esters of silicon acis, stirring at room 3～8h is dried under 50～100 ℃ of conditions, puts into Muffle furnace again, at the uniform velocity is warmed up to 450～550 ℃ in 2～3h, roasting 2～6h again; D, repetitive operation step c one to three time; E, dipping: adopt equi-volume impregnating or vacuum impregnation technology in maceration extract, to flood in the molecular sieve after steps d is handled; F, hydrothermal treatment consists: the molecular sieve after will flooding carries out hydrothermal treatment consists; Promptly obtain solid acid catalyst.
In the present embodiment among the step a molecular sieve be the molecular sieve that window is made up of 10～12 atoms, the quality of ammonium chloride solution is 5～20 times of molecular sieve.Positive esters of silicon acis is methyl silicate or ethyl orthosilicate among the step c, and non-polar organic solvent is cyclohexane, n-hexane or benzene.The vacuum impregnation technology step is as follows among the present embodiment step e: the molecular sieve after steps d is handled is joined in the maceration extract, flooded 0.1～4 hour, vacuum dehydration drying is then promptly finished the molecular sieve vacuum impregnation.Maceration extract is PO
4 3-Mixed solution with boric acid; PO wherein
4 3-Mass concentration be 0.01～10%, preferred mass concentration is 2～5%; The boric acid mass concentration is 0.01～10%, and preferred mass concentration is 1～4%.PO
4 3-Be to provide by phosphoric acid, ammonium dihydrogen phosphate (ADP) or diammonium hydrogen phosphate.Phosphoric acid, boric acid modified meeting descend molecular sieve strong acid center quantity, and the weak acid centric quantity increases.Simultaneously, phosphoric acid, boric acid modified meeting change molecular sieve window diameter, make the window diameter be suitable for reacting requirement.
Chemical liquid deposition is a strong polarity of utilizing the organosilicon acid esters, under the effect of minor amount of water, with the silicon hydroxyl and the aluminium hydroxyl reaction of molecular sieve outer surface, after roasting, forms one deck silicon hydroxyl on the molecular sieve surface.Select the molecular diameter of organosilicon acid esters to make the organosilicon acid esters can not enter molecular sieve inside like this, like this silicon hydroxyl and the aluminium hydroxyl reaction of organosilicon acid esters and molecular sieve outer surface greater than the aperture of molecular sieve.Be a kind of molecular sieve inner surface acidity and structure of not changing, only change a kind of method of molecular sieve outer surface acidity.Simultaneously, the silicon hydroxyl that forms at the molecular sieve window can make molecular sieve window diameter reduce, and can reach the purpose of regulating molecular sieve bore diameter.
The specific embodiment ten: what present embodiment and the specific embodiment one were different is that the hydrothermal treatment consists method is steam treated method or crucible facture among the step f.
The present embodiment steam treated is meant in roasting and feeds water vapour and Air mixing gas or water vapour in the molecular sieve process of impregnation process, and sintering temperature is 150～600 ℃, and the processing time is 2～10h; Water vapour and air Mixture steam account for 50～99% of cumulative volume.
The crucible facture is that the molecular sieve after impregnation process is put into crucible, compress behind the lid crucible cover, join in the Muffle furnace, evenly heat up, be warming up to 140～160 ℃ in the 1h, constant temperature 0.5～1.5h evenly heats up again, is warming up to 280～310 ℃ in the 1h, constant temperature 0.5～1.5h, evenly heat up again, be warming up to 550 ℃ in the 1h, constant temperature 3～6h.
The specific embodiment 11: the preparation process of present embodiment solid acid catalyst is as follows: the ammoniumization of a, molecular sieve: under 120～200 ℃ of conditions with 50gH beta molecular sieve drying 1～5h, dried molecular sieve is put into 0.5～2mol/L ammonium chloride solution, react 1.5～3h down at 80～100 ℃, 60-100 ℃ of hot water, washing is to there not being chlorion, dry 12～24h under 100～150 ℃ of conditions obtains ammonium type molecular sieve then; B, the moisture absorption: is the moisture absorption 10～20 days under 40～80% conditions with ammonium type molecular sieve in air humidity; C, chemical liquid deposition: add in the mixed liquor of 10ml silester and 50ml cyclohexane, stirring at room 3～8h is dried under 50～100 ℃ of conditions, puts into Muffle furnace again, at the uniform velocity is warmed up to 450～550 ℃ in 2～3h, roasting 2～6h again; D, repetitive operation step c one to three time; E, dipping: 20g dealuminzation molecular sieve is joined 200ml NH
4H
2PO
4And H
3BO
3In the mixed liquor, react 1～2h under 90-100 ℃ of condition, vacuum is steamed water, NH
4H
2PO
4Mass concentration be 3%, H
3BO
3Mass concentration be 1%; F, hydrothermal treatment consists: the molecular sieve after impregnation process is put into crucible, compress behind the lid crucible cover, join in the Muffle furnace, evenly heat up, be warming up to 150 ℃ in the 1h, constant temperature 1h evenly heats up again, is warming up to 300 ℃ in the 1h, constant temperature 1h evenly heats up again, is warming up to 550 ℃ in the 1h, constant temperature 4h; Obtain the 24.5g solid acid catalyst.
