CN107866264A - A kind of synthesis DEMMA catalyst and preparation method thereof, application - Google Patents
A kind of synthesis DEMMA catalyst and preparation method thereof, application Download PDFInfo
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- CN107866264A CN107866264A CN201711168342.4A CN201711168342A CN107866264A CN 107866264 A CN107866264 A CN 107866264A CN 201711168342 A CN201711168342 A CN 201711168342A CN 107866264 A CN107866264 A CN 107866264A
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/12—Noble metals
- B01J29/126—Y-type faujasite
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
The invention discloses a kind of supported modified zeolite molecular sieve catalyst, including modified zeolite molecular sieve carrier and the active component of load, wherein, the modified zeolite molecular sieve carrier is modified via zeolite molecular sieve and prepared, including：By the alkaline solution mixed processing of molecular sieve and alkali metal, washing, dry, roasting obtain preliminary modified support；The preliminary modified support is impregnated using the soluble compound solution containing lanthanide series and boron, is dried, roasting obtains the modified zeolite molecular sieve carrier containing lanthanide oxide and diboron trioxide.Application invention additionally discloses the preparation method of above-mentioned catalyst and in DEMMA is synthesized.Using the catalyst of the present invention, feed stock conversion is high, and the selectivity of product is good, and accessory substance is few, meanwhile, catalyst preparation process is simple, good economy performance, has preferable application prospect.
Description
Technical field
The present invention relates to a kind of preparation method of green alkyl substituent aromatic diamines, a kind of conjunction is more particularly to
Into aromatic liquid diamines 3, the catalyst of 3'- diethyl -4,4'- MDA (DEMMA) and preparation method thereof, and
Application in DEMMA is prepared.
Background technology
3,3'- diethyl -4,4'- MDAs, also known as 4,4'- di-2-ethylhexylphosphine oxides (2- MEAs), referred to as
DEMMA, it is a kind of faint yellow to brown transparent oily liquid under normal temperature.Structural formula is following (formula 1)：
(formula 1)
3,3'- diethyl -4,4'- MDAs mainly have following several purposes：
(1) it is used for aerospace composite raw material and the coating material of such as rocket envelope, the anti-of product can be greatly improved
Swollen intensity, tearing strength and carrying crushing resistance and resistance to elevated temperatures.
(2) it is used for the corrosion-inhibiting coating of the band large-scale metals such as drilling platforms, marine ship, bullet train, bridge structure facility, reason
Change excellent performance.
(3) it is used as the Amino End Group chain extender of polyureas spraying elastomer (Spray Polyurea Elastomer), with substitution
Ethocure-l00\Jeffamine D2000。
At present, the main synthesis technique of 3,3'- diethyl -4,4'- MDA is in strong acid especially hydrochloric acid
In the presence of, carried out by the condensation of alkyl substituted benzene amine and formaldehyde.
Specific reaction equation is as follows：
In addition, also there is document (thermosetting resin 1995,10 (2):17-21) report passes through the mixed of aniline and o ethyl aniline
Compound adds formaldehyde condensation and obtained under normal temperature as the 3,3'- diethyl -4,4'- MDAs (DEMMA) of liquid, 3- second
The ternary blends of base -4,4'- MDAs (MEDDM) and 4,4'- MDAs (DDM).
JP47031961-A discloses prepares 3,3'- diethyl -4,4'- diaminourea by o ethyl aniline and formaldehyde condensation
The method of diphenyl-methane.
CN 1288128C disclose a kind of system of aromatic liquid diamines 3,3'- diethyl -4,4'- MDAs
Preparation Method.The preparation technology needs to pass through into the step ability such as salt, condensation, neutralization, desolventizing, washing, dehydration and de- unhindered amina
Product is obtained, exists in reaction process complexity and last handling process and produces a large amount of wastewater problems.
CN102584598B disclose it is a kind of using hydrochloric acid or sulfuric acid activated treated kaolin is catalyst, with benzene, first
Benzene or dimethylbenzene are solvent, and o ethyl aniline prepares the side of 3,3'- diethyl -4,4'- MDAs with formaldehyde condensation
Method.Although the patent, without using strong acid and strong base, will produce in synthesis process in kaolin catalyst processing procedure
, the problem of being difficult to handle and polluting environment be present in raw a large amount of spent acid and acid-bearing wastewater.Meanwhile after reaction terminates, it is also necessary to essence
The cut o ethyl aniline complete from higher boiling toluene solvant, unreacted and product 3,3'- diethyl -4,4'- diaminourea hexichol
Methane.
