CN111905753A - Catalyst for catalyzing amine salt conversion, preparation method of catalyst and preparation method of DAM - Google Patents

Catalyst for catalyzing amine salt conversion, preparation method of catalyst and preparation method of DAM Download PDF

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CN111905753A
CN111905753A CN202010793516.1A CN202010793516A CN111905753A CN 111905753 A CN111905753 A CN 111905753A CN 202010793516 A CN202010793516 A CN 202010793516A CN 111905753 A CN111905753 A CN 111905753A
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aniline
catalyst
reaction
solution
salt
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CN111905753B (en
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李永锋
邢津铭
章靓
吴雪峰
张宏科
陈良进
崔成成
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Wanhua Chemical Group Fujian Isocyanate Co ltd
Wanhua Chemical Group Co Ltd
Wanhua Chemical Ningbo Co Ltd
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Wanhua Chemical Ningbo Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium
    • B01J23/868—Chromium copper and chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C07C209/78—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton from carbonyl compounds, e.g. from formaldehyde, and amines having amino groups bound to carbon atoms of six-membered aromatic rings, with formation of methylene-diarylamines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/82—Purification; Separation; Stabilisation; Use of additives
    • C07C209/84—Purification
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention relates to a catalyst for catalyzing amine salt conversion, a preparation method thereof and a preparation method of DAM (dimethyl formamide), wherein the catalyst comprises a carrier and active components, wherein the active components comprise praseodymium oxide, cuprous oxide, chromium trioxide and tin oxide; the preparation method of the DAM comprises the following steps: (a) mixing aniline acid salt and formaldehyde solution for condensation reaction; (b) transferring H + in a salified amino group of diphenylmethane series diamine and polyamine in the reaction liquid prepared in the step (a) to an amino group of aniline existing in a molecular form in the reaction liquid obtained in the step (a) by using the catalyst, so that the diamine and the polyamine in the reaction liquid are converted into a molecular state; (c) phase separation is carried out on the reaction liquid obtained in the step (b). The method of the invention obviously reduces the manufacturing cost of diamine and polyamine (DAM) of diphenylmethane series and the generation amount of waste brine, and simultaneously ensures the stable quality of the DAM.

Description

Catalyst for catalyzing amine salt conversion, preparation method of catalyst and preparation method of DAM
Technical Field
The invention relates to the technical field of preparation of diamine and polyamine of diphenylmethane series, and mainly relates to a catalyst for catalyzing amine salt conversion, a preparation method and a preparation method of DAM.
Background
MDI is one of the main raw materials in the polyurethane industry. The synthesis of MDI by reacting aniline and formaldehyde in the presence of an acidic catalyst to produce polymethylene polyphenyl polyamines (DAM) and then reacting the DAM with phosgene is a well known process in the industry.
In the conventional process for preparing diamines and polyamines (DAM) of the diphenylmethane series, aniline and formaldehyde are subjected to a condensation reaction under the action of an acid catalyst to obtain an acidic reaction mixture containing diamines and polyamines (DAM) of the diphenylmethane series, the reaction solution containing the salt of the DAM is then completely neutralized with an alkaline solution and is separated into an organic phase and a brine phase, and the organic phase is further refined to obtain crude DAM. The process of neutralizing the reaction solution with a base is usually carried out at 90 to 110 ℃, and hydroxides of alkali metal and alkaline earth metal elements are suitable as the base, for example, aqueous NaOH is used. In the process of completely neutralizing diamine salts and polyamine salts of diphenylmethane series with alkali to obtain diamine and polyamine of diphenylmethane series, since the amount of acid catalyst used in the front end salt formation reaction is large, such as hydrochloric acid catalyst, a large amount of caustic soda is consumed for sufficiently neutralizing hydrochloric acid, and the cost of caustic soda accounts for nearly 10% of the manufacturing cost of DAM. Meanwhile, due to the addition of caustic soda, a large amount of waste brine containing organic amine is generated, and great pressure is also caused on environmental-friendly discharge or recycling. In addition, due to the particularity of the neutralization reaction, if the adding amount of caustic soda is insufficient or the control is unstable, the excessive acidic reaction liquid will corrode downstream non-acid-resistant equipment, and the long-period stable operation of the device is influenced.
At present, many domestic and foreign patent documents relate to the neutralization reaction and phase separation technology of diamine and polyamine of diphenylmethane series, for example, patent document EP1652835a1 describes how to neutralize diamine salt and polyamine salt of diphenylmethane series with alkali liquor, and the separation of the resulting salt-containing aqueous phase from the product-containing organic phase. Therefore, how to create a method and a catalyst which can directly convert amine salt to prepare corresponding diamine and polyamine becomes a problem to be solved urgently in the industry.
Disclosure of Invention
The invention aims to provide a catalyst for catalyzing amine salt conversion and a preparation method thereof, and a preparation method of diamine and polyamine of diphenylmethane series.
In order to achieve the above object, the present invention provides a catalyst for catalyzing the conversion of an amine salt, the catalyst comprising a support and an active component; the carrier is TiO2The active components comprise praseodymium oxide, cuprous oxide, chromium trioxide and tin oxide.
Preferably, the carrier is nano TiO2Preferably, the crystal grain size of the carrier is 1 to 100nm, preferably 5 to 80 nm.
Preferably, the active ingredient content comprises, based on the weight of the carrier:
praseodymium oxide: 1.0 to 8.0 wt.%, preferably 2.0 to 4.5 wt.%;
cuprous oxide: 5.0 to 14.0 wt.%, preferably 9.0 to 12.0 wt.%;
chromium oxide: 13.0 to 20.0 wt.%, preferably 14.0 to 17.0 wt.%;
tin oxide: 10.0 to 16.0 wt.%, preferably 12.0 to 15.0 wt.%.
The invention also provides a preparation method of the catalyst for catalyzing amine salt conversion, which comprises the following steps:
soluble salt solution containing active metal and carrier TiO2Contact to perform impregnation and adsorption, then adding a dispersing agent to uniformly disperse, adjusting the pH value to 8.0-9.0, then standing, performing suction filtration, washing, drying, and calcining to obtain the solid catalyst.
The support TiO2Can select commercially available TiO2The carrier is made by self.
In some preferred embodiments of the present invention, the carrier is prepared by a method comprising: taking titanate as a titanium source, adding a mixed solution of micromolecular alcohol and pure water as a solvent, and adding micromolecular acid to inhibit hydrolysis. Gradually and slowly adding a solution prepared from precipitator urea and micromolecular alcohol into the mixed solution, simultaneously heating to the urea decomposition temperature of 155-2And (3) a carrier.
