CN107999089A - Catalyst for producing diethyl toluene diamine and preparation method thereof, application - Google Patents
Catalyst for producing diethyl toluene diamine and preparation method thereof, application Download PDFInfo
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- CN107999089A CN107999089A CN201711219000.0A CN201711219000A CN107999089A CN 107999089 A CN107999089 A CN 107999089A CN 201711219000 A CN201711219000 A CN 201711219000A CN 107999089 A CN107999089 A CN 107999089A
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- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
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- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8953—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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- 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
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Abstract
The invention discloses a kind of loaded catalyst for being used to produce diethyl toluene diamine, including modified support and the active component of load；Wherein, the modified support is after soluble silicon-containing compound and boron-containing compound are introduced carrier, by drying, to roast, obtained to contain the SiO decomposed by the soluble silicon-containing compound and boron-containing compound2And B2O3Modified support；The invention also discloses the preparation method and application of above-mentioned catalyst.The catalyst of the present invention is suitable for the alkylated reaction of aromatic amine, has high activity and selectivity particularly with toluenediamine alkylation continuous production diethyl toluene diamine.The catalyst preparation process is simple, good economy performance, has preferable application prospect.
Description
Technical field
It is more particularly to a kind of to be used to produce diethyl toluene diamine the present invention relates to the preparation field of diethyl toluene diamine
Loaded catalyst and preparation method thereof, application.
Background technology
Diethyl toluene diamine (vehicle economy TDA) is a kind of low viscosity, nontoxic, tasteless weak yellow liquid, it is 3,5-
Two kinds of isomers compositions of diethyl -2,4- toluenediamines (about 80%) and 3,5- diethyl -2,6- toluenediamines (about 20%)
Mixture, structural formula are as follows：
DETDA is a kind of steric hindrance type aromatic diamine, and the steric hindrance of ethyl and methyl causes its activity to compare toluenediamine
(TDA) it is much lower, its quicker than DMTDA times of reaction speed with base polyurethane prepolymer for use as, about 30 times faster than MOCA.DETDA is poly-
The chain extender of urethane and polyurea elastomer, while can also be used as polyurethane and epoxy curing agent, has that reaction speed is fast, system
Product intensity height, hydrolysis, it is heat-resisting the advantages that；In addition it can be additionally used in coating, lubricant, commercial grease antioxidant, and chemistry closes
Into intermediate etc..
DETDA is typically using toluenediamine and ethene as raw material, in the presence of a catalyst, is issued in high-temperature and high-pressure conditions
Raw alkylated reaction, obtains DETDA crude products, further separation removal catalyst, and DETDA sterlings are made by rectifying.
Reaction process is as follows：
Main reaction：
Deamination side reaction：
Demethylation side reaction：
N- is alkylated side reaction：
From above chemical reaction process, the alkylated reaction of toluenediamine has following problem：
1) the problem of reaction is complicated, and accessory substance is more, and product selectivity is poor；
2) post processing is needed by alkali neutralization, filtering, extraction, rectifying, and there are last handling process is cumbersome, quantity of three wastes
Greatly, solid waste is difficult and the problems such as environmental pollution；
3) product needs qualified by rectifying ability, but since the boiling point of accessory substance and principal product is very close, there is production
The problems such as product separation is difficult.
Patent US4760185, US5103059, US5124483 and US5072047 are disclosed by toluenediamine and ethene alkane
The method that base is combined to DETDA.These methods using aluminium, zinc, aluminum/zinc alloy (aluminium/copper alloy, aluminum/magnesium alloy etc.),
Friedel-Crafts catalyst (AlCl3、SnCl4、FeCl3、BCl3Deng) it is catalyst, first by catalyst fines and fragrance
Amine mix and at a certain temperature stir a few hours formed such as " arylamine-aluminium " catalyst system, be passed through afterwards high-pressure ethylene and
TDA is alkylated reaction synthesis DETDA.Reaction temperature is generally 250~350 DEG C, and reaction pressure is generally up to 10~
20MPa, a few hours in reaction time.Ethene belongs to inflammable and explosive hazardous gas, and alkylated reaction carries out at high temperature under high pressure, exist compared with
Big security risk.
Chinese invention patent (application number：96102856.4) disclose a kind of TDA and be combined to the side of DETDA with vinyl alkyl
Method, this method, as catalyst, are catalyzed TDA after aromatic amine activates and vinyl alkyl are combined to DETDA, its is preferred using aluminium powder
Reaction temperature be 180~270 DEG C, 2~6MPa of reaction pressure, on this condition react a few hours obtain DETDA.The catalyst
Activity it is not high, it is higher to react the temperature and pressure of needs, and there are security risk, reaction completion needs longer time.