In general, there is following defect in prior art：
(1) above-mentioned several research only both at home and abroad, is laboratory synthesis, no determination and ripe technique, product
All it is its mixture with isomers, major product 3,3'- diethyl -4,4'- MDA contents are not high, and product glues
Degree, free amine content and toxicity are higher, can not form industrialized production.
(2) during the course of the reaction, the presence of strong acid can bring serious etching problem, in addition, the addition of strong acid causes
It must be neutralized at the end of reaction with aqueous slkali, the disposal of resulting neutral salt solution is also a serious problems.
(3) due to making catalyst using strong acid, excessively condensation is difficult to avoid, without substituent arylamine or with substituent
While arylamine reaction generates product, it may occur that further condensation reaction generation is not intended to the obtained more amine resinses shapes of three rings
The more amine resinses shape materials of material and Fourth Ring, influence the purity of product.
(4) separated and purified, it is necessary to be evaporated under reduced pressure under high temperature high vacuum to obtain the higher product of purity, deposited
In technique and equipment challenge.
In addition, in the presence of a zeolite catalyst, cycloalkylation aromatics is produced using the catalytic reaction of aromatic amine and alkene
Amines is known in the art.Aromatic amine is selected using acidic crystallization molecular sieve as United States Patent (USP) US4740620 discloses
Product of the selecting property cycloalkylation into ortho-alkylating.The invention is disadvantageous in that severe reaction conditions, particularly with ethene
Alkylated reaction need higher temperature and pressure (temperature is up to 375 DEG C, and pressure is up to 3000psig).Meanwhile raw material turns
Rate is low, and alkylate is mainly mono-substituted ortho position cycloalkylation product, and it is secondary that a large amount of N- alkylations are produced in course of reaction
Product.
Therefore, the alkylation that 4,4'- MDAs and ethene are carried out using acidic zeolite catalyst is anti-
Problems with should be primarily present：
(1) severe reaction conditions, more than 300 DEG C of reaction temperature, reaction pressure is up to 3000psig.
(2) poor catalyst activity, causes raw material 4, and the conversion per pass of 4'- MDAs is low.
(3) catalyst choice is poor, causes target product 3, the selectivity of 3'- diethyl -4,4'- MDAs
It is low, exist substantial amounts of 4,4'- MDAs disproportionation accessory substance, single ethyl substitution product, N- alkylate by-products and
More ethyls substitute accessory substance, and the height of target product selectivity is directly connected to the economy of the technique.
(4) wherein, the boiling point of N- alkylate by-products and target product is sufficiently close to, and the separation means using routine are difficult to
It is isolated, so as to increase separating difficulty, equipment investment and energy consumption.
The content of the invention
It is used to synthesize 3,3'- diethyl -4,4'- MDAs it is an object of the present invention to provide a kind of
Supported modified zeolite molecular sieve catalyst, by being modified processing to zeolite molecular sieve, urged with improving in DEMMA is synthesized
Change activity and reaction selectivity.
It is a further object of the invention to provide a kind of method for preparing supported modified zeolite molecular sieve catalyst.
It is a further object of the invention to provide application of the above-mentioned catalyst in DEMMA is synthesized.
One side for achieving the above object, the present invention use following technical scheme：
A kind of supported modified zeolite molecular sieve catalyst, including modified zeolite molecular sieve carrier and the activearm of load
Point, wherein, the modified zeolite molecular sieve carrier is modified via zeolite molecular sieve and prepared, and comprises the following steps：
(1) by the alkaline solution mixed processing of the zeolite molecular sieve and alkali metal, by the wet molecular sieve after processing
Washed, dried, be calcined and obtain preliminary modified support；
(2) the preliminary modified support is impregnated using containing the soluble compound solution of lanthanide series and boron, to dipping
Preliminary modified support after processing is dried, is calcined, and obtains containing changing described in lanthanide oxide and diboron trioxide
Property zeolite molecular sieve carrier.