The titanate can be any one of butyl titanate, isopropyl titanate, tetraisobutyl titanate and the like.
The small molecular alcohol can be any one of methanol, ethanol, propanol, isopropanol and the like;
the small molecular acid can be any one of formic acid, acetic acid, propionic acid and the like;
preferably, after separating out the precipitate, the precipitate is ultrasonically cleaned for 3 to 5 times by using absolute ethyl alcohol.
Preferably, the drying temperature of the carrier is 155-170 ℃ and the carrier is dried for 30-60 min.
Preferably, during the preparation of the carrier, the carrier is finally calcined for 1.5 to 3 hours at the temperature of 300-350 ℃ in the air atmosphere to obtain the nano TiO2And (3) a carrier. According to the preparation method of the catalytic amine salt conversion catalyst provided by the invention, the nano TiO is prepared2Carrier, titanate: small molecule alcohol: pure water: the addition volume ratio of the small molecular acid is 5-15:40-55:40-60: 8-12.
The precipitating agent urea is prepared into 16-23 wt% solution by using small molecular alcohol as solvent. The addition amount of the micromolecule alcohol solution of the precipitator urea and the micromolecule alcohol solution of the precipitator urea with the volume ratio of 0.3-0.8:1 of the mixed solution are completed within 30-60min, preferably 45-55min, the system is heated to 155-170 ℃ within 15-20min after the addition is started, and the system temperature is maintained at 155-170 ℃ until 5-10min after the addition of the precipitator is completed.
In the catalytic amine salt conversion catalyst provided by the invention, the TiO carrier is prepared by the above process2The carrier has the particle size range of 1-80nm, good crystallization degree, large specific surface area, and continuous flocculent and reticular porous particle structure, and can improve the attachment rate of soluble salts of active metals, especially the attachment rate of chlorides of the active metals, thereby obviously improving the catalytic efficiency.
In a preferred embodiment of the invention, the soluble salt containing the active metal may be a nitrate and/or a chloride solution containing the active metal, and may be, for example, praseodymium nitrate, copper chloride, chromium nitrate, and tin chloride. Wherein, praseodymium nitrate: copper chloride: chromium nitrate: the molar ratio of stannic chloride is 1-2: 2-5: 6-15: 5-12.
The addition of a dispersant is a matter of routine choice in the art, preferably the dispersant is polyethylene glycol 2000, and in a particular embodiment of the invention, the mass of the dispersant added is 5-15%, preferably 7-10% of the mass of the support in the catalyst.
In a preferred embodiment of the present invention, the preparation method of the catalytic amine salt conversion catalyst specifically comprises: placing soluble salt containing active metal (such as praseodymium nitrate, copper chloride, chromium nitrate and stannic chloride) in a beaker, adding pure water, stirring to dissolve, and adding self-made TiO2Carrier material, finally adding dispersing agent, such as polyethylene glycol 2000, dispersing uniformly by ultrasonic wave, stirring for 1-3h at constant temperature at room temperature, dripping ammonia water while stirring until the pH value is 8.0-9.0, then standing, filtering, washing, drying, and the process conditions of drying include: the drying temperature is 70-90 ℃; the drying time is 15-40h, more preferably 20-30 h; then calcining at 480 ℃ and 600 ℃, preferably 500 ℃ and 550 ℃ in air atmosphere for 3-7h, preferably 3.5-5.5h to obtain the catalyst with the solid network structure.
The invention adopts the combination of a uniform precipitation method and an impregnation method, and active metal oxides are loaded in the form of spherical nano particlesNano TiO on high specific surface2The carrier surface has small particle size and uniform dispersion, and the carrier structure limits the migration of the nano particles and can prevent the nano particles from agglomerating, thereby fully playing the characteristic of huge specific surface area of the nano catalyst. In addition, the catalyst has multiple surface active points and strong adsorption capacity, and the high-content active component can effectively reduce the activation energy of amine salt conversion and show excellent catalytic effect.
It is another object of the present invention to provide a process for the preparation of di-and polyamines of the diphenylmethane series, comprising the steps of:
(a) in the presence of an acid catalyst, aniline is subjected to a salt forming reaction to generate aniline acid salt; then mixing aniline acid salt and formaldehyde solution for condensation reaction to obtain reaction liquid containing diamine salt and polyamine salt of diphenylmethane series;
(b) mixing an organic solvent with the reaction liquid prepared in the step (a), introducing the mixture into a reactor filled with the catalyst of the invention, and leading the diamine salt of diphenylmethane series in the reaction liquid and the H in the amino group on the polyamine salt+Transferring the reaction solution obtained in the step (a) to an amino group of aniline existing in a molecular form, so that diphenylmethane series diamine salt and polyamine salt in the reaction solution are converted into diphenylmethane series diamine and polyamine and aniline acid salt;
(c) phase separation is carried out on the reaction liquid obtained in the step (b) to obtain an organic phase containing diphenylmethane series diamine and polyamine and a water phase containing aniline salt;
(d) and (c) carrying out a small amount of alkali washing and distillation on the organic phase obtained in the step (c) to obtain diphenyl methane series diamine and polyamine (DAM), and distilling the water phase obtained in the step (c) to remove part of water to obtain the water phase serving as a raw material for the condensation reaction in the step (a).
The aqueous phase obtained in the step (c) contains an acidic catalyst, and can be recycled to provide an acidic environment for condensation reaction, so that the use amount of acid is greatly reduced.
According to the method provided by the invention, the reaction of the anilinium salt and formaldehyde in the step (a) under the catalysis of acid can be carried out by the existing method.
The acidic catalyst in step (a) is selected from sulfuric acid and/or hydrochloric acid, preferably a hydrochloric acid solution with a mass concentration of 10-25% and/or a sulfuric acid solution with a mass concentration of 10-25%, more preferably a hydrochloric acid solution with a mass concentration of 15-20%.
In a preferred embodiment of the present invention, aniline is salified with a hydrochloric acid solution in step (a) to form aniline hydrochloride.
Preferably, H in the acidic catalyst+The molar ratio to aniline is 0.1-1.0:1, more preferably 0.15-0.6:1, still more preferably 0.2-0.4: 1;
preferably, the molar ratio of formaldehyde to aniline in the formaldehyde solution is from 0.1 to 0.6:1, more preferably from 0.3 to 0.5: 1; the mass concentration of the formaldehyde solution is preferably 36.0-37.5%.
