CN106631826B - A kind of preparation method of diamino-dicyclohexyl methane - Google Patents
A kind of preparation method of diamino-dicyclohexyl methane Download PDFInfo
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- 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
- C07C209/70—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 by reduction of unsaturated amines
- C07C209/72—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 by reduction of unsaturated amines by reduction of six-membered aromatic rings
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Abstract
The invention discloses a kind of preparation method of diamino-dicyclohexyl methane.The method is with diaminodiphenyl-methane (MDA) for raw material, in hydrogenation reaction, utilize the acid activity for improving catalyst of phenolic compound, reduce the generation of higher boiling tar in reaction process, at the same time, product alicyclic ring alcohol compound effectively can take the higher boiling tar that catalyst surface wraps up out of reaction system after phenolic compound hydrogenation, the problem of greatly improving filtration difficulty caused by being adsorbed due to catalyst surface higher boiling tar, improves diamino-dicyclohexyl methane (H12MDA reaction yield), makes the activity of catalyst significantly be extended, and improves production efficiency.
Description
Technical field
The present invention relates to a kind of aromatic ring method of hydrotreating, is more particularly to a kind of diaminodiphenyl-methane hydrogenation reaction and prepares
The method of diamino-dicyclohexyl methane.
Background technology
4,4 ' -- diamino-dicyclohexyl methane (4,4 '-H12MDA) be production superior performance of new generation anti-aging poly- ammonia
Ester-dicyclohexyl methyl hydride diisocyanate (H12MDI primary raw material), which can be used for preparing lightweight and performance is steady
Fixed polyurethane coating and paint.4,4’-H12MDA also acts as the amine component of epoxy curing agent and transparent nylon.
Due to the aromatic ring structure and space steric effect of diaminodiphenyl-methane (MDA), while also to ensure product two
The ratio of three kinds of isomers in amino bicyclic hexyl methane, especially ensures anti-body ratio between 17-24%, diamino
The hydrogenation difficulty of base dicyclohexyl methyl hydride is very big.Most of catalytic hydrogenation patent on MDA is urged using carried noble metal
Agent, on fixed bed reactors or stirred-tank reactor, carries out interval catalytic reaction, to obtain satisfaction under high temperature and pressure
Yield and anti-body ratio.Due to the use of noble metal catalyst it is expensive, in order to reduce production cost, catalyst circulation
It is very necessary to apply mechanically link.It is to use built-in filter or external filtering that the catalyst circulation referred in most of patent, which is applied mechanically,
Product liquid is isolated reactor by device, and fresh MDA raw materials are put into the reaction of lower batch, and then is catalyzed next batch reaction.
And during the reaction, as a result of the higher noble metal catalyst of activity, also result in the generation of by-product higher boiling tar.
As catalyst applies mechanically increasing for number, higher boiling tar is constantly covered and wrapped up in catalyst surface, and tar constantly tires out
On the one hand product makes catalyst activity constantly decline, and then increase the reaction time and make H12MDA yields decline and anti-body selectivity
Rise；On the other hand change the apparent property of catalyst, catalyst granules is more sticky, so as to cause the filtering of product liquid tired
Difficulty, greatly extends filtration time, overall production efficiency is declined to a great extent.Therefore, higher boiling in reaction process how is reduced
The tar adhesion amount for generating and how reducing catalyst surface of tar is extremely important for improving production run efficiency.
US3591635 discloses a kind of reducing process of efficient more phenyl ring aromatic amine compounds, it uses 1-
20wt%Rh/Al2O3For catalyst, using isopropanol as solvent, the semicontinuous of MDA is carried out under 25-200 DEG C and 3-20MPa and has been added
Hydrogen reacts.After reaction, catalyst filtration is isolated, is handled at 60-80 DEG C with ammonium hydroxide aqueous solution, after dry
Catalyst repeat be used for be catalyzed MDA hydrogenation reactions.
US3071551 discloses a kind of high temperature regeneration technique of inactivation Rh catalyst.In one-step reaction, by poisoning and deactivation
Rh catalyst be heated to 200-300 DEG C, and continue 2-24h and regenerated.