By the preparation of the method in the specific embodiment seven 4,4 '-diaminodiphenyl-methane.The conversion ratio of formaldehyde: 100%; 4, the yield of 4 '-diaminodiphenyl-methane: 71.15%; 2, the yield of 4 '-diaminodiphenyl-methane: 13.65%, the yield of triamine and polyamines: 15.2%.
Claims (8)
1. the preparation method of a solid acid catalyst, the preparation method who it is characterized in that solid acid catalyst is realized by following step: one, the ammoniumization of molecular sieve: under 120～200 ℃ of conditions with molecular sieve drying 1～5h, again dried molecular sieve is put into the ammonium chloride solution that concentration is 0.5～2mol/L, under 80～100 ℃ of conditions, react 1.5～3h, thereafter with 60～100 ℃ water washing to there not being chlorion, dry 12～24h under 100～150 ℃ of conditions obtains ammonium type molecular sieve then; Two, roasting:, obtain hydrogen type molecular sieve with ammonium type molecular sieve roasting 2～4h under 400～600 ℃ of conditions; Three, dealuminzation: use hydrochloric acid room temperature dealuminzation method or oxalic acid dealuminzation method with the hydrogen type molecular sieve dealuminzation, wherein the dealuminzation degree reaches 2～80% (weight), obtains the dealuminzation molecular sieve; Four, dipping adopts equi-volume impregnating or vacuum impregnation technology to flood 0.1～4h in maceration extract in the dealuminzation molecular sieve; Five, hydrothermal treatment consists: the molecular sieve after will flooding carries out hydrothermal treatment consists; Promptly obtain solid acid catalyst; Molecular sieve is the molecular sieve that window is made up of 10～12 atoms in the step 1; When using oxalic acid dealuminzation method with the hydrogen type molecular sieve dealuminzation in the step 3, the mol ratio of the aluminium of taking off and the oxalic acid dihydrate of adding is 1: 4; Maceration extract is PO in the step 4
4 3-With the mixed solution of boric acid, PO in the mixed solution wherein
4 3-Mass concentration be 0.01～10%, mixed solution mesoboric acid mass concentration is 0.01～10%.
2. the preparation method of a kind of solid acid catalyst according to claim 1, the step that it is characterized in that hydrochloric acid room temperature dealuminzation method in the step 3 is as follows: hydrogen type molecular sieve is added in 0.1～1mol/L hydrochloric acid, wherein the consumption of hydrochloric acid is 8～12 times of hydrogen type molecular sieve quality, stir 12～20h at ambient temperature, hot wash is to there not being chlorion behind the vacuum filtration, at 110 ℃ of drying 12～24h, at 450～600 ℃ of roasting 4～12h, promptly obtain the dealuminzation molecular sieve thereafter.
3. the preparation method of a kind of solid acid catalyst according to claim 1, the step that it is characterized in that step 3 mesoxalic acid dealuminzation method is as follows: hydrogen type molecular sieve is added in the distilled water, wherein the consumption of distilled water is 8～12 times of hydrogen type molecular sieve quality, stir with 300～600r/min rotating speed, add oxalic acid dihydrate, be heated to 90～100 ℃ then, insulation reaction 0.5～4h, hot wash is three to five times behind the vacuum filtration, at 110 ℃ of drying 12～24h, thereafter at 450～600 ℃ of roasting 4～12h, promptly obtain the dealuminzation molecular sieve.
4. the preparation method of a kind of solid acid catalyst according to claim 1 is characterized in that PO
4 3-Be to provide by phosphoric acid, ammonium dihydrogen phosphate (ADP) or diammonium hydrogen phosphate.
