CN107382745B - A kind of method of nitrobenzene continuous liquid phase hydrogenation synthesis aniline - Google Patents
A kind of method of nitrobenzene continuous liquid phase hydrogenation synthesis aniline Download PDFInfo
- Publication number
- CN107382745B CN107382745B CN201710803255.5A CN201710803255A CN107382745B CN 107382745 B CN107382745 B CN 107382745B CN 201710803255 A CN201710803255 A CN 201710803255A CN 107382745 B CN107382745 B CN 107382745B
- Authority
- CN
- China
- Prior art keywords
- reactor
- nitrobenzene
- metal
- hydrogen
- liquid phase
- 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.)
- Expired - Fee Related
Links
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 title claims abstract description 108
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000007791 liquid phase Substances 0.000 title claims abstract description 31
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 21
- 230000015572 biosynthetic process Effects 0.000 title claims description 13
- 238000003786 synthesis reaction Methods 0.000 title claims description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 78
- 239000002184 metal Substances 0.000 claims abstract description 78
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000003054 catalyst Substances 0.000 claims abstract description 61
- 239000001257 hydrogen Substances 0.000 claims abstract description 49
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 49
- 239000007788 liquid Substances 0.000 claims abstract description 49
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000012856 packing Methods 0.000 claims abstract description 41
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 36
- 239000007789 gas Substances 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 238000010792 warming Methods 0.000 claims abstract description 16
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 238000006073 displacement reaction Methods 0.000 claims abstract description 3
- 239000012530 fluid Substances 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 30
- 239000000945 filler Substances 0.000 claims description 29
- 150000003839 salts Chemical class 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 239000008246 gaseous mixture Substances 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical compound [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 claims description 2
- 229910001630 radium chloride Inorganic materials 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 57
- 230000000694 effects Effects 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 2
- 230000036632 reaction speed Effects 0.000 abstract description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 30
- 230000008569 process Effects 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- 239000000470 constituent Substances 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- 239000010948 rhodium Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 4
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910000792 Monel Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- MWZNPHHDRLXXHO-UHFFFAOYSA-N rhodium;hydrate Chemical compound O.[Rh] MWZNPHHDRLXXHO-UHFFFAOYSA-N 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012546 transfer Methods 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
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention is a kind of method that nitrobenzene continuous liquid phase hydrogenation synthesizes aniline.Method includes the following steps: reactor is warming up to 60~200 equipped with after active metal/metal packing catalyst reactor 8~12 minutes with nitrogen displacementoThen C will be preheating to 40~120 respectivelyoThe nitrobenzene and hydrogen of C is continuously added to be reacted in reactor, 0.01~3h of liquid air speed of nitrobenzene‑1, the gas air speed of hydrogen is 100~2000h‑1, the pressure in reactor is 0.3~2.0MPa；The gas-liquid mixture come out from reactor is after condenser condenses, and hydrogen is back to reactor, and liquid phase obtains reaction product aniline.Catalyst activity metal of the present invention utilizes high with rate, and activity is good, and heat and mass surface area is big, and resistance is small, and for reaction process without effect of intraparticle diffusion, reaction speed is fast, equipment and simple production process, high production efficiency, and catalyst can maintain a long-term stability operation.
Description
Technical field
The invention belongs to field of catalytic reactions, more particularly to using metal packing as carrier prepare carried-type active metal/
Metal packing catalyst, the method for then carrying out nitrobenzene continuous liquid phase hydrogenation synthesis aniline using the catalyst.