Chinese invention patent (application number：200410042698.X) disclose a kind of Aluminium Trichloride as Catalyst TDA and ethene alkane
The method that base is combined to DETDA, reaction condition is very harsh, and 200~400 DEG C of reaction temperature, reaction pressure is up to 15~50MPa.
Reaction needs to carry out under high-temperature and high-pressure conditions, there are security risk, AlCl in addition3Easy coking during the reaction, and point
Solution discharges HCl, to serious corrosion of equipment.
Document (synthesis and application of diethyl toluene diamine, dawn chemical industry, 1995, (1):32-35) report, be alkylated aluminium
Available for catalysis TDA DETDA is combined to vinyl alkyl.During especially with triethyl aluminum as catalyst, TDA conversion ratios and
DETDA selectivity is higher, but reaction condition is more harsh, and reaction temperature is up to 300 DEG C, reaction pressure 10.0MPa, reaction
When time 7 is small.Reaction needs to carry out under high-temperature and high-pressure conditions, and there are security risk, and alkylation aluminium has stronger toxicity.
Chinese invention patent (application number：200710156324.4) disclose a kind of method of synthesis DETDA.This method makes
It is catalyst with aluminium, zinc, alchlor and alkylation aluminium, catalyst and TDA is stirred 1~1.5 at 105~200 DEG C first
Hour forms " arylamine-aluminium " catalyst system, is passed through high-pressure ethylene afterwards and is alkylated reaction synthesis DETDA.With individually making
Compared with alkylation aluminium or aluminum trichloride catalyst, be somebody's turn to do the active higher of " arylamine-aluminium " catalyst system, reaction pressure can be reduced
Power, shortens the reaction time.But reaction temperature is still up to 290~330 DEG C, 6~8MPa of reaction pressure.
In conclusion the catalyst that the prior art uses includes alchlor, aluminium, aluminium, zinc, aluminium alloy, trichlorine are alkylated
Change the mixed system of aluminium, or aluminium, zinc, alchlor and the mixed system for being alkylated aluminium.This few class catalyst is required for
Catalytic alkylation reaction under high temperature and pressure, there are security risk；When alchlor is used alone as catalyst, material is in high temperature
Easy coking under high pressure, and decompose and discharge HCl, to serious corrosion of equipment；When alkylation aluminium is used alone as catalyst, urge
Agent is expensive and with the presence of problems such as very strong toxicity.Meanwhile using above-mentioned catalyst system and catalyzing, there are last handling process
Cumbersome (including alkali neutralization, filtering, extraction, rectifying), quantity of three wastes is big, solid waste is difficult and the problems such as environmental pollution.
In the presence of a zeolite catalyst, cycloalkylation aromatics amine compounds are produced using the catalytic reaction of aromatic amine and alkene
Thing is known in the art.Product purity, low input and the operation of liquid-phase alkylation technology Yin Qigao based on zeolite
Out-of-date, the low technology based on aluminium chloride of efficiency that cost instead of.
As United States Patent (USP) US4740620 is disclosed the cycloalkylation of aromatic amine selectivity using acidic crystallization molecular sieve into neighbour
The alkylated product in position.The invention is disadvantageous in that severe reaction conditions, is needed particularly with the alkylated reaction of ethene
The temperature and pressure of higher (temperature is up to 375 DEG C, and pressure is up to 3000psig).Meanwhile feed stock conversion is low, alkylate
Predominantly mono-substituted ortho position cycloalkylation product, produces a large amount of N- alkylate by-products in reaction process.
The content of the invention
It is an object of the present invention to provide a kind of loaded catalyst for being used to produce diethyl toluene diamine, this is urged
Agent is used for the alkylated reaction production diethyl toluene diamine of toluenediamine, has very high activity and selectivity.
It is a further object of the invention to provide the preparation method of the loaded catalyst, which prepares
Technique is simple, good economy performance, has good application prospect.
It is a further object of the invention to provide be alkylated using the loaded catalyst in toluenediamine and ethene
Reaction, prepares the application in diethyl toluene diamine.