Catalyst according to the invention, it is preferable that the zeolite molecular sieve is H type zeolite molecular sieves, is preferably selected from ZSM-
5th, the one or more in Beta, MCM-22, MCM-49, modenite and Y-type zeolite molecular sieve, more preferably mercerising are boiled
Stone and/or Y type molecular sieve, such as Y-type zeolite molecular sieve.Certainly, it will be appreciated by those skilled in the art that the zeolite molecular sieve carrier
It can also be Na type zeolite molecular sieves, now, carry out the before processing of step (1), H type molecules can be translated into first
Sieve, specific method for transformation are well known in the art, for example roasting obtains H type molecular sieves after ammonium salt solution is handled.
In the present invention, it is contemplated that reacting middle catalyst duct that may be present blocks deactivation prob, and the carrier is put down
Equal aperture can be 10-50A, such as 15,20 or 30A, having mesoporous pore size, can effectively avoiding because blocking duct asking for inactivating
Topic.In one embodiment, the Si of the carrier:Al atomic ratios can be 20-60, such as 30,40 or 50, total specific surface area
Can be 200-600m2/ g, such as 300,400 or 500m2/g。
In the present invention, the alkaline solution of the alkali metal described in step (1) can be NaOH, Na2CO3、NaHCO3、
KOH and K2CO3Middle one or more alkaline solution, it is preferable that in step (1), the molar concentration 0.01- of the alkaline solution
1mol/L, preferably 0.05-0.5mol/L；Mixed processing condition is：Reaction temperature is 20-100 DEG C, preferably 50-70 DEG C；Liquid is consolidated
Than for 30-70ml/g, preferably 40-60ml/g；Reaction time is 1-8h, preferably 3-5h.It is further preferred that the alkalescence
Solution can be NaHCO3Solution.
In step (1), wet molecular sieve washing, dry, roasting after alkaline solution is handled obtain preliminary modified support；On
The process of stating is well known in the art, such as in the present invention, alkali metal ion concentration is washed with deionized into filtrate and is not higher than
1wt%, and when drying, can dry to the weight content of the water of the physical absorption of product be no more than 5%, such as 1%, 2% or
3%.
In the present invention, step (2) is further to utilize the soluble compound solution containing lanthanide series and boron to carrying
Body is modified processing；Wherein, it will be appreciated by those skilled in the art that the modification can be completed in one or multi-step, such as lanthanum
Series elements and boron can repeat no more here simultaneously or distribution is to support modification.
In the present invention, the soluble metal salt includes but is not limited to the halide, nitrate and organic acid of metal
One or more in salt etc., it is known in the art, repeats no more here.
Catalyst according to the invention, it is preferable that in the catalyst, the weight/mass percentage composition of lanthanide oxide is
0.05%-3.5%, preferably 0.1%-3%, further preferred 0.5%-2.5%, such as 1%, 1.5% or 2%；B2O3Quality
Percentage composition is 0.01%-2.5%, preferably 0.1%-2%, further preferred 0.5%-1.5%, for example, 0.8%, 1% or
1.2%；In a preferred embodiment, the lanthanide series is cerium.Cerium source in the dipping solution is cerous nitrate and second
Sour cerium, preferably cerous nitrate；Boron source is boric acid, ammonium pentaborate and tetraboric acid ammonium, preferred boric acid.
In the above-mentioned methods, it is well known in the art using the method for metal salt solution described in carrier adsorption, art technology
Personnel understand, can adjust solution concentration, dip time etc. to adjust the adsorbance of metal salt in carrier, and then control catalyst
The content of middle active component or auxiliary agent, adsorption process can also be the multiple progress once or repeated.In a kind of embodiment
In, the volume ratio of metal salt solution and carrier can also be controlled in proper range, for example carry out incipient impregnation so that gold
Category salting liquid can be fully absorbed substantially by carrier or carrier and the solidliquid mixture of solution to obtaining are evaporated drying,
So as to remove excess of solvent.
Catalyst according to the invention, it is preferable that in the catalyst, the weight/mass percentage composition of active component is 0.01-
2%, preferably 0.05-1%, such as 0.1%, 0.2% or 0.5%；In the present invention, the active component can be catalyzed and synthesized
The active component commonly used in DEMMA molecular sieve catalyst, it is preferable that the active component is in Pt, Pd, Ru, Rh and Ir
One or more, the preferably one or more in Pt, Pd and Ru, more preferably Pt.
Other side for achieving the above object, the preparation method of above-mentioned catalyst provided by the invention include：
The soluble salt solutions corresponding with the active component are prepared, and using the soluble salt solutions to the modified zeolite molecule
Sieve carrier and carry out impregnation, obtained wet modified zeolite molecular sieve carrier is dried, be calcined, reduced, it is described to obtain
Catalyst.