Background technique
Aniline is a kind of important organic chemical industry's intermediate, is widely used in urethane raw diphenylmethane diisocyanate
The production of ester (MDI), fuel, medicine, rubber chemicals, pesticide and fine-chemical intermediate, market potential are larger.Aniline is raw at present
The process route of production at most, accounts for about the 85% of aniline total productive capacity with the application of nitrobenzene (NB) catalytic hydrogenation method.Industrial nitre
Base benzene catalytic hydrogenation method has fixed-bed catalytic that hydrogen, fluidized bed catalytic is added to add three kinds of techniques of hydrogen and liquid-phase hydrogenatin.Fixed Bed Gas Phase adds
Hydrogen aniline mostly uses Ni system or Cu series catalysts, and 150~300 DEG C of reaction temperature, 200~1500kPa of pressure.The technique has
Technology maturation, reaction temperature be low, equipment and it is easy to operate, maintenance cost is low, good product quality the advantages that, shortcoming is reaction
Pressure is high, Yi Fasheng hot-spot and cause side reaction and catalyst inactivation.Fluidized-bed hydrogenation technique can avoid the office of fixed bed
Frequent parking caused by portion's overheat and more catalyst changeout, is able to maintain continuous run in long period.Such as BASF AG's fluidized-bed hydrogenation
Technology is fed using nitrobenzene, hydrogen mixed atomizing, and hydrogenation reaction carries out under 250~300 DEG C, 400~1000kPa of pressure,
Technique and operation are relative complex.Nitrobenzene liquid-phase hydrogenatin industrial production equipment generallys use high activity noble metal catalyst.The U.S.
Patent US2293879 discloses a kind of liquid phase continuous catalytic hydrogenation technique, and using aniline as solvent, hydrogenation temperature is boiled close to solvent
Point, reaction pressure are less than 10kPa, and reaction heat is partly or entirely absorbed by product evaporation, and a large amount of aniline pass back into reactor, with
Keep the stabilization of operating condition.Liquid-phase hydrogenatin is with reaction temperature is low, side reaction is few, catalyst loading is high, equipment capacity
Greatly, advantages, the shortcomings such as gross investment is low are that reactant must be separated with catalyst, reactant with solvent, the behaviour of equipment
It is higher to make maintenance cost.
The present inventor discloses one kind in the immobilized active component preparation active reaction component of reactor component surface, utilizes work
Property reactive means carry out the method (CN201410526666.0) of synthesizing amino benzene by hydrogenation of nitrobenzene, the method includes by gold-supported
Load type metal catalyst, aqueous solvent and the promotor for belonging to active component are put into the reactor with metal component, are being stirred
With handled 1~10 hour under certain temperature in hydrogen atmosphere, supported catalyst is then recovered by filtration.Repeat the above process 3-4
Secondary, reactor component surface forms high activity reaction center.To equipped with active reaction component reactor in be added nitrobenzene into
Row reaction reacts 3h, nitrobenzene conversion rate and aniline yield rate are under the conditions of 120 DEG C of reaction temperature, Hydrogen Vapor Pressure 1.0MPa
99.5%.Although the above method may be implemented in direct supported active metals on metal material surface and be used for nitrobenzene liquid phase
Hydrogenation synthesis aniline reaction, but catalyst preparation need to be completed by loaded catalyst, treatment process needs, which are separated by filtration, urges
Agent, it is not only complicated for operation, but also need the recycling and utilization of used loaded catalyst active metal after solution processing
Problem, while also having considerable restraint to handled metal component structure, it is only applicable to reactor metal wall, agitating paddle, heat
Thermowell, cooling coil and can be a small amount of with additional metal plate washer, metal tube, wire mesh component pattern, reacted
The surface area that the available metal component of journey is contacted with reaction solution is small, and reaction needs intermittently to carry out in reaction kettle, production efficiency
It is low.