To realize the one side of above goal of the invention, the technical solution adopted by the present invention is as follows：
A kind of loaded catalyst for being used to produce diethyl toluene diamine, the catalyst include modified support and load
Active component；Wherein, the modified support is after soluble silicon-containing compound and boron-containing compound are introduced carrier, through overdrying
Dry, roasting, it is obtained to contain the SiO decomposed by the soluble silicon-containing compound and boron-containing compound2And B2O3Modification
Carrier.
In the present invention, solubility preferably refers to water-soluble.The solubility silicon-containing compound can be sodium metasilicate
Or ammonium fluosilicate, it is preferably ammonium fluosilicate.The solubility boron-containing compound can be in boric acid, ammonium pentaborate, tetraboric acid ammonium
One or more, preferred boric acid.
In the present invention, the soluble silicon-containing compound and soluble boron-containing compound can respectively or be synchronously incorporated into
On carrier, such as first soluble silicon-containing compound can be incorporated on carrier, then again be incorporated into soluble boron-containing compound
In catalyst carrier；Or soluble silicon-containing compound and soluble compound containing canopy are incorporated into catalyst carrier at the same time.
It will be appreciated by those skilled in the art that its incorporation way can have a variety of, such as spraying or infusion process etc. can be used, it is preferred to use
Infusion process, it is simple and convenient.
It will be appreciated by those skilled in the art that solution concentration, dip time or fountain height etc. can be adjusted to adjust mesh in carrier
The adsorbance of material is marked, and then controls its content, introducing process can also be once or what is repeated repeatedly carries out.A kind of real
Apply in mode, can also by the volume ratio of metal salt solution and carrier control in proper range or the carrier to obtaining with it is molten
The solidliquid mixture of liquid is evaporated, so as to remove excess of solvent.Wherein, infusion process can be incipient impregnation or
Excessive dipping；Can be multiple dipping or single-steeping.To improve efficiency, preferably using an incipient impregnation,
So that solution can be fully absorbed by carrier substantially.
In the preparation method step 1) of catalyst of the present invention, the solubility silicon-containing compound is introduced into the silicone content in carrier
The 0.5%~10% of catalyst carrier weight is accounted in terms of silica, is preferably 3.0%~8.0%, more preferably
4.0%~6.0%.The Boron contents that the solubility boron-containing compound is introduced into carrier account for catalyst carrier in terms of diboron trioxide
The 0.05%-5% of weight, is preferably 0.1%~3.0%, and more preferably 0.5%~1.0%.
Loaded catalyst according to the present invention, SiO can be decomposed into after the soluble silicon-containing compound of introducing is fired2,
Soluble boron-containing compound can be decomposed into B2O3；Preferably, the SiO decomposed2Account for the modified support weight 0.5%~
10%, it is preferably 3.0%~8.0%, more preferably 4.0%~6.0%；Decompose obtained B2O3Account for the modified support
The 0.05%-5% of weight, is preferably 0.1%~3.0%, and more preferably 0.5%~1.0%.
Loaded catalyst according to the present invention, the active component can be catalysis toluenediamines commonly used in the art
Alkylated reaction produces the active component of diethyl toluene diamine, it is preferable that the active component is selected from Pt, Pd, Ru, Rh and Ir
In one or more, the one or more being preferably selected from Pt, Pd and Ru, it is highly preferred that the active component at least contains
The mass content of Ru can be no less than 20%, 40%, 60% or 80% in Ru, such as active component.In terms of overall catalyst weight,
The content of the active component is preferably 0.05-5wt%, more preferably 0.5-3.0wt%, more preferably 1.0-2.5wt%,
Such as 2wt%.
In a preferred embodiment of the present invention, the catalyst is by carrier, active component and optional auxiliary agent group
Into.It should be noted that in the present invention, " optional " expression can be with or without.
One or more of the auxiliary agent in Ni, Cu, Fe, Zn, Cr, Co, Ti, V, Mo, Mn, Bi, preferably Ni, Cu,
One or more in Fe, Zn and Mo, more preferably Ni and/or Cu；In terms of overall catalyst weight, the content of the auxiliary agent is 0-
15wt%, is preferably 2.0-10.0wt%, more preferably 4.0-8.0wt%, such as 6wt%, to further improve its catalytic effect.
In the present invention, when the content of certain component is 0%, that is, represent to be free of the component.