The conventional processing step being roasted in the catalyst preparation of this area, to be known in the art, in the present invention, each step
When being related to roasting in rapid, roasting condition can be at 400-650 DEG C, for example be calcined 4-24h at 450,500,550 or 600 DEG C, than
Such as 6-12h, 8h or 10h.
Active component is oxidation state in catalyst after roasting, to make it have activity, it will be appreciated by those skilled in the art that also
Need to carry out reduction activation processing to the catalyst, such as reduction activation is carried out under pure hydrogen atmosphere, reducing condition can be
Pure hydrogen atmosphere reduces 5-10h, such as 6,7h or 8h at 200-500 DEG C, such as 250,300,350,400 or 450 DEG C.
Another aspect for achieving the above object, the invention provides above-mentioned catalyst in synthesis 3,3'- diethyls
Application in base -4,4'- MDAs.
Application according to the present invention, it is preferable that under catalyst action, utilize ethene and 4,4'- MDAs
The mol ratio of reaction synthesis 3,3'- diethyl -4,4'- MDAs, the ethene and 4,4'- MDA
For (5-35)：1, preferably (10-20):1, such as 15:1.
Involved chemical reaction process is as follows.
Main reaction：
Overalkylated side reaction：
4,4'- MDAs are disproportionated side reaction：
The alkylation side reaction of disproportionation products：
N- is alkylated side reaction：
Wherein, it is anti-to belong to the electrophilic alkylation that acid site is catalyzed for 4,4'- MDAs and ethylene alkylation
Should, its target product is 3,3'- diethyl -4,4'- MDAs, and accessory substance is N- ethyl -4,4'- diaminourea hexichol
Methane, N, N- diethyl -4,4'- MDAs, triethyl group -4,4'- MDAs and the substitution of more ethyls -
4,4'- MDAs etc..Research thinks that being formed as 3- ethyls -4,4'- MDA (MEDDM) is primary
Alkylated reaction, 3,3'- diethyl -4,4'- MDAs (DEMMD) are formed as secondary alkylated reaction, and 3,3'-
Triethyl group -4,4'- diaminourea two is then formd after diethyl -4,4'- MDAs (DEMMD) overalkylated reaction
The heavy constituent such as phenylmethane and more ethyl substitution -4,4'- MDAs.In addition, 4,4'- MDAs except
Outside generation alkylated reaction, disproportionated reaction generation p-phenylenediamine and aniline can also occur, and p-phenylenediamine and aniline continue to occur
Alkylated reaction generates more ethyl substitution accessory substances.Simultaneously as 4,4'- MDAs contain two amino, solid
N- alkylation side reactions easily occur on body acid catalyst.
Preferably, 100-300 DEG C of reaction temperature, preferably 150-250 DEG C, such as about 200 DEG C；Reaction pressure 10bar-
70bar, preferably 30bar-50bar, such as about 40bar.
During reaction, it will be appreciated by those skilled in the art that can be measured according to the activated centre of unit mass catalyst anti-to adjust
The relative usage of seasonable catalyst, it is preferable that catalyst space velocities are 0.5-15g/g (cat)/h, more preferably 5.0-10.0g/g
(cat)/h。
The beneficial effects of the present invention are：
The catalyst of the present invention be used for 4,4'- MDAs and ethylene alkylation prepare 3,3'- diethyl-
4,4'- MDAs, under more gentle reaction condition, while feed stock conversion reaches 100%, greatly suppression
Make disproportionation, N- alkylations and side reaction, the product selectivity such as overalkylated and reach more than 99.0%, product yield 99.0%
More than, the content of accessory substance is less than 1.0wt%；
The mild acidity of modified zeolite molecular sieve in the present invention, particularly suitable for 4,4'- MDAs and ethene
Alkylated reaction in because the alkylated reaction of 4,4'- MDAs and ethene is had been generally acknowledged that according to carbonium ion
Mechanism is carried out, and ethene activates to form carbonium ion by catalyst Bronst acid sites first, then with 4, the 4'- diaminourea of absorption
Diphenyl-methane reaction generation target product.And synthesis material properties affect of the selectivity by zeolite molecular sieve of target product is generated,
Want the target product of acquisition high selectivity, it is desirable to acid inside zeolite molecular sieve outer surface acid site intensity and distribution, duct
Center power and pore size and aperture size are coordinated, and prevent that the pairs such as disproportionation, N- alkylations and overalkylated reaction are anti-
Should.The present invention uses NaHCO first3Processing is modified to zeolite molecular sieve carrier, increases molecular sieve mesoporous area, mesoporous
