CN106631826A - Preparation method of H12MDA (diaminodicyclohexylmethane) - Google Patents
Preparation method of H12MDA (diaminodicyclohexylmethane) Download PDFInfo
- Publication number
- CN106631826A CN106631826A CN201611071703.9A CN201611071703A CN106631826A CN 106631826 A CN106631826 A CN 106631826A CN 201611071703 A CN201611071703 A CN 201611071703A CN 106631826 A CN106631826 A CN 106631826A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- methane
- diaminodiphenyl
- reaction
- raw material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Oc1ccccc1 Chemical compound Oc1ccccc1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/70—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
Abstract
The invention discloses a preparation method of H12MDA (diaminodicyclohexylmethane). According to the method, MDA (diaminodiphenyl-methane) is used as a raw material; in a hydrogenation reaction, the acidity of a phenolic compound is used for improving the catalyst activity; the generation of high-boiling-point tar in the reaction process is reduced; meanwhile, high-boiling-point tar covering the surface of the catalyst can be effectively brought out of a reaction system by a phenolic compound hydrogenation product of alicyclic alcohol type compounds; the problem of filtering difficulty due to high-boiling-point tar adsorption due to high-boiling-point tar adsorption on the surface of the catalyst can be solved; the reaction yield of H12MDA is improved, so that the activity of the catalyst can be greatly improved; the production efficiency is improved.
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), the isocyanates can be used to prepare 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 with regard to 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 HTHP
Yield and anti-body ratio.Because the noble metal catalyst for using is expensive, in order to reduce production cost, catalyst is circulated
Apply mechanically link very necessary.The catalyst recycled referred in most of patent is using built-in filter or external filtration
Product liquid is isolated reactor by device, and fresh MDA raw materials are put in the reaction of lower batch, and then is catalyzed next batch reaction.
And during the course of 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 of times, higher boiling tar is constantly covered and wrapped up in catalyst surface, and the continuous of tar is tired out
On the one hand product makes catalyst activity constantly decline, and then increases 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, it is tired so as to cause product liquid to filter
Difficulty, greatly extends filtration time, makes overall production efficiency decline to a great extent.Therefore, higher boiling in course of reaction how is reduced
The generation of tar is extremely important for production run efficiency is improved with the tar adhesion amount for how reducing catalyst surface.
US3591635 discloses a kind of reducing process of efficient many phenyl ring aromatic amine compounds, and it adopts 1-
20wt%Rh/Al2O3For catalyst, with 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 terminates, catalyst filtration is isolated, with ammonium hydroxide aqueous solution process at 60-80 DEG C, after being dried
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 adopts load Rh/Al2O3Catalysis
Agent, in high temperature relative superiority or inferiority MDA hydrogenation reactions are carried out, continuous logical after Rh catalyst and product are separated by filtration after reaction terminates
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 discloses one kind and can obtain preselecting 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 double-component
The mass ratio of agent, wherein rhodium and ruthenium is 3:7, carrier is aluminum oxide, barium sulfate etc., before catalytic reaction, adds 0.1-
The base-modified catalyst of 15wt%, while with THF as solvent, reacting under 170-195 DEG C and 700-1500psig, the reaction time
Less than 300min.
US6075167 provides a kind of aromatic diamine compound reduction work of the ruthenium catalysis with metal sulphite as accelerator
Skill, improves reaction rate, reduces the amount of high boiling point by-products produced tar.It adopts Ru for catalyst, activated carbon, calcium carbonate or
Aluminum oxide etc. is carrier, and the content of Ru metals is the 1-10wt% of carrier, then makees molten in alcohols, ethers or cyclo other compounds
Under agent, catalytic reaction is carried out with the solid-carried catalyst of aromatic diamines quality 0.1-5wt%, while adding 5-20 times of Ru mole of metal
The natrium nitrosum of amount is 100-200 DEG C as accelerator, reaction temperature, and reaction pressure is 500-2000psig.