US3856862 discloses a kind of efficient 4,4 '-MDA hydrogenation techniques of Rh catalysis.It uses load Rh/Al2O3Catalysis
Agent, MDA hydrogenation reactions are carried out in high temperature relative superiority or inferiority, after reaction, continuous logical after Rh catalyst and product are separated by filtration
Enter the O that volume fraction is 0.5-5%2And N2Air-flow, activates 2-6h at 300-450 DEG C, and then completes catalyst regeneration.
US4754070, which discloses one kind, can obtain pre-selection H12(anti-trans isomer ratio is 17- to MDA isomer proportions
24%) new method.It is raw material with thick 4, the 4'-MDA containing 10-30wt% oligomers, is urged using immobilized rhodium-ruthenium two-component
The mass ratio of agent, wherein rhodium and ruthenium is 3:7, carrier is aluminium oxide, barium sulfate etc., before catalytic reaction, adds 0.1-
The base-modified catalyst of 15wt%, while using THF as solvent, reacted under 170-195 DEG C and 700-1500psig, the reaction time
No more than 300min.
US6075167 provides the aromatic diamine compound that a kind of ruthenium using metal sulphite as accelerating agent is catalyzed and reduces work
Skill, improves reaction rate, reduces the amount of high boiling point by-products produced tar.It uses Ru as catalyst, activated carbon, calcium carbonate or
Aluminium oxide etc. is carrier, and the content of Ru metals is the 1-10wt% of carrier, is then made in alcohols, ethers or cyclo other compounds molten
Under agent, catalytic reaction is carried out with the solid-carried catalyst of aromatic diamines quality 0.1-5wt%, while add 5-20 times of Ru moles of metal
The sodium nitrite of amount is as accelerating agent, and reaction temperature is 100-200 DEG C, reaction pressure 500-2000psig.
There are following defect for the prior art：
1) need to add alkali metal salt as accelerating agent, reacted by alkali metal salt with supported precious metal catalyst to reduce
Catalyst system and catalyzing activity, so as to reduce the amount of high boiling point by-products produced tar.In order to ensure relatively low tar content, it is necessary to subsequently urge
Agent adds new accelerating agent incessantly in applying mechanically, and therefore, the continuous residual accumulation of alkali metal salt, can make to bear in catalyst system and catalyzing
The performance of supported noble metal catalyst obtains irreversible infringement, so that the reaction time constantly extends, and anti-trans contents are continuous
Rise, beyond index.
2) when catalyst due to tar constantly accumulate cause activity decline when, the above section prior art need reaction tie
Shu Hou, after catalyst and the filtering of product liquid, individually washs catalyst, is roasted and drying process, make its regeneration.This will
Significantly reduce H12The production efficiency of MDA, makes production procedure more cumbersome, production cost dramatically increases.
3) prior art does not refer to and solves batch reactor formula hydrogenation reaction and prepares H12During MDA, catalyst with
Product liquid be separated by filtration the time number increase can be applied mechanically with catalyst and the problem of dramatically increase.With Jiao of catalyst surface
Oily cumulant gradually increases, and filtration time can be caused significantly to extend, so as to greatly reduce overall production efficiency, causes cost to show
Write increase.
The content of the invention
The present invention provides a kind of MDA hydrogenation reactions to prepare H12The method of MDA, this method is by MDA raw materials, adding
Phenolic compound, using the acid activity for improving catalyst of phenolic compound, reduces the life of higher boiling tar in reaction process
Into so as to improve H12The yield of MDA, while the tar of catalyst surface is cleaned online, it highly shortened product liquid
With the time that is separated by filtration of catalyst, and then the activity of catalyst is significantly extended, improve production efficiency well.
To achieve the above objectives, technical scheme is as follows：
The present invention provides a kind of H12The preparation method of MDA, includes the following steps：In MDA raw materials, phenols chemical combination is added
Thing, carries out hydrogenation reaction and prepares H under certain temperature and pressure in reactor packed with catalyst12MDA。
H of the present invention12MDA yields are 97-99%, wherein anti-trans isomer accounts for H12The ratio of MDA is 17-24%, burnt
Oil yield≤2%, other yield≤1%.