Volume and aperture, make more acidic sites be distributed in bigger outer surface, thus make reactant be more easy to contact with acid centre,
Also the product of generation is soon diffused into from activated centre outside catalyst, and then prevent disproportionation and N- alkylation side reactions
Generation, improve catalyst activity and selectivity；
Zeolite molecular sieve passes through NaHCO3After solution modification, the activity and selectivity of catalyst is improved to some extent,
But the overalkylated side reaction of target product is promoted, this just needs to be adjusted the overall acidity of catalyst, this hair
It is bright that zeolite molecular sieve carrier is modified again using specific soluble cerium-containing compound and boron-containing compound, pass through suitable heat
Processing, Ce and the good coordinative roles of B, form the hydroxyl being more evenly distributed in carrier surface ad-hoc location, make carrier table
Face forms more acid suitable acid centres, and is engaged with original acidic site in carrier, makes the acid and sour of carrier
Property distribution it is more reasonable, reduce strong acid content, there is provided more B acid sites, while effectively increase the ratio of B acid/L acid,
And then catalyst activity and selectivity is finally greatly improved；
Zeolite molecular sieve passes through NaHCO3Solution and Ce, B are modified twice, and the activity and selectivity of catalyst has significantly
Degree improves, but it is difficult to ensure that the selectivity of feed stock conversion and target product is maintained at preferable level.The present invention is in zeolite
With the method introducing active component Pt, active component Pt of incipient impregnation and the B acid centres of carrier association in framework of molecular sieve
The activity and selectivity of catalyst is brought up into ultimate attainment level with effect；
Corrosion-free to equipment material using solid acid catalyst, reaction is easily isolated after terminating with reaction product, without entering
The cumbersome post processing (including the step such as alkali neutralization, filtering, extraction, rectifying) of row can obtain qualified products, almost without liquid and waste slag produced
Produce；
Using fixed-bed process, technological process is simple, easy to operation, belongs to environment-friendly green preparation process, can be with
The serialization large-scale production of 3,3'- diethyl -4,4'- MDAs is realized, while improves production efficiency, is reduced
Energy consumption, has saved production cost, is the developing direction of futurity industry metaplasia production；
This method is converted into liquid, low toxicity, user by solid-state, high poison, using limited 4,4'- MDAs
Just 3,3'- diethyl -4, the 4'- MDA high with added value, meanwhile, the catalyst prepared using this method is former
Expect high conversion rate, product selectivity is good, and product viscosity and free amine content are low, and production cost is low, is adapted to industrialization extensive raw
Production.
Embodiment
With reference to embodiment, the present invention is further described, but the invention is not restricted to listed embodiment,
The equivalent improvement and deformation of the technical scheme that the present patent application appended claims define should be also included in.
Gas chromatograph：Shimadzu GC-2014 (FID) detector, DB-5 capillary columns (φ 0.30mm × 30m), injection port
300 DEG C, 320 DEG C of detector；Heating schedule：230 DEG C are risen to by 80 DEG C with 10 DEG C/min, then 300 DEG C of guarantors are risen to 20 DEG C/min
12min is held, to determine product.
Alkylation reactor is fixed bed reactors in embodiment.
Y type molecular sieve, average pore size 20A, Si:Al atomic ratios are 30, and total specific surface area is 300m2/g；
ZSM-5, average pore size 10A, Si:Al atomic ratios are 50, and total specific surface area is 400m2/g；
Beta, average pore size 40A, Si:Al atomic ratios are 40, and total specific surface area is 500m2/g；
Mordenite molecular sieve, average pore size 30A, Si:Al atomic ratios are 20, and total specific surface area is 600m2/g。
4,4'- MDAs, purchased from Wanhua Chemical Group Co., Ltd.MDA-100
Product.
If not otherwise specified, chemicals used below is pure to analyze.
Embodiment 1-1
Catalyst A-1 preparation
(1)NaHCO3Solution modification
In confined conditions, the NaHCO for being 0.2mol/L with concentration by HY molecular sieves3Solution is with 40ml/g liquid/solid ratio
In 65 DEG C of stirring reactions, cooling stopping reaction after 3h, filtering are reacted, deionized water is washed to neutrality, obtains modified molecular screen load
Body M-1.