Preferably, the process of step (a) comprises: the salt-forming reaction of aniline and an acid catalyst is an instant reaction, and the reaction temperature is 40-50 ℃; the reaction time of the aniline acid salt and the formaldehyde is 3-5h, and the reaction temperature is 45-70 ℃. Preferably, the reaction solution containing diamine salts and polyamine salts of diphenylmethane series obtained in step (a) of the present invention is subjected to catalytic reaction while controlling the molar amount of aniline in the reaction solution to be higher than H+And thus aniline can be optionally supplemented to the reaction solution before or after the addition of the organic solvent.
Preferably, when H is present in the acidic catalyst in step (a)+When the molar ratio of aniline to aniline is higher than 0.2:1, aniline is added to the reaction solution before or after the addition of the organic solvent. The molar amount of aniline post-replenished should be greater than or equal to the H in the acid catalyst above this value+The molar amount is such that the molar amount of the total aniline in the reaction solution is higher than the molar amount of H + in the acid catalyst, but the ratio of the increase is preferably not more than 10%.
Preferably, the organic solvent in the step (b) can be any one of toluene or chlorobenzene, the volume ratio of the organic solvent to the reaction liquid obtained in the step (a) is 0.3-1:1, preferably 0.5-0.8:1, and the mixing temperature is 80-100 ℃.
Preferably, the packing volume of the catalyst: the volume of the reaction liquid of diamine salt and polyamine salt of diphenylmethane series is 1:2-10, and the reaction liquid containing diamine salt and polyamine salt of diphenylmethane series, aniline and solvent can be catalytically converted by a reactor loaded with a catalyst.
In a preferred embodiment of the invention, the reactor in which the catalytic conversion is carried out is selected from fixed bed reactors.
Preferably, the process conditions for the catalytic conversion include: the reaction pressure is 10 to 300KpaG, and more preferably 20 to 100 KpaG; the reaction temperature is 80-105 ℃, preferably 90-100 ℃, and the volume space velocity of the reactor feed (comprising the reaction liquid obtained in the step a, the added organic solvent and the selectively supplemented aniline) is 2.5-10h-1Further preferably 4 to 6 hours-1。
Preferably, in step (c), the reaction liquid obtained in step (b) is subjected to phase separation, the phase separation temperature is 80-100 ℃, and the retention time is 40-60 min.
Preferably, in the step (d), the organic phase containing diamine and polyamine (DAM) of diphenylmethane series is washed with a small amount of dilute alkali solution and separated into an organic phase and an aqueous phase again; feeding the water phase containing aniline, diamine and polyamine into a brine treatment process for treatment, and distilling the organic phase containing diamine and polyamine of diphenylmethane series to separate the organic solvent, aniline and water in the organic phase to obtain diamine and polyamine of diphenylmethane series; the gaseous phase of the distilled organic phase is cooled and recycled for use as organic solvent in step (b).
Preferably, the dilute alkali liquor washing process comprises the following steps: a1-3% sodium hydroxide solution is mixed thoroughly with an organic phase comprising diamines and polyamines of the diphenylmethane series in a mixer at 80-100 ℃. Traces of aniline acid salts, diamine hydrochloride salts and polyamine hydrochloride salts remaining in the organic phase containing diamines and polyamines of the diphenylmethane series are removed by alkali washing. Then the mixture is sent into an oil-water separator for phase separation. And (3) the water phase after washing and layering by the dilute alkali liquor contains a trace amount of aniline and MDA, enters a buffer tank, and is sent to a brine treatment process for treatment. The washed organic phase containing di-and polyamines of the diphenylmethane series can also be passed to a storage tank. Wherein the temperature of the organic phase is 80-100 ℃. Preferably, the volume ratio of the sodium hydroxide solution to the organic phase is 1-1.5: 10.
In the purification step, the organic solvent, aniline, and water are preferably separated by distillation from an organic phase containing diamines and polyamines of the diphenylmethane series. The specific operation process can be carried out by referring to the process described in patent document CN 105324361A. And (3) refining to obtain diamine and polyamine (DAM) of diphenylmethane series, wherein the mass content of the DAM can reach more than 99.9 wt%.
Preferably, in the step (d), a distillation method is adopted to remove part of water from the aqueous phase containing aniline acid salt generated in the step (c), the dehydrated aniline acid salt aqueous solution is cooled to 30-50 ℃ to be used as a raw material for the condensation reaction in the step (a), the dehydration amount is basically consistent with the total amount of water brought in by other materials (except an acid catalyst) in the condensation reaction process and generated in the reaction, and the water content in the condensation reaction process is stable and balanced. The gas phase produced by distillation is cooled and then combined with the aqueous phase produced by the alkaline washing of the organic phase, and then sent to the brine treatment process for treatment.
The technical scheme of the invention has the following beneficial effects:
(1) the nano catalyst has large specific surface area, multiple surface active points, good adsorption selectivity to amine salt structure, and high content of active components capable of effectively reducing H in macromolecular amine salt+The activation energy for converting to small molecule amine shows excellent catalytic effect.
(2) The method for preparing the diamine and polyamine of the diphenylmethane series saves the raw material cost, because the catalyst catalyzes the diamine salt and the polyamine salt of the diphenylmethane series to be converted into molecular state and further to be dissolved in an organic solvent for separation to replace the traditional caustic soda neutralization process, and a large amount of caustic soda consumption can be reduced each year;
(3) the method for preparing diamine and polyamine of diphenylmethane series avoids the generation of high-concentration saline water containing organic amine, thereby reducing the environmental protection pressure or recycling pressure of qualified discharge in treatment. The acidic catalyst is basically recycled after phase separation, and the wastewater generated by washing the dilute alkali liquor of the subsequent organic phase and the wastewater generated by distilling the aniline-containing acid salt have low salt content and small amount and can be sent to a reclaimed water recycling unit for further treatment and recycling after biochemical treatment, so that the environmental protection pressure is solved;
(4) the method for preparing diamine and polyamine of diphenylmethane series has high water content in order to ensure that the problem of solid aniline acid salt precipitation does not exist in the recycled aniline acid salt-containing catalyst, so that the water content in the condensation reaction process is increased, the quality of the condensation reaction is improved, the blockage is relieved, and the N-methyl content in DAM is reduced.
Drawings
FIG. 1 is a process flow diagram for the preparation of di-and polyamines of the diphenylmethane series using the process of the present invention.