MDA raw materials of the present invention, include following components：The 4,4 '-MDA of 96-100wt%, the 2,4 ' of 0-2wt%-
Other impurity of N- methyl -4 of MDA, 0-1wt%, 4 '-MDA and 0-1wt%, in terms of MDA raw material weights；It is preferred that 99-
The 4,4 '-MDA of 100wt%, the 2,4 '-MDA of 0-0.5wt%, the N--MDA of methyl -4,4 ' and 0-0.1wt% of 0-0.4wt%
Other impurity, in terms of MDA raw material weights.
The one or more in compound of the phenolic compound selected from structural formula I and II in step 1) of the present invention.
Wherein R is selected from H or-(CH2)n-CH3, the integer of n=0~10；The phenolic compound is preferably phenol, to methyl
Phenol, m-methyl phenol, ortho-methyl phenol, the one or more of bisphenol-A；More preferably phenol and/or bisphenol-A.
The content of phenolic compound of the present invention is 0.1-20wt%；Preferably 1-10wt%；More preferably 3-
5wt%, in terms of MDA raw material weights.
Catalyst of the present invention is metal load type catalyst, and wherein metal is the one or more of group VIIIB metal,
It is preferred that the one or more of Pt, Rh, Ru, Ir and Pd, the carrier is rare earth, diatomite, aluminium oxide, activated carbon, lithium aluminate, point
The one or more of spar, silica and sieve and silica-sesquioxide, the content of metal is 1-10wt%, with metal load type catalyst weight
Calculated on the basis of amount.
Preferably, catalyst of the present invention is Rh/Al2O3And Ru/Al2O3Mixture, the weight ratio of wherein Rh and Ru
For 1-50：1, it is preferably 30-40：1；The content of Rh is 1-10wt%, is preferably 3-7wt%, more preferably 4-6wt%, with Rh/
Al2O3Meter；The content of Ru is 1-10wt%, is preferably 3-7wt%, more preferably 4-6wt%, with Ru/Al2O3Meter.
When catalyst of the present invention uses Rh/Al2O3And Ru/Al2O3Mixture when, Rh/Al2O3Dosage be 0.5-
5wt%, is preferably 1-3wt%, in terms of the weight of MDA raw materials.
Reactor of the present invention is the high pressure batch autoclave reactor with catalyst filtration device, its catalyst mistake
Filter device is preferably built-in filter and external filter, more preferably autoclave built-in filter.
Hydrogenation reaction of the present invention can carry out under conditions of with or without solvent, preferably comprise solvent.Such as
Fruit uses solvent, then the concentration of MDA raw materials in the solution is 40-70wt%, is preferably 50-60wt%, in terms of solution weight.Institute
State solution and include MDA raw materials and solvent.
Solvent of the present invention is selected from hexamethylene, dioxane, tetrahydrofuran, cyclohexylamine, dicyclohexyl amine, methanol, second
One or more in alcohol, isopropanol, n-butanol, 2- butanol and hexahydrotoluene, preferably tetrahydrofuran.
100-250 DEG C of reaction temperature of the present invention, is preferably 150-200 DEG C, more preferably 170-190 DEG C；It is described
Reaction absolute pressure be 3-15MPa, be preferably 5-10MPa, more preferably 6-8MPa.
The positive effect of the present invention：
1) present invention participates in catalytic hydrogenation reaction using phenolic compound, using its acid on-line control catalyst activity come
The content of high boiling point by-products produced tar is reduced, without adding inorganic matter alkali metal salt as accelerating agent, therefore, will not cause to load
The irreversible lesion of noble metal catalyst and carrier, can keep catalyst activity and the selection to anti-body well
Property.
2) the present invention provides a kind of every batch of can on-line cleaning catalyst surface accumulation tar method, phenols chemical combination
Product alicyclic ring alcohol compound effectively can take the higher boiling tar that catalyst surface wraps up out of reaction system after thing hydrogenation,
Solve that catalyst and product liquid are separated by filtration that the time can apply mechanically number increase with catalyst well and what is dramatically increased ask
Topic, drastically increases H12The production efficiency of MDA, simplifies Process planning flow, and saves production cost.
Embodiment
With reference to embodiment, the present invention is further described, but the invention is not restricted to listed embodiment.
4wt%Rh/Al2O3And 5wt%Ru/Al2O3It is purchased from village letter Wan Feng companies.