5. the preparation method of a kind of solid acid catalyst according to claim 1 is characterized in that the hydrothermal treatment consists method is steam treated method or crucible facture in the step 5; Wherein steam treated is meant in roasting and feeds water vapour and Air mixing gas or water vapour in the molecular sieve process of impregnation process, and sintering temperature is 150～600 ℃, and the processing time is 2～10h; Steam accounts for 50～99% of water vapour and air Mixture cumulative volume; Wherein the crucible facture is that the molecular sieve after impregnation process is put into crucible, compress behind the lid crucible cover, join in the Muffle furnace, evenly heat up, be warming up to 140～160 ℃ in the 1h, constant temperature 0.5～1.5h evenly heats up again, is warming up to 280～310 ℃ in the 1h, constant temperature 0.5～1.5h, evenly heat up again, be warming up to 550 ℃ in the 1h, constant temperature 3～6h.
6. the preparation method of a solid acid catalyst, the preparation method who it is characterized in that solid acid catalyst is realized by following step: the ammoniumization of a, molecular sieve: under 120～200 ℃ of conditions with molecular sieve drying 1～5h, dried molecular sieve is put into 0.5～2mol/L ammonium chloride solution, react 1.5～3h down at 80～100 ℃, with 60～100 ℃ water washings to there not being chlorion, dry 12～24h under 100～150 ℃ of conditions obtains ammonium type molecular sieve then; B, the moisture absorption: is the moisture absorption 10～20 days under 40～80% conditions with ammonium type molecular sieve in air humidity; C, chemical liquid deposition: add in the non-polar organic solvent solution of positive esters of silicon acis, stirring at room 3～8h is dried under 50～100 ℃ of conditions, puts into Muffle furnace again, at the uniform velocity is warmed up to 450～550 ℃ in 2～3h, roasting 2～6h again; D, repetitive operation step c one to three time; E, dipping: adopt equi-volume impregnating or vacuum impregnation technology in maceration extract, to flood in the molecular sieve after steps d is handled; F, hydrothermal treatment consists: the molecular sieve after will flooding carries out hydrothermal treatment consists; Promptly obtain solid acid catalyst; Molecular sieve is the molecular sieve that window is made up of 10～12 atoms among the step a; Maceration extract is PO among the step e
4 3-Mixed solution with boric acid; PO wherein
4 3-Mass concentration be 0.01～10%; The boric acid mass concentration is 0.01～10%, PO
4 3-Be to provide by phosphoric acid, ammonium dihydrogen phosphate (ADP) or diammonium hydrogen phosphate.
7. the preparation method of a kind of solid acid catalyst according to claim 6 is characterized in that positive esters of silicon acis is methyl silicate or ethyl orthosilicate among the step c, and non-polar organic solvent is cyclohexane, n-hexane or benzene.
8. the preparation method of a kind of solid acid catalyst according to claim 6 is characterized in that the hydrothermal treatment consists method is steam treated method or crucible facture among the step f; Wherein steam treated is meant in roasting and feeds water vapour and Air mixing gas or water vapour in the molecular sieve process of impregnation process, and sintering temperature is 150～600 ℃, and the processing time is 2～10h; Water vapour in water vapour and the air Mixture accounts for 50～99% of cumulative volume; The crucible facture is that the molecular sieve after impregnation process is put into crucible, compress behind the lid crucible cover, join in the Muffle furnace, evenly heat up, be warming up to 140～160 ℃ in the 1h, constant temperature 0.5～1.5h evenly heats up again, is warming up to 280～310 ℃ in the 1h, constant temperature 0.5～1.5h, evenly heat up again, be warming up to 550 ℃ in the 1h, constant temperature 3～6h.
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| KR20170031157A (en) * | 2014-07-07 | 2017-03-20 | 코베스트로 도이칠란트 아게 | Process for the production of di- and polyamines of the diphenylmethane series |
| CN113799230A (en) * | 2021-08-27 | 2021-12-17 | 北京林业大学 | Furfuryl alcohol modified liquid and preparation method and application thereof |
| CN115007198B (en) * | 2022-07-07 | 2023-07-14 | 扬州晨化新材料股份有限公司 | ZSM-48 molecular sieve containing composition for continuously synthesizing tertiary amine catalyst for polyurethane and preparation method thereof |
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