The numbers in the figures illustrate the following:
1-aniline formaldehyde condensation reaction liquid, 2-fresh aniline, 3-organic solvent/recycled organic solvent, 4-static mixer, 5-amine salt catalytic conversion reactor, 6-oil-water separator, 7-aniline hydrochloride-containing aqueous phase storage tank, 8-dehydration process of aniline hydrochloride-containing aqueous phase, 9-DAM-containing organic phase storage tank, 10-dilute alkali solution, 11-static mixer, 12-washing stirring tank, 13-oil-water phase separator, 14-alkaline washing wastewater storage tank, 15-wastewater treatment process, 16-DAM-containing organic phase storage tank after washing, and 17-DAM-containing organic phase (crude DAM) refining process.
Detailed Description
The technical solution and the effects of the present invention are further described by the following specific examples. The following examples are merely illustrative of the present invention and are not intended to limit the scope of the present invention. Simple modifications of the invention applying the inventive concept are within the scope of the invention as claimed.
The technological process for preparing diamine and polyamine of diphenylmethane series by adopting the method of the invention is shown in figure 1: reacting acid catalyst with aniline according to a certain mole ratio to generate aniline acid salt, carrying out condensation reaction on the aniline acid salt and formaldehyde solution to generate reaction liquid 1 containing DAM acid salt, aniline acid salt, DAM and aniline, and adding H in the acid catalyst before the condensation reaction+The molar ratio of aniline to aniline, whether aniline is added or not and the amount of aniline added, aniline 2, and then the organic solventA solvent 3 is mixed by a static mixer 4, then is introduced into a fixed bed reactor 5 filled with an amine salt conversion catalyst, under the action of the catalyst, H & lt + & gt of salified amino on DAM in a reaction solution is transferred to amino of aniline existing in a molecular state in the reaction solution, and DAM in the reaction solution is converted into a molecular state and is dissolved in an added organic solvent; introducing the reaction liquid after catalytic conversion into an oil-water separator 6, introducing the phase-separated water phase into a water phase storage tank 7 containing aniline acid salt, and then sending the water phase into a dehydration process 8 to remove part of water to be used as a catalyst and part of raw materials in the aniline salt forming reaction step; the organic phase generated by the phase splitting of the oil-water separator 6 enters an organic phase storage tank 9 containing DAM, the organic phase is conveyed to a static mixer 11 by a pump to be mixed with dilute alkali liquor 10, the mixed solution is conveyed to a washing stirring tank 12, then overflows into an oil-water separator 13 to be divided into two phases, the water phase is conveyed to a wastewater treatment process after passing through an alkali washing wastewater storage tank 14 to be treated, and the washed organic phase is conveyed to a DAM refining process 17 after passing through a storage tank 16 to be treated to obtain a DAM product.
First, the main equipment model and raw material source used in the embodiment of the invention
The catalytic amine salt conversion reactor, the static mixer, the oil-water separator, the alkaline washing stirring tank, the material storage tank and the material conveying pump are all purchased from Nicotiana Kogyo chemical engineering equipment Co., Ltd;
muffle furnace, model VULCAN3-1750, available from Neytech, USA;
aniline, formaldehyde, hydrochloric acid, sodium hydroxide solution, from wanhua chemistry;
butyl titanate, urea, ethanol, acetic acid, praseodymium nitrate, copper chloride, chromium nitrate, stannic chloride, polyethylene glycol 2000 and ammonia water, which are analytically pure and purchased from national pharmaceutical group chemical reagent limited;
example 1: preparation of catalyst # 1
a) Preparation of nano TiO2Carrier: a1000 mL three-necked flask was charged with 24mL of butyl titanate, and a mixed solution of 150mL of ethanol and 150mL of pure water was added thereto, followed by addition of 30mL of acetic acid and stirring at 25 ℃ and 300r/min for 10 min. 180mL of ethanol solution dissolved with 20 wt% of urea is measured, slowly added into the flask at the speed of 3.6mL/min, and stirred for 300r/minHeating the solution in the flask to 160 ℃ at a heating rate of 10 ℃/min, maintaining the temperature at 160 ℃, cooling to 50 ℃ after the urea ethanol solution is added for 8min, separating out precipitates, and ultrasonically cleaning the precipitates for 5 times by using absolute ethyl alcohol, wherein the dosage of the ethyl alcohol is 20mL each time. Then placing the cleaned solid in an oven to dry for 40min at 160 ℃, and then calcining for 2h in a muffle furnace at 320 ℃ to obtain TiO with the average particle size of 15nm2And (3) a carrier.
b) Loading active components: 1.96g of praseodymium nitrate (0.006mol), 2.69g of copper chloride (0.02mol), 11.90g of chromium nitrate (0.05mol) and 11.72g of tin chloride (0.045mol) are weighed respectively, and the molar ratio is 1.2: 4.0: 10.0: 9.0, adding into a beaker, adding 80g of pure water, stirring and dissolving at 300r/min, and after completely dissolving, adding the TiO prepared by the step a)220g of carrier, adding 1.5g of polyethylene glycol 2000 as a dispersing agent at 25 ℃, uniformly dispersing by ultrasonic waves, stirring for 2 hours at constant temperature of 25 ℃ and stirring frequency of 300r/min, dripping ammonia water in the stirring process until the pH value is 8.0-9.0, standing for 1 hour, performing suction filtration by using a suction filtration machine to obtain a solid, adding 50g of distilled water, washing under the condition that the stirring frequency is 300r/min, drying for 30 hours at 80 ℃, and finally calcining for 4 hours at 520 ℃ in the air atmosphere to obtain the catalyst with the solid reticular structure. In the prepared catalyst, the mass fraction of each metal oxide in the carrier is measured by the conventional analysis method (ICP elemental analysis) in the field as follows: 1.8 wt% of praseodymium oxide, 11.3 wt% of cuprous oxide, chromium oxide: 14.9 wt% and 13.6 wt% tin oxide.