There is following defect in prior art：
1) need to add alkali metal salt as accelerator, react to reduce with supported precious metal catalyst by alkali metal salt
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, needs are subsequently being urged
Agent adds incessantly new accelerator in applying mechanically, 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
Raise, beyond index.
2) when catalyst due to tar constantly accumulate cause activity decrease when, above section prior art need reaction knot
Shu Hou, after catalyst and product liquid are filtered, is individually washed, roasting and dried process to catalyst so as to regenerated.This will
Significantly reduce H12The production efficiency of MDA, makes production procedure more loaded down with trivial details, and production cost is dramatically increased.
3) prior art does not refer to and solves that batch reactor formula hydrogenation reaction prepares H12During MDA, catalyst with
Product liquid is separated by filtration the problem that can be dramatically increased as catalyst apply mechanically number of times increase the time.With Jiao of catalyst surface
Oily cumulant gradually increases, and filtration time can be caused significantly to extend, and so as to greatly reduce overall production efficiency, causes cost to show
Writing increases.
The content of the invention
The invention provides a kind of MDA hydrogenation reactions prepare H12The method of MDA, the method is by MDA raw materials, adding
Phenolic compound, using the acidity of phenolic compound the activity of catalyst is improved, and reduces the life of higher boiling tar in course of reaction
Into so as to improve H12The yield of MDA, while the online tar to catalyst surface is cleaned, highly shortened product liquid
With the time that is separated by filtration of catalyst, and then the activity of catalyst is significantly extended, production efficiency is improve well.
To reach object above, technical scheme is as follows：
The present invention provides a kind of H12The preparation method of MDA, comprises the steps：In MDA raw materials, add phenols chemical combination
Thing, hydrogenation reaction is carried out under certain temperature and pressure in reactor packed with catalyst and prepares H12MDA。
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, comprising following components：The 4,4 '-MDA of 96-100wt%, the 2,4 ' of 0-2wt%-
N- methyl -4 of MDA, 0-1wt%, other impurity of 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 the 0-0.5wt%,-MDA of N- methyl -4,4 ' of 0-0.4wt% and 0-0.1wt%
Other impurity, in terms of MDA raw material weights.
Step 1 of the present invention) in one or more in the compound of structure Formulas I and II of phenolic compound.
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, 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 one or more of group VIIIB metal,
It is preferred that one or more of Pt, Rh, Ru, Ir and Pd, the carrier is rare earth, diatomite, aluminum oxide, activated carbon, lithium aluminate, point
One or more of spar, silica and sieve and silica-sesquioxide, the content of metal is 1-10wt%, with metal load type catalyst weight
Calculate 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, preferably 30-40：1；The content of Rh is 1-10wt%, preferably 3-7wt%, more preferably 4-6wt%, with Rh/
Al2O3Meter；The content of Ru is 1-10wt%, preferably 3-7wt%, more preferably 4-6wt%, with Ru/Al2O3Meter.
When catalyst of the present invention uses Rh/Al2O3And Ru/Al2O3Mixture when, Rh/Al2O3Consumption be 0.5-
5wt%, 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 be carried out under conditions of with or without solvent, preferably comprise solvent.Such as
Fruit uses solvent, then MDA raw materials concentration in the solution is 40-70wt%, preferably 50-60wt%, in terms of solution weight.Institute
Solution is stated comprising MDA raw materials and solvent.
Solvent of the present invention is selected from hexamethylene, dioxane, tetrahydrofuran, cyclohexylamine, dicyclohexyl amine, methyl alcohol, second
One or more in alcohol, isopropanol, n-butanol, 2- butanol and hexahydrotoluene, preferred tetrahydrofuran.
Reaction temperature 100-250 DEG C of the present invention, preferably 150-200 DEG C, more preferably 170-190 DEG C；It is described
Reaction absolute pressure be 3-15MPa, more preferably preferably 5-10MPa, 6-8MPa.
The positive effect of the present invention：
1) present invention using phenolic compound participate in catalytic hydrogenation reaction, using its acid on-line control catalyst activity come
The content of high boiling point by-products produced tar is reduced, without the need for adding inorganic matter alkali metal salt as accelerator, therefore, do not result in load
The irreversible lesion of noble metal catalyst and carrier, can well keep catalyst activity and the selection to anti-body
Property.