Summary of the invention
The technical problems to be solved by the present invention are: providing one kind for the deficiency of existing liquid-phase hydrogenatin production aniline process
Metal supported catalyst directly is prepared on Large ratio surface metal packing surface, it is continuous then to carry out nitrobenzene in the catalyst surface
The method of liquid-phase hydrogenatin synthesis aniline.The catalyst preparation process carries out in the pole dilute aqueous solution of metal salt, by metal
The formation of particle controls in extremely dilute metal salt solution, its concentration, which is in, at this time is conducive to the monatomic existing state of metal,
Metallic atom insert material surface is formed into stable activated centre, treatment process by the kinetic energy that stirring and treatment temperature provide
It is special to any type of metal material there is no the separation problem of solid catalyst in CN201410526666.0 and processing material
It is not that can complete to load to bigger serface metal packing, preparation method is simple.Catalyst activity metal of the present invention utilizes
Rate is high, and activity is good, and heat and mass surface area is big, and resistance is small, and for reaction process without effect of intraparticle diffusion, reaction speed is fast, equipment and life
Production. art is simple, high production efficiency, and catalyst can maintain a long-term stability operation.
The technical scheme is that
A kind of method of nitrobenzene continuous liquid phase hydrogenation synthesis aniline, comprising the following steps:
With nitrogen displacement equipped with after active metal/metal packing catalyst reactor 8~12 minutes, reactor is heated up
To 60~200 DEG C, then the nitrobenzene and hydrogen that are preheating to 40~120 DEG C respectively are continuously added to react in reactor,
0.01~3h of liquid air speed of nitrobenzene-1, the gas air speed of hydrogen is 100~2000h-1, the pressure in reactor is 0.3~
2.0MPa；For the gas-liquid mixture come out from reactor after condenser condenses, hydrogen is back to reactor, and liquid phase obtains reaction and produces
Object aniline；
The reactor is preferably tubular fixed-bed reactor or trickle bed reactor；
The liquid air speed of the nitrobenzene feed is preferably 0.2~1.2h-1, the gas air speed of hydrogen is preferably 160~900h-1；
The active metal/metal packing catalyst, is prepared by following methods, comprising the following steps:
Metal packing is fitted into reactor by the first step, and the admission space of filler is the 80%~90% of reactor volume；
Then nitrogen replacement Treatment device and pipe-line system are used；Final reactor is warming up to 80~200 DEG C；
Treatment fluid in solution reservoir is squeezed into preheater with pump by second step, then into the reactor of the first step,
0.15~2.0MPa of reactor pressure；It is vented after the gas condensation ejected by reactor, the liquid of discharge is collected into described
In solution reservoir, processing is continued to participate in as treatment fluid；After 1~2h of reactor continuous processing, active metal/metal packing is obtained
Catalyst；
Wherein, the temperature of the preheater is 80~200 DEG C, and the treatment fluid enters the mode of the first stage reactor
Enter in the reactor of the first step in reactor to enter directly into the first step, or after being mixed with nitrogen hydrogen mixeding gas；Nitrogen
The air speed of hydrogen gaseous mixture is 500~800h-1, nitrogen hydrogen ratio is 10:0.01~1；
The treatment fluid is the metal salt of active component and the mixed liquor that water is hybridly prepared into, the gold in terms of active component
The concentration for belonging to salt is 0.1~10ppm；The metal salt of the active component is the salt of platinum, palladium, rhodium, ruthenium, gold or nickel；
The metal packing is stainless steel, filler made of zirconium or alloy, the specific surface area of filler is 200~
5000m2/m3。
The metal salt of the active component is preferably chloroplatinic acid, palladium chloride, ruthenium trichloride or radium chloride.
Metal packing in the first step is preferably that specific surface area is 501~3700m2/m3θ ring filler or ripple
Filler.
In the second step, metal salt solution liquid air speed is preferably 50~100h-1。
In the second step, nitrogen hydrogen is than being preferably 10:1 in nitrogen hydrogen mixeding gas；
In the second step, the concentration of the metal salt of active component meter is preferably 0.5~3ppm in treatment fluid.