Example 2: preparation of catalyst # 2
a) Preparation of nano TiO2Carrier: a1000 mL three-necked flask was charged with 20mL of butyl titanate, and a mixed solution of 150mL of ethanol and 150mL of pure water was added thereto, followed by addition of 40mL of acetic acid and stirring at 25 ℃ and 300r/min for 10 min. Measuring 180mL of ethanol solution dissolved with 18 wt% of urea, slowly adding the ethanol solution into a flask at the speed of 3.6mL/min, keeping stirring for 300r/min, heating the solution in the flask to 160 ℃ at the heating rate of 10 ℃/min, maintaining the temperature at 160 ℃, cooling to 50 ℃ after the urea ethanol solution is added, separating out precipitates after 6min, and ultrasonically cleaning for 3 times by adopting absolute ethyl alcohol, wherein the dosage of the ethyl alcohol is 30mL each time. Then theDrying the cleaned solid in an oven at 160 ℃ for 50min, and calcining the dried solid in a muffle furnace at 320 ℃ for 2.5h to obtain TiO with the average particle size of 48nm2And (3) a carrier.
b) Loading active components: 2.45g of praseodymium nitrate (0.0075mol), 2.02g of copper chloride (0.015mol), 17.85g of chromium nitrate (0.075mol) and 7.81g of tin chloride (0.03mol) are respectively weighed, and the molar ratio is 1.5: 3.0: 15.0: 6.0, adding into a beaker, adding 80g of pure water, stirring and dissolving at 300r/min, and after completely dissolving, adding the TiO prepared by the step a)225g of carrier, adding 2.0g of polyethylene glycol 2000 as a dispersing agent at 25 ℃, uniformly dispersing by ultrasonic waves, stirring for 1.5h at constant temperature of 25 ℃ and stirring frequency of 300r/min, dripping ammonia water in the stirring process until the pH value is 8.0-9.0, standing for 1h, performing suction filtration by using a suction filtration machine to obtain a solid, adding 50g of distilled water, washing under the condition that the stirring frequency is 300r/min, drying for 25h at 85 ℃, and finally calcining for 3h at 520 ℃ in the air atmosphere to obtain the catalyst with the solid mesh structure. In the prepared catalyst, the mass fraction of each metal oxide in the carrier is measured by the conventional analysis method (ICP elemental analysis) in the field as follows: 4.6 wt% of praseodymium oxide, 9.4 wt% of cuprous oxide, chromium oxide: 18.7 wt% and 12.1 wt% tin oxide.
Example 3: preparation of No. 3 catalyst
a) Preparation of nano TiO2Carrier: a1000 mL three-necked flask was charged with 42mL of butyl titanate, and a mixed solution of 150mL of ethanol and 150mL of pure water was added thereto, followed by addition of 30mL of acetic acid and stirring at 25 ℃ and 300r/min for 10 min. Measuring 180mL of ethanol solution dissolved with 22 wt% of urea, slowly adding the ethanol solution into a flask at the speed of 3.6mL/min, keeping stirring for 300r/min, heating the solution in the flask to 160 ℃ at the heating rate of 10 ℃/min, maintaining the temperature at 160 ℃, cooling to 50 ℃ after the urea ethanol solution is added, separating out precipitates, and ultrasonically cleaning for 3 times by adopting absolute ethyl alcohol, wherein the dosage of ethyl alcohol is 40mL each time. Then placing the cleaned solid in an oven to dry for 40min at 160 ℃, and then calcining for 3h at 320 ℃ in a muffle furnace to obtain TiO with the average particle size of 29nm2And (3) a carrier.
b) Loading active components: weighing 2.94g respectivelyPraseodymium nitrate (0.009mol), 1.35g of copper chloride (0.01mol), 9.52g of chromium nitrate (0.04mol) and 15.62g of tin chloride (0.06mol) in a molar ratio of 1.8: 2.0: 8.0: 12.0, adding into a beaker, adding 80g of pure water, stirring and dissolving at 300r/min, and after completely dissolving, adding the TiO prepared by the step a)220g of carrier, adding 1.2g of polyethylene glycol 2000 as a dispersing agent at 25 ℃, uniformly dispersing by ultrasonic waves, stirring for 2.5h at constant temperature of 25 ℃ and stirring frequency of 300r/min, dripping ammonia water in the stirring process until the pH value is 8.0-9.0, standing for 1h, performing suction filtration by using a suction filtration machine to obtain a solid, adding 50g of distilled water, washing under the condition that the stirring frequency is 300r/min, drying for 20h at 85 ℃, and finally calcining for 5h in an air atmosphere at 500 ℃ to obtain the catalyst with the solid mesh structure. In the prepared catalyst, the mass fraction of each metal oxide in the carrier is measured by the conventional analysis method (ICP elemental analysis) in the field as follows: 3.9 wt% of praseodymium oxide, 7.9 wt% of cuprous oxide, chromium oxide: 14.2 wt% and 15.3 wt% tin oxide.
Example 4: preparation of DAM according to the method of the invention Using catalyst # 1
The technological process for preparing diamine and polyamine of diphenylmethane series is shown in figure 1, acid catalyst hydrochloric acid solution (mass concentration is 15%) 1177.4g/h and aniline (mass concentration is 99.9%) 1500.0g/h are mixed, the molar ratio of the two is 0.30:1, and aniline hydrochloride is generated by reaction at 40 ℃. A formaldehyde solution material (with the concentration of 37.0 wt%) 549.3g/h is mixed with an aniline hydrochloride solution for reaction, the molar ratio of formaldehyde to aniline in the formaldehyde solution is 0.42:1, and the mixture is reacted for 4 hours at 70 ℃ to generate a reaction solution 1 containing DAM acid salt, aniline acid salt, DAM and aniline. In the condensation reaction process, the molar ratio of hydrochloric acid to aniline is 0.30:1 and is higher than 0.20:1, aniline with the amount higher than the ratio is added for 150g/h, then solvent chlorobenzene with the volume ratio of 0.5:1 to reaction liquid 1 is added for 1500mL/h, the mixture is mixed by a static mixer 4 and then is introduced into a fixed bed reactor 5 filled with amine salt conversion catalyst, the filling amount of the catalyst is 1.2L, and the reaction liquid 1 mixed with aniline and solvent is catalytically converted in the reactor 5. The reaction pressure is 50KpaG, the reaction temperature is 90 ℃, and the volume space velocity of the reactor feeding is 4h-1. Introducing the reaction solution after catalytic conversionFeeding into an oil-water separator 6, wherein the phase separation temperature is 90 ℃, the retention time is 40min, the water phase enters a water phase storage tank 7 containing aniline acid salt, and then is fed into a dehydration procedure 8 to be dehydrated and used as a catalyst in the aniline salt forming reaction step; the organic phase generated by the phase separation of the oil-water separator 6 enters an organic phase storage tank 9 containing DAM, and then is conveyed to a static mixer 11 to be mixed with 1% sodium hydroxide solution 462.2g/h, the volume flow ratio of sodium hydroxide to the organic phase is 1.5:10, and the temperature after mixing is 90 ℃; and (3) sending the mixed solution into a washing stirring tank 12, then overflowing the mixed solution into an oil-water separator 13, staying for 30min at 90 ℃ for phase separation, sending the water phase to a wastewater treatment process after passing through an alkaline washing wastewater storage tank 14 for treatment, sending the washed organic phase to a DAM refining process 17 after passing through a storage tank 16 at 90 ℃, and obtaining a DAM product. The data of the conversion rate of DAM acid salt to molecular state, the consumption of sodium bicarbonate, the yield of wastewater, the quality of DAM and the like in this example are shown in Table 1.