MDA raw materials come from ten thousand China WANAMINE MDA-100.Wherein 4,4 '-MDA contents are 99.5wt%, N- methyl -4,
4 '-MDA contents are 0.35wt%, and other impurity contents are 0.15wt%.
Gas-chromatography is the series of agilent company 6890, and DB capillary chromatographic columns, fid detector temperature is 300 DEG C, starting
Column temperature is 160 DEG C, and 10 DEG C/min rises to 300 DEG C, stops 20min.
Embodiment 1
It is that 2L carries built-in filter autoclave in volume, adds 5g Rh/Al2O3With 0.125g Ru/Al2O3Urge
Agent, while 500gMDA raw materials and 500g tetrahydrofurans and 15g phenol are added, respectively with the N of 10bar (absolute pressure)2With
H2After displacement three times, then use H2Ftercompction to 45-50bar (absolute pressure), rise temperature passes through hydrogen to 190 DEG C in reaction process
Flow controller continues to be passed through H into reaction kettle2, ensure that reaction pressure maintains 80bar (absolute pressure), when hydrogen flowing quantity control
When the hydrogen flowing quantity registration of device processed is less than 100sccm, stopping is passed through H2, when reactor pressure drop is less than 0.1bar/min, stop
Only react, cooling pressure release is carried out to reaction kettle, when temperature of reaction kettle is down to 50 DEG C, using no more than 6bar's (absolute pressure)
N2Product liquid is separated with catalyst filtration by built-in filter, and gas chromatographic analysis is carried out to product liquid, the results are shown in Table
1.After the filtering of product liquid is clean, 500gMDA raw materials and 500g tetrahydrofurans and 15g phenol are continuously added, repeats to walk above
Suddenly, the recycled of catalyst is carried out.
The catalyst of 1 embodiment 1 of table applies mechanically reaction result
* the reaction time is timing after reaching reaction temperature to stopping reacting.
Comparative example 1
It is that 2L carries built-in filter autoclave in volume, adds 5g Rh/Al2O3With 0.125g Ru/Al2O3Urge
Agent, while 500gMDA raw materials and 500g tetrahydrofurans are added, respectively with the N of 10bar (absolute pressure)2And H2Displacement is three times
Afterwards, then H is used2Ftercompction to 45-50bar (absolute pressure), rise temperature is controlled to 190 DEG C in reaction process by hydrogen flowing quantity
Device continues to be passed through H into reaction kettle2, ensure that reaction pressure maintains 80bar (absolute pressure), when the hydrogen of hydrogen flowing quantity controller
When throughput registration is less than 100sccm, stopping is passed through H2, when reactor pressure drop is less than 0.1bar/min, stop reaction, it is right
Reaction kettle carries out cooling pressure release, when temperature of reaction kettle is down to 50 DEG C, using the N no more than 6bar (absolute pressure)2By interior
Put filter to separate product liquid with catalyst filtration, and gas chromatographic analysis is carried out to product liquid, the results are shown in Table 2.Work as product
After liquid filtering is clean, 500gMDA raw materials and 500g tetrahydrofurans are continuously added, above step is repeated, carries out the circulation of catalyst
Apply mechanically.
The catalyst of 2 comparative example 1 of table applies mechanically reaction result
From table 2 it can be seen that in the reaction of Run1, catalyst is since fully activation, reaction time are not up to 425min.
Then, in Run2-10, reaction time and filtration time do not have notable rising.After Run10, the reaction time from
240min is gradually increased to 320min, and filtration time significantly extends to 300min from 25min, and tar yield from 7.5% significantly
Increase to 11.2%, H12MDA yields are then down to 86.1%, and the reactivity worth and strainability of catalyst are remarkably decreased.