In the present invention, the carrier can be catalyst porous oxide carrier commonly used in the art, the porous gold
Category oxide is Al2O3、ZrO2、TiO2、SiO2And SiO2-Al2O3One or more in complex, preferably SiO2-Al2O3It is compound
Body, in the complex, Si/Al atomic ratios can be 20-100, such as 40,50,80.The preparation method of above-mentioned porous oxide is this
Known to field, such as Al2O3, by Al2(SO4)36wt% aqueous solutions are made into, add 20wt%NH3·H2O is being stirred strongly
Lower reaction 1h is mixed, obtains Al (OH)3Precipitation, then aluminium hydroxide product that is filtered, washing, be dried to obtain, extruded moulding,
Calcination activation 4h, obtains Al at 550 DEG C2O3.The specific surface area of the carrier typically 200-600m2/ g, such as 300,
400 or 500m2/ g, aperture typically 50-100nm, such as 80nm.
The shape of carrier of the present invention can have any shape, and the concrete shape of carrier can be according to reactor (such as root
Can be autoclave according to being actually needed, fixed bed, fluid bed, shell and tube or bubble tower type etc.) selection is designed, including but not
The one or more being limited in sheet, strip and cloverleaf pattern etc..
Catalyst of the present invention is suitable for the alkylated reaction of aromatic amine, and two are prepared particularly with toluenediamine alkylation
Ethyltoluene diamines has high activity and selectivity.
Other side for achieving the above object, the preparation method of above-mentioned catalyst provided by the invention include：
1) after soluble silicon-containing compound and boron-containing compound being introduced carrier, by drying, roasting, it is made modified and carries
Body.
2) preparation and the active component and the corresponding soluble salt solutions of optional auxiliary agent, and utilize the soluble-salt
Solution carries out impregnation to the modified support, obtains wet modified support；
3) obtained wet modified support is dried, roasted, reduced, to obtain the loaded catalyst.
Common processing step that is dry, being roasted in the catalyst preparation of this area, is known in the art.In the present invention
In, drying condition can be：At 50 DEG C -150 DEG C, carried out at preferably 100 DEG C -120 DEG C；Drying time 1h-12h, preferably 5-
10h, such as 3,8h.
In step 1), calcination temperature can be 100 DEG C -700 DEG C, preferably 200 DEG C -600 DEG C, such as 300,400 or 500
℃；Roasting time 1h-10h, preferably 2h-8h, such as 3,5 or 7h.In step 3), calcination temperature can be 200 DEG C -600 DEG C, excellent
Select 300 DEG C -500 DEG C, such as 350,400 or 450 DEG C；Roasting time 2h-12h, preferably 4h-10h, such as 6,7 or 9h.
In step 2), the metal salt in the salting liquid includes but not limited to the halide of metal, nitrate and organic
One or more in hydrochlorate etc., be preferably the metal nitrate, formates, acetate and oxalates etc. in one kind or
It is a variety of, it is more preferably the nitrate of the metal.The amount ratio of each metallic element can be according to Above-mentioned catalytic in the metal salt
The ratio-dependent of each active component and adjuvant component in agent.As described above, dipping process is known in the art, it is no longer superfluous here
State.
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, reduction temperature 100
DEG C -400 DEG C, preferably 200 DEG C -300 DEG C, such as 250 DEG C；Recovery time is 1h-24h, preferably 4h-16h, for example, 6,8h, 10 or
12h。
Another aspect for achieving the above object, the present invention provides above-mentioned catalyst in toluenediamine and ethene
Reaction is alkylated, prepares the application in diethyl toluene diamine；
The preparation method of diethyl toluene diamine of the present invention may be carried out batchwise, and can also be carried out continuously, preferably connect
It is continuous to carry out.It is in the form of liquid phase reactor or anti-with gas phase in tubular reactor that continuity method prepares diethyl toluene diamine
Form is answered to carry out.
Application according to the present invention, it is preferable that the molar ratio of the ethene and toluenediamine is (1-50)：1, it is further excellent
Select (5-35):1, more preferably (10-25):1, such as 15：1 or 20：1；Preferably, reaction temperature is 100-300 DEG C, preferably 150-
250 DEG C, such as 180,200 or 220 DEG C；Reaction pressure 10bar-70bar, preferably 30bar-50bar, for example, 35,40 or
45bar。
Application according to the present invention, it is preferable that, the reaction carries out in fixed bed reactors, the catalyst space velocities
Every liter of catalyst of toluenediamine is risen for 0.01-15 per hour, and preferably 0.5-10 rises every liter of catalyst of toluenediamine per hour, more excellent
2.0-7.0 is selected, for example every liter of catalyst of 4 or 5 liters of toluenediamines is per hour.