Example 5: preparation of DAM according to the method of the invention Using catalyst # 1
The technological process for preparing diamine and polyamine of diphenylmethane series is shown in figure 1, acid catalyst hydrochloric acid solution (mass concentration is 20%) 735.9g/h and aniline (mass concentration is 99.9%) 1500g/h are mixed, the molar ratio of the two is 0.25:1, and aniline hydrochloride is generated by reaction at 50 ℃. 614.7g/h of formaldehyde solution material (with the concentration of 37.0 wt%) is mixed with aniline hydrochloride solution for reaction, the molar ratio of formaldehyde to aniline in the formaldehyde solution is 0.47:1, and the mixture is reacted for 5h at 70 ℃ to generate reaction liquid 1 containing DAM acid salt, aniline acid salt, DAM and aniline. In the condensation reaction process, hydrochloric acid and aniline are 0.25:1 and higher than 0.20:1, aniline with the amount higher than the specific value is added for 75g/h, then solvent chlorobenzene with the volume ratio of 1700mL/h is added according to the volume ratio of 0.6:1 to reaction liquid 1, the mixture is mixed by a static mixer 4 and then is introduced into a fixed bed reactor 5 filled with amine salt conversion catalyst, the loading amount of the catalyst is 0.9L, and the reaction liquid 1 mixed with aniline and solvent is catalytically converted in the reactor 5. The reaction pressure is 80KpaG, the reaction temperature is 90 ℃, and the volume space velocity of the reactor feeding is 5h-1. Introducing the reaction solution after catalytic conversion into an oil-water separator 6, separating the phase at 90 deg.C for 60min, introducing the water phase into a water phase storage tank 7 containing phenylamate, and delivering into a dewatering toolThe dehydrated product of the step 8 is used as a catalyst for the salt forming reaction step of the aniline; the organic phase generated by the phase separation of the oil-water separator 6 enters an organic phase storage tank 9 containing DAM, and then is conveyed to a static mixer 11 to be mixed with 329.1g/h of 2% sodium hydroxide solution, the volume flow ratio of sodium hydroxide to the organic phase is 1:10, and the temperature is 90 ℃ after the mixing; and (3) sending the mixed solution into a washing stirring tank 12, overflowing the mixed solution into an oil-water separator 13, staying for 40min at 90 ℃ for phase splitting, sending the water phase to a wastewater treatment process after passing through an alkaline washing wastewater storage tank 14 for treatment, sending the washed organic phase to a DAM refining process 17 after passing through a storage tank 16 at 90 ℃, and obtaining a DAM product. The data of the conversion rate of DAM acid salt to molecular state, the consumption of sodium bicarbonate, the yield of wastewater, the quality of DAM and the like in this example are shown in Table 1.
Example 6: preparation of DAM according to the method of the invention Using catalyst # 2
The process flow for preparing di-and polyamines of the diphenylmethane series is shown in FIG. 1, acid catalyst hydrochloric acid solution
The mass concentration is 18 percent) 1144.7g/h and aniline (the mass concentration is 99.9 percent) 1500g/h are mixed, the molar ratio of the two is 0.35:1, and aniline hydrochloride is generated by reaction at 40 ℃. 523.4g/h of formaldehyde solution material (with the concentration of 37.0 wt%) is mixed with aniline hydrochloride solution for reaction, the molar ratio of formaldehyde to aniline in the formaldehyde solution is 0.40:1, and the mixture is reacted for 4h at the temperature of 60 ℃ to generate reaction liquid 1 containing DAM acid salt, aniline acid salt, DAM and aniline. In the condensation reaction process, hydrochloric acid and aniline are 0.35:1 and higher than 0.20:1, aniline with the amount higher than the specific value is added for 225g/h, then solvent chlorobenzene with the amount higher than the specific value is added for 2500mL/h according to the volume ratio of the hydrochloric acid and the aniline to reaction liquid 1, the mixture is mixed by a static mixer 4 and then is introduced into a fixed bed reactor 5 filled with amine salt conversion catalyst, the filling amount of the catalyst is 0.8L, and the reaction liquid 1 mixed with aniline and solvent is catalytically converted in the reactor 5. The reaction pressure is 30KpaG, the reaction temperature is 90 ℃, and the volume space velocity of the reactor feeding is 7h-1. Introducing the reaction liquid after catalytic conversion into an oil-water separator 6, wherein the phase separation temperature is 90 ℃, the retention time is 50min, and the water phase enters a water phase storage tank 7 containing aniline acid salt and then is sent to a dehydration procedure 8 to be dehydrated and used as a catalyst for the aniline salt forming reaction step; the organic phase generated by the phase separation of the oil-water separator 6 enters the oil-water separatorAn organic phase storage tank 9 of DAM, then conveying to a static mixer 11 to be mixed with 530.1g/h of 1.5 wt% sodium hydroxide solution, wherein the volume flow ratio of sodium hydroxide to the organic phase is 1.3:10, and the temperature after mixing is 90 ℃; and (3) sending the mixed solution into a washing stirring tank 12, overflowing the mixed solution into an oil-water separator 13, staying at 90 ℃ for 35min for phase separation, sending the water phase to a wastewater treatment process after passing through an alkaline washing wastewater storage tank 14 for treatment, sending the washed organic phase to a DAM refining process 17 after passing through a storage tank 16 for treatment at 90 ℃, and obtaining a DAM product. The data of the conversion rate of DAM acid salt to molecular state, the consumption of sodium bicarbonate, the yield of wastewater, the quality of DAM and the like in this example are shown in Table 1.