Embodiment 2
It is that 2L carries built-in filter autoclave in volume, adds 15g Rh/Al2O3With 0.5g Ru/Al2O3Catalysis
Agent, while 500gMDA raw materials and 500g tetrahydrofurans and 25g bisphenol-As are added, respectively with the N of 10bar (absolute pressure)2And H2
After displacement three times, then use H2Ftercompction to 45-50bar (absolute pressure), rise temperature passes through hydrogen to 170 DEG C in reaction process
Flow controller continues to be passed through H into reaction kettle2, ensure that reaction pressure maintains 60bar (absolute pressure), when hydrogen flowing quantity control
When the hydrogen flowing quantity registration of device processed is less than 100sccm, stopping is passed through H2, when reactor pressure drop is less than 0.1bar/min, stop
Only react, cooling pressure release is carried out to reaction kettle, when temperature of reaction kettle is down to 50 DEG C, using no more than 6bar's (absolute pressure)
N2Product liquid is separated with catalyst filtration by built-in filter, and gas chromatographic analysis is carried out to product liquid, the results are shown in Table
3.After the filtering of product liquid is clean, 500gMDA raw materials and 500g tetrahydrofurans and 25g bisphenol-As are continuously added, repeats to walk above
Suddenly, the recycled of catalyst is carried out.
The catalyst of 3 embodiment 2 of table applies mechanically reaction result
Embodiment 3
It is that 2L carries built-in filter autoclave in volume, adds 5g Rh/Al2O3With 0.125g Ru/Al2O3Urge
Agent, while 500gMDA raw materials and 500g tetrahydrofurans are added, respectively with the N of 10bar (absolute pressure)2And H2Displacement is three times
Afterwards, then H is used2Ftercompction to 45-50bar (absolute pressure), rise temperature is controlled to 190 DEG C in reaction process by hydrogen flowing quantity
Device continues to be passed through H into reaction kettle2, ensure that reaction pressure maintains 80bar (absolute pressure), when the hydrogen of hydrogen flowing quantity controller
When throughput registration is less than 100sccm, stopping is passed through H2, when reactor pressure drop is less than 0.1bar/min, stop reaction, it is right
Reaction kettle carries out cooling pressure release, when temperature of reaction kettle is down to 50 DEG C, using the N no more than 6bar (absolute pressure)2By interior
Put filter to separate product liquid with catalyst filtration, and gas chromatographic analysis is carried out to product liquid, the results are shown in Table 4.Work as product
After liquid filtering is clean, 500gMDA raw materials and 500g tetrahydrofurans are continuously added, above step is repeated, carries out the circulation of catalyst
Apply mechanically.Wherein 15g phenol is in addition added in Run30-50, every batch of.
The catalyst of 4 embodiment 3 of table applies mechanically reaction result
Embodiment 4
It is that 2L carries built-in filter autoclave in volume, adds 15g Rh/Al2O3With 0.3g Ru/Al2O3Catalysis
Agent, while 500gMDA raw materials and 500g tetrahydrofurans are added, respectively with the N of 10bar (absolute pressure)2And H2After displacement three times,
H is used again2Ftercompction to 45-50bar (absolute pressure), rise temperature is held to 170 DEG C in reaction process by hydrogen flowing quantity controller
H is passed through in continuing toward reaction kettle2, ensure that reaction pressure maintains 60bar (absolute pressure), when the hydrogen stream of hydrogen flowing quantity controller
When amount registration is less than 100sccm, stopping is passed through H2, when reactor pressure drop is less than 0.1bar/min, stop reaction, to reaction
Kettle carries out cooling pressure release, when temperature of reaction kettle is down to 50 DEG C, using the N no more than 6bar (absolute pressure)2Pass through built-in mistake
Filter separates product liquid with catalyst filtration, and carries out gas chromatographic analysis to product liquid, the results are shown in Table 5.When product liquid mistake
After being filtered dry only, 500gMDA raw materials and 500g tetrahydrofurans are continuously added, repeats above step, carries out the recycled of catalyst.
Wherein 25g bisphenol-As are in addition added in Run30-50, every batch of.
The catalyst of 5 embodiment 4 of table applies mechanically reaction result
Embodiment 5
It is that 2L carries built-in filter autoclave in volume, adds 15g Rh/Al2O3With 0.3g Ru/Al2O3Catalysis
Agent, while 600gMDA raw materials and 400g tetrahydrofurans and 0.6g phenol are added, respectively with the N of 10bar (absolute pressure)2And H2
After displacement three times, then use H2Ftercompction to 45-50bar (absolute pressure), rise temperature passes through hydrogen to 180 DEG C in reaction process
Flow controller continues to be passed through H into reaction kettle2, ensure that reaction pressure maintains 60bar (absolute pressure), when hydrogen flowing quantity control
When the hydrogen flowing quantity registration of device processed is less than 100sccm, stopping is passed through H2, when reactor pressure drop is less than 0.1bar/min, stop
Only react, cooling pressure release is carried out to reaction kettle, when temperature of reaction kettle is down to 50 DEG C, using no more than 6bar's (absolute pressure)
N2Product liquid is separated with catalyst filtration by built-in filter, and gas chromatographic analysis is carried out to product liquid, the results are shown in Table
6.After the filtering of product liquid is clean, 600gMDA raw materials and 400g tetrahydrofurans and 0.6g phenol are continuously added, repeats to walk above
Suddenly, the recycled of catalyst is carried out.