(2) Ce and B is modified
Using equi-volume impregnating, modified molecular screen carrier M-1 is immersed in containing 2.549g cerous nitrates and 1.432g boron
In the 100ml solution of acid, 12h balances to be adsorbed are impregnated, then, 120 DEG C of baking 2h in an oven is put, is finally transferred to Muffle furnace,
450 DEG C of roasting 6h.Obtain containing 0.1%CeO2And 0.8%B2O3Modified support N-1.
(3) equi-volume impregnating is used, modified molecular screen carrier N-1 is immersed in the 100ml containing 0.164g platinum nitrates
In solution, 12h balances to be adsorbed are impregnated, then, 120 DEG C of baking 3h in an oven is put, transfers to Muffle furnace, 400 DEG C are calcined 7h,
Finally reduce 6h under 300 DEG C of pure hydrogen atmospheres again.Obtain the zeolite molecular sieve catalyst of support type containing 0.1%Pt A-1.
Embodiment 1-2
Catalyst A-2 preparation
(1)NaHCO3Solution modification
In confined conditions, the NaHCO for being 0.1mol/L with concentration by mordenite molecular sieve3Solution is with 50ml/g's
Liquid/solid ratio cools after 50 DEG C of stirring reactions, reaction 5h stops reaction, filtering, and deionized water is washed to neutrality, obtains being modified and divides
Son sieve carrier M-2.
(2) Ce and B is modified
Using equi-volume impregnating, modified molecular screen carrier M-2 is immersed in containing 1.794g cerous nitrates and 0.822g boron
In the 100ml solution of acid, 10h balances to be adsorbed are impregnated, then, 110 DEG C of baking 4h in an oven is put, is finally transferred to Muffle furnace,
500 DEG C of roasting 8h.Obtain containing 2.5%CeO2And 1%B2O3Modified support N-2.
(3) equi-volume impregnating is used, modified molecular screen carrier N-2 is immersed in the 100ml containing 0.822g platinum nitrates
In solution, 16h balances to be adsorbed are impregnated, then, 120 DEG C of baking 5h in an oven is put, transfers to Muffle furnace, 550 DEG C are calcined 7h,
Finally reduce 6h at 450 DEG C again.Obtain the zeolite molecular sieve catalyst of support type containing 0.5%Pt A-2.
Embodiment 1-3
Catalyst A-3 preparation
(1) NaHCO3 solution modifications
In confined conditions, by Beta molecular sieves be 0.4mol/L with concentration NaHCO3 solution with 60ml/g liquid/solid
Than the cooling stopping reaction after 60 DEG C of stirring reactions, reaction 4h, filter, deionized water is washed to neutrality, obtains modified molecular screen
Carrier M-3.
(2) Ce and B is modified
Using equi-volume impregnating, modified molecular screen carrier M-3 is immersed in containing 2.575g cerous nitrates and 2.157g boron
In the 100ml solution of acid, 16h balances to be adsorbed are impregnated, then, 120 DEG C of baking 4h in an oven is put, is finally transferred to Muffle furnace,
350 DEG C of roasting 8h.Obtain containing 2%CeO2 and 1.2%B2O3Modified support N-3.
(3) equi-volume impregnating is used, modified molecular screen carrier N-3 is immersed in the 100ml containing 0.328g platinum nitrates
In solution, 10h balances to be adsorbed are impregnated, then, 120 DEG C of baking 5h in an oven is put, transfers to Muffle furnace, 650 DEG C are calcined 6h,
Finally reduce 10h at 350 DEG C again.Obtain the zeolite molecular sieve catalyst of support type containing 0.2%Pt A-3.
Embodiment 1-4
Catalyst A-4 preparation
(1)NaHCO3Solution modification
In confined conditions, the NaHCO for being 0.3mol/L with concentration by ZSM-5 molecular sieve3Solution is with 70ml/g liquid/solid
Than the cooling stopping reaction after 70 DEG C of stirring reactions, reaction 4.5h, filter, deionized water is washed to neutrality, obtains modified molecules
Sieve carrier M-4.