Heretofore described pressure is relative pressure.
The beneficial effects of the present invention are：
The catalyst of the present invention is used for toluenediamine and ethylene alkylation prepares diethyl toluene diamine, more warm
Under the reaction condition of sum, while feed stock conversion reaches 100%, greatly inhibit deamination, demethylation and N- alkylations secondary
The generation of reaction, product selectivity reach more than 99.0%, and product yield more than 99.0%, the content of accessory substance is less than
1.0wt%；
Carrier prepared by the present invention, using specific soluble silicon-containing compound and boron-containing compound to support modification,
By suitable heat treatment, the good coordinative role of Si, B energy loaded, forms in carrier surface specific location and is evenly distributed
Silicon boron hydroxyl, carrier surface is formed more acid suitable acid centres, and match with original acidic site in carrier
Close, make the acidity of carrier and acid distribution more reasonable, reduce strong acid content, may advantageously facilitate the progress of expected response；
The cooperation of the acid centre of active component Ru, Ru and carrier is added in catalyst, substantially increases catalyst
Catalytic activity, one or more additions in auxiliary element such as Ni, Cu, Fe, Zn, Cr, Co, Ti, V, Mo, Mn, Bi, pass through
Active component and the cooperative effect of auxiliary element substantially increase the selectivity of product.
Compared with batch technology, using fixed-bed process, the serialization large-scale production of diethyl toluene diamine is realized,
Improve production efficiency at the same time.
Using the fixed-bed process, qualified products are can obtain without carrying out cumbersome post processing, the three wastes is thoroughly solved and asks
Topic and problem of environmental pollution, while energy consumption is reduced, save production cost.
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 solution that the present patent application the appended claims define should be also included in.
Gas chromatograph：Shimadzu GC-2014 (FID) detector, DB-5 capillary columnsSample introduction
300 DEG C of mouth, 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 are risen to 20 DEG C/min
12min is kept, to measure product.
Alkylation reactor is fixed bed reactors in embodiment.
It is described to be described below with carrier：
Al2O3Carrier, specific surface area 400m2/ g, aperture 80nm；
ZrO2Carrier, specific surface area 550m2/ g, aperture 70nm；
SiO2Carrier, specific surface area 450m2/ g, aperture 85nm；
SiO2-Al2O3Carrier, specific surface area 500m2/ g, aperture 100nm, Si:Al atomic ratios are 40.
SiO2-Al2O3Carrier, specific surface area 600m2/ g, aperture 90nm, Si:Al atomic ratios are 80.
Embodiment 1-1
2wt%Ru-4%Ni-6%Cu/ is modified SiO2-Al2O3Preparation
At normal temperatures, by 100g bar shapeds SiO2-Al2O3Carrier (Si:Al atomic ratios contain 40) to be completely infused in 100ml
In the mixed aqueous solution of 26.0g ammonium fluosilicates and 1.4g boric acid, 12h balances to be adsorbed are impregnated, then, put 130 DEG C in an oven
6h is dried, finally shifts Muffle furnace, 500 DEG C of roasting 7h, obtain the 8%SiO containing introducing2And 0.7%B2O3Modification SiO2-Al2O3
Carrier.
6.9g nitric acid ruthenium, 21.7g Nickelous nitrate hexahydrates and 24.8g Gerhardites are dissolved in 100ml deionized waters,
Stir evenly, add above-mentioned modified SiO2-Al2O3Carrier, impregnates 18h balances to be adsorbed, then, puts 120 DEG C of bakings in an oven
10h, finally shifts Muffle furnace, 400 DEG C of roasting 6h.Obtain 2wt%Ru-4%Ni-6%Cu/ and be modified SiO2-Al2O3Catalyst
Precursor A-1.
Embodiment 1-2
1wt%Pd-8%Ni-2%Fe/ is modified SiO2-Al2O3Preparation
At normal temperatures, by 100g bar shapeds SiO2-Al2O3Carrier (Si:Al atomic ratios contain 80) to be completely infused in 100ml
In the mixed aqueous solution of 19.0g ammonium fluosilicates and 0.9g boric acid, 18h balances to be adsorbed are impregnated, then, put 100 DEG C in an oven
9h is dried, finally shifts Muffle furnace, 450 DEG C of roasting 3h, obtain the 6%SiO containing introducing2And 0.5%B2O3Modification SiO2-Al2O3
Carrier.