2) the invention provides it is a kind of per batch 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 is wrapped up out of reaction system after thing hydrogenation,
Solve well catalyst and product liquid be separated by filtration the time can be with asking that catalyst applies mechanically that number of times increases and dramatically increase
Topic, drastically increases H12The production efficiency of MDA, simplifies Process planning flow, and saves production cost.
Specific 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 are from ten thousand China WANAMINE MDA-100.Wherein 4,4 '-MDA contents be 99.5wt%, N- methyl -4,
4 '-MDA contents are 0.35wt%, and other impurity contents are 0.15wt%.
Gas-chromatography is that Agilent company 6890 is serial, DB capillary chromatographic columns, and 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 2L with 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 rises high-temperature to 190 DEG C to 45-50bar (absolute pressure), and hydrogen is passed through in course of reaction
Flow controller continues to be passed through H toward reactor2, it is ensured 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 reactor, when temperature of reaction kettle is down to 50 DEG C, adopt less than 6bar (absolute pressure)
N2Product liquid is separated with catalyst filtration by built-in filter, and gas chromatographic analysis is carried out to product liquid, be the results are shown in Table
1.After product liquid is filtered totally, 500gMDA raw materials and 500g tetrahydrofurans and 15g phenol are continuously added, repeat to walk above
Suddenly, the recycled of catalyst is carried out.
The catalyst of the embodiment 1 of table 1 applies mechanically reaction result
* the reaction time for reach reaction temperature after timing to stop reaction.
Comparative example 1
It is 2L with 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 three times
Afterwards, then H is used2Ftercompction rises high-temperature to 190 DEG C, by hydrogen flowing quantity control in course of reaction to 45-50bar (absolute pressure)
Device continues to be passed through H toward reactor2, it is ensured 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
Reactor carries out cooling pressure release, when temperature of reaction kettle is down to 50 DEG C, using the N less 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 is filtered totally, 500gMDA raw materials and 500g tetrahydrofurans are continuously added, repeat above step, carry out the circulation of catalyst
Apply mechanically.
The catalyst of the comparative example 1 of table 2 applies mechanically reaction result
From table 2 it can be seen that in the reaction of Run1, due to fully not activating, the reaction time is up to 425min to catalyst.
Subsequently, in Run2-10, reaction time and filtration time do not have significantly 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 2L with 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 rises high-temperature to 170 DEG C to 45-50bar (absolute pressure), and hydrogen is passed through in course of reaction
Flow controller continues to be passed through H toward reactor2, it is ensured 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 reactor, when temperature of reaction kettle is down to 50 DEG C, adopt less than 6bar (absolute pressure)
N2Product liquid is separated with catalyst filtration by built-in filter, and gas chromatographic analysis is carried out to product liquid, be the results are shown in Table
3.After product liquid is filtered totally, 500gMDA raw materials and 500g tetrahydrofurans and 25g bisphenol-As are continuously added, repeat to walk above
Suddenly, the recycled of catalyst is carried out.
The catalyst of the embodiment 2 of table 3 applies mechanically reaction result
Embodiment 3
It is 2L with 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 three times
Afterwards, then H is used2Ftercompction rises high-temperature to 190 DEG C, by hydrogen flowing quantity control in course of reaction to 45-50bar (absolute pressure)
Device continues to be passed through H toward reactor2, it is ensured 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
Reactor carries out cooling pressure release, when temperature of reaction kettle is down to 50 DEG C, using the N less 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 is filtered totally, 500gMDA raw materials and 500g tetrahydrofurans are continuously added, repeat above step, carry out the circulation of catalyst
Apply mechanically.Wherein in Run30-50, per batch 15g phenol is added in addition.
The catalyst of the embodiment 3 of table 4 applies mechanically reaction result
Embodiment 4
It is 2L with 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 rises high-temperature to 170 DEG C to 45-50bar (absolute pressure), is held by hydrogen flowing quantity controller in course of reaction
Continue and H is passed through toward reactor2, it is ensured 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 less than 6bar (absolute pressure)2By 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, repeat above step, carry out the recycled of catalyst.