(2) Ce and B is modified
Using equi-volume impregnating, modified molecular screen carrier M-4 is immersed in containing 2.562g cerous nitrates and 0.893g boron
In the 100ml solution of acid, 24h balances to be adsorbed are impregnated, then, 150 DEG C of baking 2h in an oven is put, is finally transferred to Muffle furnace,
600 DEG C of roasting 4h.Obtain containing 1.5%CeO2And 0.5%B2O3Modified support N-4.
(3) equi-volume impregnating is used, modified molecular screen carrier N-4 is immersed in the 100ml containing 1.652g platinum nitrates
In solution, 14h balances to be adsorbed are impregnated, then, 120 DEG C of baking 8h in an oven is put, transfers to Muffle furnace, 600 DEG C are calcined 6h,
Finally reduce 7h at 500 DEG C again.Obtain the zeolite molecular sieve catalyst of support type containing 1%Pt A-4.
Embodiment 2-1
The loaded catalyst A-1 for dissipating that heap volume is 50ml is loaded in fixed bed reactors, when reaction temperature reaches 200
DEG C, system pressure (absolute pressure, similarly hereinafter) starts to feed when rising to 50bar, and air speed is 10.0g/g (cat)/h, ethene/4,4'- diamino
Base diphenyl-methane mol ratio is 20：1, through gas chromatographic analysis, 4,4'- MDAs do not detect, and 3,3'- diethyl-
4,4'- MDA contents are 99.5%, and other accessory substances do not detect, feed stock conversion 100%, and product yield is
99.5%.
Embodiment 2-2
The loaded catalyst A-2 for dissipating that heap volume is 50ml is loaded in fixed bed reactors, when reaction temperature reaches 150
DEG C, system pressure (absolute pressure, similarly hereinafter) starts to feed when rising to 30bar, and air speed is 6.0g/g (cat)/h, ethene/4,4'- diamino
Base diphenyl-methane mol ratio is 10：1, through gas chromatographic analysis, 4,4'- MDAs do not detect, and 3,3'- diethyl-
4,4'- MDA contents are 99.0%, and other accessory substances do not detect, feed stock conversion 100%, and product yield is
99.0%.
Embodiment 2-3
The loaded catalyst A-3 for dissipating that heap volume is 50ml is loaded in fixed bed reactors, when reaction temperature reaches 250
DEG C, system pressure (absolute pressure, similarly hereinafter) starts to feed when rising to 40bar, and air speed is 8.0g/g (cat)/h, ethene/4,4'- diamino
Base diphenyl-methane mol ratio is 15：1, through gas chromatographic analysis, 4,4'- MDAs do not detect, and 3,3'- diethyl-
4,4'- MDA contents are 99.2%, and other accessory substances do not detect, feed stock conversion 100%, and product yield is
99.2%.
Embodiment 2-4
The loaded catalyst A-1 for dissipating that heap volume is 50ml is loaded in fixed bed reactors, when reaction temperature reaches 300
DEG C, system pressure (absolute pressure, similarly hereinafter) starts to feed when rising to 60bar, and air speed is 7.0g/g (cat)/h, ethene/4,4'- diamino
Base diphenyl-methane mol ratio is 30：1, through gas chromatographic analysis, 4,4'- MDAs do not detect, and 3,3'- diethyl-
4,4'- MDA contents are 99.3%, and other accessory substances do not detect, feed stock conversion 100%, and product yield is
99.3%.
Comparative example 1
Difference with embodiment 1-1 is that the molecular sieve obtains catalyst D-1 without modification.
Then catalyst D-1 catalytic performance is being tested under the same conditions with embodiment 2-1.Through gas-chromatography
Analysis, 4,4'- MDAs do not detect, 3- ethyl -4,4'- MDAs content be 25.5%, N- ethyls -
4,4'- MDA contents are 14.5%, N, and N- diethyl -4,4'- MDAs content is 1.5%, three
Ethyl -4,4'- MDA content is 3%, and more ethyl substitution -4,4'- MDAs contents are 1%, 3,
3'- diethyl -4,4'- MDAs content is 54.5%, feed stock conversion 100%, product yield 54.5%.
Comparative example 2
Difference with embodiment 1-2 is that the molecular sieve obtains catalyst D-2 without modification.