The catalyst of 6 embodiment 5 of table applies mechanically reaction result
Embodiment 6
It is that 2L carries built-in filter autoclave in volume, adds 15g Rh/Al2O3With 0.3g Ru/Al2O3Catalysis
Agent, while 600gMDA raw materials and 400g tetrahydrofurans and 120g bisphenol-As are added, respectively with the N of 10bar (absolute pressure)2With
H2After displacement three times, then use H2Ftercompction to 45-50bar (absolute pressure), rise temperature passes through hydrogen to 180 DEG C in reaction process
Flow controller continues to be passed through H into reaction kettle2, ensure that reaction pressure maintains 60bar (absolute pressure), when hydrogen flowing quantity control
When the hydrogen flowing quantity registration of device processed is less than 100sccm, stopping is passed through H2, when reactor pressure drop is less than 0.1bar/min, stop
Only react, cooling pressure release is carried out to reaction kettle, when temperature of reaction kettle is down to 50 DEG C, using no more than 6bar's (absolute pressure)
N2Product liquid is separated with catalyst filtration by built-in filter, and gas chromatographic analysis is carried out to product liquid, the results are shown in Table
7.After the filtering of product liquid is clean, continuously add 600gMDA raw materials and 400g tetrahydrofurans and 120g bisphenol-As, repeat more than
Step, carries out the recycled of catalyst.
The catalyst of 7 embodiment 6 of table applies mechanically reaction result
Claims (20)
1. a kind of preparation method of diamino-dicyclohexyl methane, includes the following steps：In diaminodiphenyl-methane raw material,
Phenolic compound is added, in reactor packed with catalyst, hydrogenation reaction is carried out under certain temperature and pressure and prepares two
Amino bicyclic hexyl methane；Wherein, the one or more in compound of the phenolic compound selected from structural formula I and II,
Wherein R is selected from H or-(CH2)n-CH3, the integer of n=0~10；The catalyst is metal load type catalyst, wherein
Metal is the one or more of group VIIIB metal, and the carrier is rare earth, diatomite, aluminium oxide, activated carbon, lithium aluminate, point crystalline substance
The one or more of stone, silica and sieve and silica-sesquioxide, the content of metal is 1-10wt%, with metal load type catalyst weight
On the basis of calculate.
2. according to the method described in claim 1, it is characterized in that, the phenolic compound be selected from for phenol, p-methyl phenol,
One or more in m-methyl phenol, ortho-methyl phenol and bisphenol-A.
3. method according to claim 1 or 2, it is characterised in that the diaminodiphenyl-methane raw material include with
Lower component：The 4,4 ' of 96-100wt%-diaminodiphenyl-methane, 2,4 '-diaminodiphenyl-methane of 0-2wt%, 0-
Other impurity of N- methyl -4 of 1wt%, 4 '-diaminodiphenyl-methane and 0-1wt%, with diaminodiphenyl-methane raw material
Weight meter.
4. according to the method described in claim 3, it is characterized in that, the diaminodiphenyl-methane raw material is included with the following group
Point：The 4,4 ' of 99-100wt%-diaminodiphenyl-methane, 2,4 '-diaminodiphenyl-methane of 0-0.5wt%, 0-
Other impurity of N- methyl -4 of 0.4wt%, 4 '-diaminodiphenyl-methane and 0-0.1wt%, with diaminodiphenyl-methane
Raw material weight meter.
5. method according to claim 1 or 2, it is characterised in that the content of the phenolic compound is 0.1-
20wt%, in terms of diaminodiphenyl-methane raw material weight.