Example 7: preparation of DAM according to the method of the invention Using catalyst # 3
The process flow for preparing di-and polyamines of the diphenylmethane series is shown in FIG. 1, acid catalyst hydrochloric acid solution
The mass concentration of 511.9g/h is 23 percent, aniline (the mass concentration is 99.9 percent) is mixed with 1500g/h, the molar ratio of the two is 0.20:1, and aniline hydrochloride is generated by reaction at 50 ℃. 497.0g/h of formaldehyde solution material (with the concentration of 37.0 wt%) is mixed with aniline hydrochloride solution for reaction, the molar ratio of formaldehyde to aniline in the formaldehyde solution is 0.38:1, and the reaction solution 1 containing DAM acid salt, aniline acid salt, DAM and aniline is generated after reaction for 3.5h at 60 ℃. In the condensation reaction process, the ratio of hydrochloric acid to aniline is 0.20:1, aniline does not need to be supplemented, then a solvent toluene is added according to the volume ratio of 0.4:1 to the reaction solution 1, the solvent toluene is 1000mL/h, the mixture is mixed by a static mixer 4 and then is introduced into a fixed bed reactor 5 filled with an amine salt conversion catalyst, the loading amount of the catalyst is 1.2L, and the reaction solution 1 mixed with aniline and solvent is subjected to catalytic conversion in the reactor 5. The reaction pressure is 100KpaG, the reaction temperature is 95 ℃, and the volume space velocity of the reactor feeding is 3h-1. Introducing the reaction liquid after catalytic conversion into an oil-water separator 6, wherein the phase separation temperature is 90 ℃, the retention time is 50min, and the water phase enters a water phase storage tank 7 containing aniline acid salt and then is sent to a dehydration procedure 8 to be dehydrated and used as a catalyst for the aniline salt forming reaction step; the organic phase generated by the phase separation of the oil-water separator 6 enters an organic phase storage tank 9 containing DAM, and then is conveyed to a static mixer 11 to be mixed with 257.4g/h of 2.5 wt% sodium hydroxide solution, wherein the volume of the sodium hydroxide and the organic phase isThe flow ratio is 1:10, and the temperature is 90 ℃ after mixing; and (3) sending the mixed solution into a washing stirring tank 12, overflowing the mixed solution into an oil-water separator 13, staying for 40min at 90 ℃ for phase splitting, sending the water phase to a wastewater treatment process after passing through an alkaline washing wastewater storage tank 14 for treatment, sending the washed organic phase to a DAM refining process 17 after passing through a storage tank 16 at 90 ℃, and obtaining a DAM product. The data of the conversion rate of DAM acid salt to molecular state, the consumption of sodium bicarbonate, the yield of wastewater, the quality of DAM and the like in this example are shown in Table 1.
Comparative example 1: DAM is prepared according to the conventional method of completely neutralizing an acid catalyst by adding alkali
519.5g/h of acid catalyst hydrochloric acid solution (with the mass concentration of 34%) and 1500.0g/h of aniline (with the mass concentration of 99.9%) are mixed, the molar ratio of the two is 0.30:1, and aniline hydrochloride is generated by reaction at 40 ℃. Mixing 549.3g/h of formaldehyde solution material (with the concentration of 37.0 wt%) with aniline hydrochloride solution for reaction, wherein the molar ratio of formaldehyde to aniline in the formaldehyde solution is 0.42:1, and reacting at 70 ℃ for 4h to generate reaction liquid containing DAM acid salt, aniline acid salt, DAM and aniline. Adding 418.06g/h (8% relative to the total mole of hydrochloric acid) of 50 wt% sodium hydroxide solution to completely neutralize the prepared reaction mixed solution, then entering an oil-water separator for phase separation, and sending the brine phase into a storage tank and a subsequent aqueous phase of a washing organic phase to a brine treatment process for treatment; and (4) sending the organic phase after phase separation to a DAM refining procedure for treatment to obtain a DAM product. The data of the conversion rate of DAM acid salt to molecular state, the consumption of sodium bicarbonate, the generation of wastewater, the quality of DAM and the like in the comparative example are shown in Table 1.
TABLE 1 reduced soda consumption, wastewater production, DAM quality data in each of the examples and comparative examples
Figure BDA0002624627440000171

Claims (9)

1. The catalyst for catalyzing the conversion of amine salt is characterized by comprising a carrier and an active component, wherein the carrier is TiO2The active components comprise praseodymium oxide, cuprous oxide, chromium trioxide and tin oxide;
preferably, the active ingredient content comprises, based on the weight of the carrier:
praseodymium oxide: 1.0 to 8.0 wt.%, preferably 2.0 to 4.5 wt.%;
cuprous oxide: 5.0 to 14.0 wt.%, preferably 9.0 to 12.0 wt.%;
chromium oxide: 13.0 to 20.0 wt.%, preferably 14.0 to 17.0 wt.%;
tin oxide: 10.0 to 16.0 wt.%, preferably 12.0 to 15.0 wt.%.
2. A method of preparing a catalytic amine salt conversion catalyst according to claim 1, comprising the steps of:
soluble salt solution containing active metal and carrier TiO2Contacting, dipping and adsorbing, adding a dispersing agent, uniformly dispersing, adjusting the pH value to 8.0-9.0, standing, performing suction filtration, washing, drying, and calcining to obtain a solid catalyst;
preferably, the dispersant is polyethylene glycol 2000; the mass of the added dispersant is 5-15% of the mass of the carrier in the catalyst, and is preferably 7-10%;
preferably, the drying temperature is 70-90 ℃; the drying time is 15-40h, more preferably 20-30 h;
preferably, the calcination process conditions are as follows: calcining at 480 ℃ and 600 ℃, preferably 500 ℃ and 550 ℃ in an air atmosphere for 3-7h, preferably 3.5-5.5 h.
3. The method of preparing a catalytic amine salt conversion catalyst according to claim 1 or 2, characterized in that: the support TiO2The preparation method comprises the following steps: taking titanate as a titanium source, adding a mixed solution of micromolecular alcohol and pure water as a solvent, adding micromolecular acid to inhibit hydrolysis, gradually and slowly adding a solution prepared from precipitator urea and micromolecular alcohol into the mixed solution, heating to the urea decomposition temperature of 155-170 ℃, keeping the temperature for 5-10min after the urea is added, separating out the precipitate, washing, drying and calcining to obtain TiO2A carrier;
preferably, the drying temperature is 155-170 ℃ and the drying time is 30-60 min;
preferably, the nano TiO is finally calcined for 1.5 to 3 hours at the temperature of 300-350 ℃ in the air atmosphere to obtain the nano TiO2And (3) a carrier.