Then catalyst D-2 catalytic performance is being tested under the same conditions with embodiment 2-2.Through gas-chromatography
Analysis, 4,4'- MDAs do not detect, and 3- ethyl -4,4'- MDAs content is 20%, N- ethyl -4,
4'- MDAs content is 15%, N, and N- diethyl -4,4'- MDAs content is 12%, triethyl group -
4,4'- MDA contents are 10%, and more ethyl substitution -4,4'- MDAs contents are 3%, 3,3'- bis-
Ethyl -4,4'- MDA content is 40%, feed stock conversion 100%, product yield 40%.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not pair
The restriction of embodiments of the present invention.For those of ordinary skill in the field, may be used also on the basis of the above description
To make other changes in different forms.Here all embodiments can not be exhaustive.It is every to belong to this hair
The obvious changes or variations that bright technical scheme is extended out is within the scope that the present invention covers.
Claims (10)
1. a kind of supported modified zeolite molecular sieve catalyst, including modified zeolite molecular sieve carrier and the active component of load,
Prepare, comprise the following steps characterized in that, the modified zeolite molecular sieve carrier is modified via zeolite molecular sieve：
(1) by the alkaline solution mixed processing of the zeolite molecular sieve and alkali metal, the wet molecular sieve after processing is carried out
Washing, dry, roasting obtain preliminary modified support；
(2) the preliminary modified support is impregnated using containing the soluble compound solution of lanthanide series and boron, to impregnation
Preliminary modified support afterwards is dried, is calcined, and obtains the modified boiling containing lanthanide oxide and diboron trioxide
Stone molecular sieve carrier.
2. catalyst according to claim 1, it is characterised in that the zeolite molecular sieve is H type zeolite molecular sieves, is preferably selected
One or more from ZSM-5, Beta, MCM-22, MCM-49, modenite and Y-type zeolite molecular sieve, more preferably
Modenite and/or Y type molecular sieve, more preferably Y-type zeolite molecular sieve.
3. catalyst according to claim 1 or claim 2, it is characterised in that in the catalyst, the quality of lanthanide oxide
Percentage composition is 0.05%-3.5%, preferably 0.1%-3%, further preferred 0.5%-2.5%；B2O3Weight/mass percentage composition
For 0.01%-2.5%, preferably 0.1%-2%, further preferred 0.5%-1.5%；
Preferably, the lanthanide series is cerium.
4. according to catalyst any one of claim 1-3, it is characterised in that in the catalyst, the matter of active component
Amount percentage composition is 0.01-2wt%, preferably 0.05-1wt%.
5. according to catalyst any one of claim 1-4, it is characterised in that the active component be selected from Pt, Pd, Ru,
One or more in one or more in Rh and Ir, preferably Pt, Pd and Ru, more preferably Pt.
6. according to catalyst any one of claim 1-5, it is characterised in that in step (1), the alkaline solution rubs
You are concentration 0.01-1mol/L, preferably 0.05-0.5mol/L；Preferably, the alkaline solution is NaHCO3Solution；
Mixed processing condition is：Reaction temperature is 20-100 DEG C, preferably 50-70 DEG C；Liquid-solid ratio is 30-70ml/g, is preferably
40-60ml/g；Reaction time is 1-8h, preferably 3-5h.
7. according to the preparation method of catalyst any one of claim 1-6, it is characterised in that methods described includes：Match somebody with somebody
The system soluble salt solutions corresponding with the active component, and using the soluble salt solutions to the modified zeolite molecular sieve
Carrier carries out impregnation, and obtained wet modified zeolite molecular sieve carrier is dried, be calcined, reduced, to obtain described urge
Agent.
8. made from the catalyst or preparation method according to claim 7 according to any one of claim 1-6
Application of the catalyst in 3,3'- diethyl -4,4'- MDAs are synthesized.
9. application according to claim 8, it is characterised in that using ethene and 4, the reaction of 4'- MDAs is closed
Into 3,3'- diethyl -4,4'- MDAs, the mol ratio of the ethene and 4,4'- MDA is (5-
35)：1, preferably (10-20):1.
10. application according to claim 9, it is characterised in that 100-300 DEG C of reaction temperature, preferably 150-250 DEG C；Instead
Answer pressure 10bar-70bar, preferably 30bar-50bar；
Preferably, during reaction, catalyst space velocities are 0.5-15g/g (cat)/h, preferably 5.0-10.0g/g (cat)/h.
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| CN111725531A (en) * | 2020-07-17 | 2020-09-29 | 大连理工大学 | High-selectivity copper-platinum alloy catalyst for hydrogen transfer system and preparation method thereof |
| CN116063190A (en) * | 2021-10-31 | 2023-05-05 | 中国石油化工股份有限公司 | Catalyst grading method for process of synthesizing diphenylamine from aniline |
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