6. according to the method described in claim 5, it is characterized in that, the content of the phenolic compound is 1-10wt%, with
Diaminodiphenyl-methane raw material weight meter.
7. according to the method described in claim 6, it is characterized in that, the content of the phenolic compound is 3-5wt%, with two
Aminodiphenylmethane raw material weight meter.
8. according to the method described in claim 1, it is characterized in that, the metal is one kind or more of Pt, Rh, Ru, Ir and Pd
Kind.
9. according to the method described in claim 1, it is characterized in that, the catalyst is Rh/Al2O3And Ru/Al2O3Mixing
The weight ratio of thing, wherein Rh and Ru is 1-50：1；The content of Rh is 1-10wt%, with Rh/Al2O3Meter；The content of Ru is 1-
10wt%, with Ru/Al2O3Meter.
10. according to the method described in claim 9, it is characterized in that, the weight ratio of the Rh and Ru is 30-40：1；Rh's contains
Measure as 3-7wt%, with Rh/Al2O3Meter；The content of Ru is 3-7wt%, with Ru/Al2O3Meter.
11. according to the method described in claim 10, it is characterized in that, the content of the Rh is 4-6wt%, with Rh/Al2O3Meter；
The content of Ru is 4-6wt%, with Ru/Al2O3Meter.
12. according to claim 9-11 any one of them methods, it is characterised in that the Rh/Al2O3Dosage be 0.5-
5wt%, in terms of the weight of diaminodiphenyl-methane raw material.
13. according to the method for claim 12, it is characterised in that the Rh/Al2O3Dosage be 1-3wt%, with diamino
The weight meter of base diphenyl methane raw material.
14. method according to claim 1 or 2, it is characterised in that the hydrogenation reaction is with or without solvent
Under the conditions of carry out.
15. according to the method for claim 14, it is characterised in that the hydrogenation reaction under conditions of containing solvent into
OK, the concentration of diaminodiphenyl-methane raw material in the solution is 40-70wt%, in terms of solution weight.
16. according to the method for claim 15, it is characterised in that the diaminodiphenyl-methane raw material is in the solution
Concentration is 50-60wt%, in terms of solution weight.
17. according to the method for claim 16, it is characterised in that the solvent is selected from hexamethylene, dioxane, tetrahydrochysene
Furans, cyclohexylamine, dicyclohexyl amine, methanol, ethanol, isopropanol, n-butanol, 2- butanol and one kind or more in hexahydrotoluene
Kind.
18. method according to claim 1 or 2, it is characterised in that the reaction temperature is 100-250 DEG C；Described
Reaction absolute pressure is 3-15MPa.
19. according to the method for claim 18, it is characterised in that the reaction temperature is 150-200 DEG C；Described is anti-
It is 5-10MPa to answer absolute pressure.
20. according to the method for claim 19, it is characterised in that the reaction temperature is 170-190 DEG C；Described is anti-
It is 6-8MPa to answer absolute pressure.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108855210A (en) * | 2018-07-24 | 2018-11-23 | 万华化学集团股份有限公司 | Handle H12The catalyst system and processing method of MDA secondary amine tar |
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| CN111804324B (en) * | 2020-07-09 | 2022-08-23 | 万华化学集团股份有限公司 | Modified metal supported catalyst, diaminodicyclohexylmethane product, and preparation method and application thereof |
| KR20230039949A (en) * | 2021-09-15 | 2023-03-22 | 금호석유화학 주식회사 | Method for preparing hydrogenated bisphenol a |
| CN115960000B (en) * | 2022-12-09 | 2024-06-25 | 万华化学集团股份有限公司 | Method for synthesizing methylcyclohexanediamine by hydrogenating diaminotoluene |
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| CN116621711B (en) * | 2023-04-18 | 2023-12-15 | 同创化学(南京)有限公司 | Continuous preparation method of 4,4' -diamino dicyclohexyl methane |
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| CN108855210A (en) * | 2018-07-24 | 2018-11-23 | 万华化学集团股份有限公司 | Handle H12The catalyst system and processing method of MDA secondary amine tar |
| CN108855210B (en) * | 2018-07-24 | 2021-01-15 | 万华化学集团股份有限公司 | Treatment H12Catalyst system and treatment method of MDA secondary amine tar |
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