2.3g palladium nitrates, 42.4g Nickelous nitrate hexahydrates and 15.4g Fe(NO3)39H2Os are dissolved in 100ml deionized waters,
Stir evenly, add above-mentioned modified SiO2-Al2O3Carrier, impregnates 14h balances to be adsorbed, then, puts 150 DEG C of bakings in an oven
4h, finally shifts Muffle furnace, 350 DEG C of roasting 9h.Obtain 1wt%Pd-8%Ni-2%Fe//modification SiO2-Al2O3Catalyst
Precursor A-2.
Embodiment 1-3
2.5wt%Ru-10%Ni-4%Mo/ Modification on Al2O3Preparation
At normal temperatures, by 100g bar shapeds Al2O3Carrier is completely infused in 100ml and contains 9.3g ammonium fluosilicates and 1.9g boric acid
Mixed aqueous solution in, impregnate 14h balances to be adsorbed, then, put 120 DEG C of baking 7h in an oven, finally shift Muffle furnace, 400
DEG C roasting 8h, obtain containing 3%SiO2And 1%B2O3Modification on Al2O3Carrier.
8.2g nitric acid ruthenium, 51.6g Nickelous nitrate hexahydrates and 8.5g ammonium molybdates are dissolved in 100ml deionized waters, stirring is equal
It is even, add above-mentioned Modification on Al2O3Carrier, impregnates 16h balances to be adsorbed, then, puts 130 DEG C of baking 6h in an oven, finally shifts
Muffle furnace, 450 DEG C of roasting 7h.Obtain 2.5wt%Ru-10%Ni-4%Mo//Modification on Al2O3The precursor A-3 of catalyst.
Embodiment 1-4
0.5wt%Pd-1%Ru-8%Cu/ is modified ZrO2Preparation
At normal temperatures, by 100g spherical Zrs O2Carrier is completely infused in 100ml and contains 15.7g ammonium fluosilicates and 1.1g boric acid
Mixed aqueous solution in, impregnate 16h balances to be adsorbed, then, put 110 DEG C of baking 8h in an oven, finally shift Muffle furnace, 300
DEG C roasting 10h, obtain containing 5%SiO2And 0.6%B2O3Modification ZrO2Carrier.
1.1g palladium nitrates, 3.3g nitric acid ruthenium and 32.0g Gerhardites are dissolved in 100ml deionized waters, stirring is equal
It is even, add above-mentioned modified ZrO2Carrier, impregnates 12h balances to be adsorbed, then, puts 120 DEG C of baking 10h in an oven, finally turns
Move Muffle furnace, 300 DEG C of roasting 10h.Obtain 0.5wt%Pd-1%Ru-8%Cu/ and be modified ZrO2The precursor A-4 of catalyst.
Embodiment 1-5
1.5%Ru-10%Cu-3%Zn/ is modified SiO2Preparation
At normal temperatures, by 100g spherical SiOs2Carrier is completely infused in 100ml and contains 22.5g ammonium fluosilicates and 1.5g boric acid
Mixed aqueous solution in, impregnate 20h balances to be adsorbed, then, put 150 DEG C of baking 5h in an oven, finally shift Muffle furnace, 600
DEG C roasting 5h, obtain the 7%SiO containing introducing2And 0.8%B2O3Modification SiO2Carrier.
5.1g nitric acid ruthenium, 40.9g Gerhardites and 14.9g zinc nitrates are dissolved in 100ml deionized waters, stirring is equal
It is even, add above-mentioned modified SiO2Carrier, impregnates 20h balances to be adsorbed, then, puts 120 DEG C of baking 12h in an oven, finally turns
Move Muffle furnace, 500 DEG C of roasting 5h.Obtain 1.5%Ru-10%Cu-3%Zn/ and be modified SiO2The precursor A-5 of catalyst.
Comparative example 1
2wt%Ru-4%Ni-6%Cu/SiO2-Al2O3Preparation
Difference lies in SiO with embodiment 1-1 for comparative example 12-Al2O3Without any modification.
6.9g nitric acid ruthenium, 21.7g Nickelous nitrate hexahydrates and 24.8g Gerhardites are dissolved in 100ml deionized waters,
Stir evenly, add 100g SiO2-Al2O3Carrier, impregnates 18h balances to be adsorbed, then, puts 120 DEG C of bakings in an oven
10h, finally shifts Muffle furnace, 400 DEG C of roasting 6h.Obtain 2wt%Ru-4%Ni-6%Cu/ and be modified SiO2-Al2O3Catalyst
Precursor A-6.