4. Preparation method of the catalytic amine salt conversion catalyst according to any one of claims 1 to 3, preparation of nano TiO2Carrier, titanate: small molecule alcohol: pure water: the addition volume ratio of the micromolecular acid is 5-15:40-55:40-60: 8-12; preparing 16-23 wt% of solution of precipitator urea by using micromolecule alcohol as a solvent, finishing the addition of the micromolecule alcohol solution of the precipitator urea and the micromolecule alcohol solution of the precipitator urea with the volume ratio of 0.3-0.8:1 of the mixed solution for 30-60min, preferably 45-55min, heating the system to 155-170 ℃ 15-20min after the addition is started, and maintaining the temperature of the system at 155-170 ℃ until 5-10min after the addition of the precipitator is finished.
5. A process for the preparation of di-and polyamines of the diphenylmethane series comprising the steps of:
(a) in the presence of an acid catalyst, aniline is subjected to a salt forming reaction to generate aniline acid salt; then mixing aniline acid salt and formaldehyde solution for condensation reaction to obtain reaction liquid containing diamine salt and polyamine salt of diphenylmethane series;
(b) mixing an organic solvent with the reaction solution obtained in the step (a), introducing the mixture into a reactor containing the catalyst of claim 1 or the catalyst prepared by the method of any one of claims 2 to 4, and reacting the diamine salt of diphenylmethane series with the H in the amino group of the polyamine salt+Transferring the reaction solution obtained in the step (a) to an amino group of aniline existing in a molecular form, so that diphenylmethane series diamine salt and polyamine salt in the reaction solution are converted into diphenylmethane series diamine and polyamine and aniline acid salt;
(c) phase separation is carried out on the reaction liquid obtained in the step (b) to obtain an organic phase containing diphenylmethane series diamine and polyamine and a water phase containing aniline salt;
(d) and (c) carrying out alkali washing and distillation on the organic phase obtained in the step (c) to obtain diphenylmethane series diamine and polyamine (DAM), removing part of water from the aqueous phase obtained in the step (c) by distillation, and returning the aqueous phase to the step (a) to be used as a raw material for condensation reaction.
6. The process according to claim 5, wherein the acidic catalyst in step (a) is selected from sulfuric acid and/or hydrochloric acid, preferably a 10-25% by mass hydrochloric acid solution and/or a 10-25% by mass sulfuric acid solution, more preferably a 15-20% by mass hydrochloric acid solution;
preferably, H in the acidic catalyst+The molar ratio to aniline is 0.1-1.0:1, more preferably 0.15-0.6:1, still more preferably 0.2-0.4: 1;
preferably, the molar ratio of formaldehyde to aniline in the formaldehyde solution is from 0.1 to 0.6:1, more preferably from 0.3 to 0.5: 1; the mass concentration of the formaldehyde solution is preferably 36.0-37.5%;
preferably, in the step (a), the reaction temperature of the salt formation reaction of aniline and the acidic catalyst is 40-50 ℃; the reaction time of the aniline acid salt and the formaldehyde is 3-5h, and the reaction temperature is 45-70 ℃.
7. The method according to claim 5 or 6,
the reaction solution containing diamine salt and polyamine salt of diphenylmethane series obtained in the step (a) needs to be controlled to have aniline molar quantity higher than H before catalytic reaction+So that aniline can be selectively added to the reaction solution before or after the addition of the organic solvent;
preferably, when H is present in the acidic catalyst in step (a)+When the molar ratio of the aniline to the aniline is higher than 0.2:1, aniline is supplemented into the reaction solution before or after the organic solvent is added; the molar amount of aniline post-replenished should be greater than or equal to the H in the acid catalyst above this value+The molar amount is such that the molar amount of the total aniline in the reaction solution is higher than the molar amount of H + in the acid catalyst, but the ratio of the increase is preferably not more than 10%.
8. The method according to any one of claims 5 to 7,
the organic solvent in the step (b) is any one of toluene or chlorobenzene, the volume ratio of the organic solvent to the reaction liquid obtained in the step (a) is 0.3-1:1, preferably 0.5-0.8:1, and the mixing temperature is 80-100 ℃;
loading volume of the catalyst: the volume of the reaction liquid of diamine salt and polyamine salt of diphenylmethane series is 1: 2-10;
preferably, the reactor in which the catalytic conversion is carried out is selected from fixed bed reactors;
preferably, the process conditions for catalytic conversion include: the reaction pressure is 10 to 300KpaG, and more preferably 20 to 100 KpaG; the reaction temperature is 80-105 ℃, the preferential temperature is 90-100 ℃, and the volume space velocity is 3-10h-1Further preferably 4 to 6 hours-1；
Preferably, in step (c), the reaction liquid obtained in step (b) is subjected to phase separation, the phase separation temperature is 80-100 ℃, and the retention time is 40-60 min.
9. The process according to any one of claims 5 to 8, wherein in step (d), the organic phase containing diamines and polyamines of the diphenylmethane series (DAM) is washed with a small amount of dilute alkali solution and separated again into an organic phase and an aqueous phase; feeding the water phase containing aniline, diamine and polyamine into a brine treatment process for treatment, and distilling the organic phase containing diamine and polyamine of diphenylmethane series to separate the organic solvent, aniline and water in the organic phase to obtain diamine and polyamine of diphenylmethane series; the gaseous phase of the distilled organic phase is recycled after cooling as organic solvent in step (b);
preferably, the dilute alkali washing process comprises: a1-3% sodium hydroxide solution is thoroughly mixed with an organic phase containing diamines and polyamines of the diphenylmethane series at 80-100 ℃ in a mixer, and trace amounts of aniline salts, diamine hydrochlorides and polyamine hydrochlorides remaining in the organic phase containing diamines and polyamines of the diphenylmethane series are removed by alkali washing. Then sending the mixture into an oil-water separator for phase splitting;
preferably, the volume ratio of the sodium hydroxide solution to the organic phase is 1-1.5: 10; preferably, in the step (d), a distillation method is adopted to remove part of water in the water phase containing the aniline acid salt generated in the step (c), the dehydrated aniline acid salt water solution is cooled to 30-50 ℃ to be used as a raw material for the condensation reaction in the step (a), the dehydration amount is basically consistent with the total amount of water brought in by other materials (except an acid catalyst) in the condensation reaction process and generated by the reaction, and the water content in the condensation reaction process is stable and balanced; the gas phase produced by distillation is cooled and then combined with the aqueous phase produced by the alkaline washing of the organic phase, and then sent to the brine treatment process for treatment.
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