Wherein in Run30-50, per batch 25g bisphenol-As are added in addition.
The catalyst of the embodiment 4 of table 5 applies mechanically reaction result
Embodiment 5
It is 2L with 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 rises high-temperature to 180 DEG C to 45-50bar (absolute pressure), and hydrogen is passed through in course of reaction
Flow controller continues to be passed through H toward reactor2, it is ensured 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 reactor, when temperature of reaction kettle is down to 50 DEG C, adopt less than 6bar (absolute pressure)
N2Product liquid is separated with catalyst filtration by built-in filter, and gas chromatographic analysis is carried out to product liquid, be the results are shown in Table
6.After product liquid is filtered totally, 600gMDA raw materials and 400g tetrahydrofurans and 0.6g phenol are continuously added, repeat to walk above
Suddenly, the recycled of catalyst is carried out.
The catalyst of the embodiment 5 of table 6 applies mechanically reaction result
Embodiment 6
It is 2L with 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 rises high-temperature to 180 DEG C to 45-50bar (absolute pressure), and hydrogen is passed through in course of reaction
Flow controller continues to be passed through H toward reactor2, it is ensured 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 reactor, when temperature of reaction kettle is down to 50 DEG C, adopt less than 6bar (absolute pressure)
N2Product liquid is separated with catalyst filtration by built-in filter, and gas chromatographic analysis is carried out to product liquid, be the results are shown in Table
7.After product liquid is filtered totally, 600gMDA raw materials and 400g tetrahydrofurans and 120g bisphenol-As are continuously added, more than repetition
Step, carries out the recycled of catalyst.
The catalyst of the embodiment 6 of table 7 applies mechanically reaction result
Claims (10)
1. a kind of preparation method of diamino-dicyclohexyl methane, comprises the steps：In diaminodiphenyl-methane raw material,
Addition phenolic compound, in reactor packed with catalyst, carries out under certain temperature and pressure hydrogenation reaction and prepares two
Amino bicyclic hexyl methane.
2. method according to claim 1, it is characterised in that described diaminodiphenyl-methane raw material is included with the following group
Point：The 4,4 ' of 96-100wt%-diaminodiphenyl-methane, the 2,4 '-diaminodiphenyl-methane of 0-2wt%, 0-1wt%
Other impurity of N- methyl -4,4 '-diaminodiphenyl-methane and 0-1wt%, in terms of diaminodiphenyl-methane raw material weight；
Preferably the 4,4 ' of 99-100wt%-diaminodiphenyl-methane, the 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.
3. method according to claim 1 and 2, it is characterised in that described phenolic compound is selected from structure Formulas I and II
One or more in compound,
Wherein R is selected from H or-(CH2)n-CH3, the integer of n=0～10；The phenolic compound is preferably phenol, to methylbenzene
One or more in phenol, m-methyl phenol, ortho-methyl phenol and bisphenol-A；More preferably phenol and/or bisphenol-A.
4. the method according to any one of claim 1-3, it is characterised in that the content of described phenolic compound is 0.1-
20wt%, preferably 1-10wt%, more preferably 3-5wt%, in terms of diaminodiphenyl-methane raw material weight.
5. the method according to any one of claim 1-4, it is characterised in that described catalyst is metal load type catalysis
Agent, wherein metal are one or more of group VIIIB metal, one or more of preferred Pt, Rh, Ru, Ir and Pd, the carrier
For one or more of rare earth, diatomite, aluminum oxide, activated carbon, lithium aluminate, spinelle, silica and sieve and silica-sesquioxide, metal
Content be 1-10wt%, on the basis of metal load type catalyst weight calculate.