Embodiment 2-1
The supported catalyst precursor A-1 for dissipating that heap volume is 50ml is loaded in fixed bed reactors, under the conditions of 300 DEG C
6h is reduced with 5% hydrogen, the gaseous mixture of 95% nitrogen to it, after to be restored, reaction temperature is down to 200 DEG C, by system pressure
Power (absolute pressure, similarly hereinafter) rises to 40bar and starts to feed, air speed for every liter of catalyst of 5.0 liters of toluenediamines per hour, ethene/first
Phenylenediamine molar ratio is 15：1, through gas chromatographic analysis, toluenediamine does not detect, and diethyl toluene diamine content is 99.5%,
Single ethyltoluene diamine contents are 0.5%, feed stock conversion 100%, product yield 99.5%.
Embodiment 2-2
The supported catalyst precursor A-2 for dissipating that heap volume is 50ml is loaded in fixed bed reactors, under the conditions of 200 DEG C
12h is reduced with 5% hydrogen, the gaseous mixture of 95% nitrogen to it, after to be restored, reaction temperature is down to 160 DEG C, by system pressure
Power (absolute pressure, similarly hereinafter) rises to 35bar and starts to feed, air speed for every liter of catalyst of 4.0 liters of toluenediamines per hour, ethene/first
Phenylenediamine molar ratio is 20：1, through gas chromatographic analysis, toluenediamine does not detect, and diethyl toluene diamine content is 99.0%,
Single ethyltoluene diamine contents are 1.0%, feed stock conversion 100%, product yield 99.0%.
Embodiment 2-3
The supported catalyst precursor A-3 for dissipating that heap volume is 50ml is loaded in fixed bed reactors, under the conditions of 250 DEG C
10h is reduced with 5% hydrogen, the gaseous mixture of 95% nitrogen to it, after to be restored, reaction temperature is down to 240 DEG C, by system pressure
Power (absolute pressure, similarly hereinafter) rises to 30bar and starts to feed, air speed for every liter of catalyst of 7.0 liters of toluenediamines per hour, ethene/first
Phenylenediamine molar ratio is 18：1, through gas chromatographic analysis, toluenediamine does not detect, and diethyl toluene diamine content is 97.5%,
Single ethyltoluene diamine contents are 2.5%, feed stock conversion 100%, product yield 97.5%.
Embodiment 2-4
The supported catalyst precursor A-4 for dissipating that heap volume is 50ml is loaded in fixed bed reactors, under the conditions of 400 DEG C
8h is reduced with 5% hydrogen, the gaseous mixture of 95% nitrogen to it, after to be restored, reaction temperature is down to 220 DEG C, by system pressure
Power (absolute pressure, similarly hereinafter) rises to 45bar and starts to feed, air speed for every liter of catalyst of 6.0 liters of toluenediamines per hour, ethene/first
Phenylenediamine molar ratio is 25：1, through gas chromatographic analysis, toluenediamine does not detect, and diethyl toluene diamine content is 98.5%,
Single ethyltoluene diamine contents are 1.5%, feed stock conversion 100%, product yield 98.5%.
Embodiment 2-5
The supported catalyst precursor A-5 for dissipating that heap volume is 50ml is loaded in fixed bed reactors, under the conditions of 350 DEG C
14h is reduced with 5% hydrogen, the gaseous mixture of 95% nitrogen to it, after to be restored, reaction temperature is down to 180 DEG C, by system pressure
Power (absolute pressure, similarly hereinafter) rises to 50bar and starts to feed, air speed for every liter of catalyst of 3.0 liters of toluenediamines per hour, ethene/first
Phenylenediamine molar ratio is 10：1, through gas chromatographic analysis, toluenediamine does not detect, and diethyl toluene diamine content is 98.7%,
Single ethyltoluene diamine contents are 1.3%, feed stock conversion 100%, product yield 98.7%.
Comparative example 2
The supported catalyst precursor A-6 for dissipating that heap volume is 50ml is loaded in fixed bed reactors, under the conditions of 300 DEG C
6h is reduced with 5% hydrogen, the gaseous mixture of 95% nitrogen to it, after to be restored, reaction temperature is down to 200 DEG C, by system pressure
Power (absolute pressure, similarly hereinafter) rises to 40bar and starts to feed, air speed for every liter of catalyst of 5.0 liters of toluenediamines per hour, ethene/first
Phenylenediamine molar ratio is 15：1, through gas chromatographic analysis, toluenediamine does not detect, and diethyl toluene diamine content is 80.0%,
Single ethyltoluene diamine contents are 3.0%, and demethylation by-products content is that 2.0%, N- alkylate by-products content is 15%, former
Expect conversion ratio 100%, product yield 80.0%.