6. method according to claim 5, it is characterised in that described catalyst is Rh/Al2O3And Ru/Al2O3Mixing
The weight ratio of thing, wherein Rh and Ru is 1-50：1, preferably 30-40：1；The content of Rh be 1-10wt%, preferably 3-7wt%,
More preferably 4-6wt%, with Rh/Al2O3Meter；The content of Ru be 1-10wt%, more preferably preferably 3-7wt%, 4-6wt%,
With Ru/Al2O3Meter.
7. method according to claim 6, it is characterised in that the Rh/Al2O3Consumption be 0.5-5wt%, preferably
1-3wt%, in terms of the weight of diaminodiphenyl-methane raw material.
8. the method according to any one of claim 1-7, it is characterised in that described hydrogenation reaction is with or without molten
Carry out under conditions of agent, preferably comprise solvent, diaminodiphenyl-methane raw material concentration in the solution is 40-70wt%, excellent
50-60wt% is elected as, in terms of solution weight.
9. method according to claim 8, it is characterised in that described solvent is selected from hexamethylene, dioxane, tetrahydrochysene furan
Mutter, one or more in cyclohexylamine, dicyclohexyl amine, methyl alcohol, ethanol, isopropanol, n-butanol, 2- butanol and hexahydrotoluene,
It is preferred that tetrahydrofuran.
10. the method according to any one of claim 1-9, it is characterised in that described reaction temperature 100-250 DEG C, it is excellent
Elect 150-200 DEG C, more preferably 170-190 DEG C as；Described reaction absolute pressure be 3-15MPa, preferably 5-10MPa, more
Preferably 6-8MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611071703.9A CN106631826B (en) | 2016-11-29 | 2016-11-29 | A kind of preparation method of diamino-dicyclohexyl methane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611071703.9A CN106631826B (en) | 2016-11-29 | 2016-11-29 | A kind of preparation method of diamino-dicyclohexyl methane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106631826A true CN106631826A (en) | 2017-05-10 |
| CN106631826B CN106631826B (en) | 2018-04-20 |
Family
ID=58813896
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611071703.9A Active CN106631826B (en) | 2016-11-29 | 2016-11-29 | A kind of preparation method of diamino-dicyclohexyl methane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106631826B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111804324A (en) * | 2020-07-09 | 2020-10-23 | 万华化学集团股份有限公司 | Modified metal supported catalyst, diaminodicyclohexylmethane product, and preparation method and application thereof |
| CN115806470A (en) * | 2021-09-15 | 2023-03-17 | 锦湖石油化学株式会社 | Process for preparing hydrogenated bisphenol A |
| CN116478048A (en) * | 2023-04-18 | 2023-07-25 | 同创化学(南京)有限公司 | Preparation method of 4,4' -diamino-dicyclohexyl methane with low trans-trans isomer content |
| CN116621711A (en) * | 2023-04-18 | 2023-08-22 | 同创化学(南京)有限公司 | Continuous preparation method of 4,4' -diamino dicyclohexyl methane |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4429155A (en) * | 1980-12-04 | 1984-01-31 | Basf Aktiengesellschaft | Preparation of aromatic amines |
| CN103265438A (en) * | 2013-05-22 | 2013-08-28 | 烟台万华聚氨酯股份有限公司 | Method for preparing diaminodicyclohexyl methane |
| CN104817459A (en) * | 2014-02-05 | 2015-08-05 | 拜耳材料科技股份有限公司 | Process for hydrogenating aromatic di- and polyamines to cycloaliphatic di- and polyamines |
-
2016
- 2016-11-29 CN CN201611071703.9A patent/CN106631826B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4429155A (en) * | 1980-12-04 | 1984-01-31 | Basf Aktiengesellschaft | Preparation of aromatic amines |
| CN103265438A (en) * | 2013-05-22 | 2013-08-28 | 烟台万华聚氨酯股份有限公司 | Method for preparing diaminodicyclohexyl methane |
| CN104817459A (en) * | 2014-02-05 | 2015-08-05 | 拜耳材料科技股份有限公司 | Process for hydrogenating aromatic di- and polyamines to cycloaliphatic di- and polyamines |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111804324A (en) * | 2020-07-09 | 2020-10-23 | 万华化学集团股份有限公司 | Modified metal supported catalyst, diaminodicyclohexylmethane product, and preparation method and application thereof |