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 variations or changes in different ways.Here all embodiments can not be exhaustive.It is every to belong to this hair
The obvious changes or variations that bright technical solution is extended out is within the scope that the present invention covers.
Claims (10)
1. a kind of loaded catalyst for being used to produce diethyl toluene diamine, the catalyst include modified support and load
Active component；It is characterized in that, the modified support is after soluble silicon-containing compound and boron-containing compound are introduced carrier, warp
Dry, roasting is crossed, it is obtained to contain the SiO decomposed by the soluble silicon-containing compound and boron-containing compound2And B2O3's
Modified support.
2. loaded catalyst according to claim 1, it is characterised in that the SiO decomposed2Account for the modified support
The 0.5%~10% of weight, is preferably 3.0%~8.0%, and more preferably 4.0%~6.0%；Decompose obtained B2O3Account for
The 0.05%-5% of the modified support weight, is preferably 0.1%~3.0%, and more preferably 0.5%~1.0%.
3. loaded catalyst according to claim 1 or 2, it is characterised in that the active component be selected from Pt, Pd, Ru,
One or more in Rh and Ir, the one or more being preferably selected from Pt, Pd and Ru, it is highly preferred that the active component is extremely
Contain Ru less；
In terms of overall catalyst weight, the content of the active component is 0.05-5wt%, is preferably 0.5-3.0wt%, more preferably
1.0-2.5wt%.
4. loaded catalyst according to any one of claim 1-3, it is characterised in that the catalyst optionally wraps
Include auxiliary agent, one or more of the auxiliary agent in Ni, Cu, Fe, Zn, Cr, Co, Ti, V, Mo, Mn, Bi, preferably Ni, Cu,
One or more in Fe, Zn and Mo, more preferably Ni and/or Cu；
In terms of overall catalyst weight, the content of the auxiliary agent is 0-15wt%, is preferably 2.0-10.0wt%, more preferably 4.0-
8.0wt%.
5. according to the loaded catalyst any one of claim 1-4, it is characterised in that the carrier is porous
Al2O3、ZrO2、TiO2、SiO2And SiO2-Al2O3The one or more of complex, preferably porous SiO2-Al2O3Complex.
A kind of 6. method for preparing the loaded catalyst any one of claim 1-5, it is characterised in that including as follows
Step：
1) after soluble silicon-containing compound and boron-containing compound being introduced carrier, by drying, roasting, modified support is made；
2) preparation and the active component and the corresponding soluble salt solutions of optional auxiliary agent, and utilize the soluble salt solutions
Impregnation is carried out to the modified support, obtains wet modified support；
3) obtained wet modified support is dried, roasted, reduced, to obtain the loaded catalyst.
7. according to the method described in claim 6, it is characterized in that, soluble silicon-containing compound is ammonium fluosilicate；Solubility contains
Boron compound is boric acid, the one or more in ammonium pentaborate, tetraboric acid ammonium, preferred boric acid.
8. the method according to the description of claim 7 is characterized in that calcination temperature is 100 DEG C -700 DEG C in step 1), preferably
200℃-600℃；Roasting time 1h-10h, preferably 2h-8h；
In step 3), calcination temperature is 200 DEG C -600 DEG C, preferably 300 DEG C -500 DEG C；Roasting time 2h-12h, preferably 4h-10h.
9. the catalyst according to any one of claim 1-6 or the preparation method system according to claim 7 or 8
The loaded catalyst obtained is alkylated reaction in toluenediamine and ethene, prepares the application in diethyl toluene diamine；
Preferably, the molar ratio of the ethene and toluenediamine is (1-50)：1, further preferred (5-35):1, more preferably (10-
25):1；
Preferably, reaction temperature is 100-300 DEG C, preferably 150-250 DEG C；Reaction pressure 10bar-70bar, preferably 30bar-
50bar。
10. application according to claim 9, it is characterised in that the reaction carries out in fixed bed reactors, described to urge
Agent air speed rises every liter of catalyst of toluenediamine per hour for 0.01-15, and it is every that preferably 0.5-10 rises every liter of catalyst of toluenediamine
Hour, more preferably 2.0-7.0 rises every liter of catalyst of toluenediamine per hour.
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