| 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 |
| CN115806470A (en) * | 2021-09-15 | 2023-03-17 | 锦湖石油化学株式会社 | Process for preparing hydrogenated bisphenol A |
| CN116478048A (en) * | 2023-04-18 | 2023-07-25 | 同创化学(南京)有限公司 | Preparation method of 4,4' -diamino-dicyclohexyl methane with low trans-trans isomer content |
| CN116621711A (en) * | 2023-04-18 | 2023-08-22 | 同创化学(南京)有限公司 | Continuous preparation method of 4,4' -diamino dicyclohexyl methane |
| CN116478048B (en) * | 2023-04-18 | 2023-12-15 | 同创化学(南京)有限公司 | Preparation method of 4,4' -diamino-dicyclohexyl methane with low trans-trans isomer content |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106631826B (en) | 2018-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106631826B (en) | A kind of preparation method of diamino-dicyclohexyl methane | |
| EP2459311B1 (en) | Deoxygenation process | |
| CN102070448B (en) | Method for preparing dimethyl succinate | |
| CN110433823B (en) | Catalyst for synthesizing diaminomethylcyclohexane, and preparation method and application thereof | |
| CN107986974B (en) | Method for preparing cyclohexane dimethylamine | |
| CN103265438B (en) | Method for preparing diaminodicyclohexyl methane | |
| CN110981705B (en) | Method for preparing cyclohexane dimethylamine | |
| CN110386856B (en) | Method for preparing 1, 3-propylene glycol by hydration and hydrogenation of acrolein | |
| CN113117743B (en) | Preparation method of hydrogenation catalyst and method for preparing hydrogenated bisphenol A | |
| EP3118181A1 (en) | Composite metal catalyst composition, and method and apparatus for preparing 1,4-cyclohexanedimethanol using same | |
| KR102472836B1 (en) | Method for hydrogenation of toluenediamine (TDA) tar | |
| CN114082428B (en) | Hydrogenation catalyst, preparation method and application thereof | |
| CN113877630B (en) | Catalyst for preparing bis [ (3-dimethylamino) propyl ] amine and application thereof | |
| CN112047843B (en) | Method for improving stability of m-xylylenediamine fixed bed hydrogenation catalyst | |
| CN108440311A (en) | A kind of Hydrogenation for diaminodiphenyl-methane method | |
| CN102574772B (en) | Process for reductive amination of aliphatic cyanoaldehydes to aliphatic diamines | |
| JPH1087572A (en) | Production of primary and/or secondary amine from oxo compound | |
| CN107857704B (en) | Method for preparing 3-aminomethyl-3, 5, 5-trimethylcyclohexylamine and catalyst used in method | |
| CN108840801B (en) | Regeneration process of catalyst in continuous production process of PACM50 | |
| CN110204447B (en) | Regeneration method of catalyst in continuous production process of 4, 4' -diaminodicyclohexyl methane | |
| CN116836067A (en) | Method for preparing diaminodiphenyl ether by continuous catalytic hydrogenation | |
| CN111574645A (en) | Hydrogenation method for high-sulfur petroleum resin | |
| CN108516939B (en) | Preparation method of 4, 4' -diaminodicyclohexylmethane with high content of trans-product | |
| CN105061176A (en) | Fixed-bed synthetic method for 3,3,5-trimethylcyclohexanone | |
| CN113101928B (en) | Catalyst for preparing 1, 4-butenediol from 1, 4-butynediol and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A preparation method of diaminodicyclohexylmethane Effective date of registration: 20211123 Granted publication date: 20180420 Pledgee: Bank of China Limited by Share Ltd. Yantai branch Pledgor: Wanhua Chemical Group Co.,Ltd. Registration number: Y2021980013026 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20220622 Granted publication date: 20180420 Pledgee: Bank of China Limited by Share Ltd. Yantai branch Pledgor: Wanhua Chemical Group Co.,Ltd. Registration number: Y2021980013026 |