The beneficial effects of the present invention are:
(1) present invention provides a kind of for nitrobenzene continuous liquid phase hydrogenation active metal/metal packing catalyst, by
In the solution of extremely dilute metal salt, metallic atom is converted by metal salt using hydrogenating reduction or thermal decomposition and reduction, then molten
Metallic atom is quickly embedded in metal packing surface under the circulation collision effect of liquid and forms metal supported catalyst.Preparation method letter
It is single easy, it can be loaded in bigger serface metal packing, to form of bio-carrier, structure without specifically limited requirement.(2) originally
Invention provides a kind of for nitrobenzene continuous liquid phase hydrogenation active metal/metal packing catalyst, catalyst activity Metal Supported
Measure low, but utilization rate is high, and activity is good, and the nitrobenzene transformation frequency in terms of active metal reaches 9.69 X 104gNB·(g·h)-1,
Much higher than the activity level of current commercial catalyst.(3) present invention provides a kind of for nitrobenzene continuous liquid phase hydrogenation activity gold
Category/metal packing catalyst, reaction can be directly carried out continuously in filler surface, and resistance to mass tranfer is small, and heat transfer coefficient is high, be reacted
Journey does not need plus solvent, equipment and simple production process, high production efficiency without effect of intraparticle diffusion.(4) present invention provides one kind
For nitrobenzene continuous liquid phase hydrogenation active metal/metal packing catalyst, catalyst performance stabilised, reaction process is not catalyzed
Agent loss and inactivation regeneration issues, can remain stable over operation.
Specific embodiment
Embodiment 1
The first step, it is 100mm that the stainless steel θ ring filler filler that 4L specification is 3 × 3mm, which is put into diameter, a height of 600mm's
In tubular fixed-bed reactor, packing specific area 2800m2/m3, heap density is 460kg/m3；
Second step, with nitrogen replacement Treatment device and pipe-line system 8~12 minutes；
Third step, using chloroplatinic acid and water be hybridly prepared into 150L platinum concentration be 0.8ppm platinum acid chloride solution as treatment fluid
It is put into solution reservoir；
4th step, with pump by the treatment fluid in third step solution reservoir with air speed 100h-1Squeeze into preheater, the temperature of preheater
Degree is 80 DEG C, is then 500h with air speed-1, nitrogen hydrogen than for 10:1 nitrogen hydrogen mixeding gas mixing after enter the first step reactor
In and act on filler surface, the temperature of reactor is 80 DEG C, pressure 0.15MPa, after the gas condensation come out by reactor
Emptying；The solution reservoir that the liquid of discharge returns to third step continues the treatment process for continuously participating in this step as treatment fluid；Reaction
Device obtains Pt/ metal packing catalyst behind continuous circular treatment 1 hour for the treatment of fluid and nitrogen and hydrogen mixture.Utilize inductance coupling
It closes plasma emission spectrometer and Pt constituent content analysis is carried out to catalyst, Pt load capacity is 32.1mgkg-1；
5th step, uses N2Replace the tubular fixed-bed reactor and its pipe equipped with Pt/ metal packing catalyst of the 4th step
Reactor after 8~12 minutes, is warming up to 150 DEG C by road system.It by raw material nitrobenzene with flow is that 1.6L/h squeezes into preheating with pump
100 DEG C are preheated in device, then autoreactor bottom enters reactor (i.e. liquid air speed is 0.4h at this time-1).It will equally be warming up to
Hydrogen (the i.e. gas air speed 300h that 100 DEG C of flows are 1200L/h-1) gas-liquid distributor of reacted device bed bottom is dispersed to raw material
In liquid, gas-liquid mixture carries out catalysis reaction in filler catalyst surface, and nitrobenzene is made to be converted into aniline.Reaction pressure is
0.8MPa.The gas-liquid mixture come out from reactor is after condenser condenses, and hydrogen is recycled, and liquid phase is reaction product, nitre
Base benzene conversion ratio is 100%, and the yield of aniline is 99.8%, and converting into the nitrobenzene transformation frequency in terms of unit mass Pt is 3.25
ⅹ104gNB·(gPt·h)-1。
Embodiment 2
The first step, it is 100mm, the tubular type of a height of 600mm that the stainless steel θ ring filler that 4L specification is 2 × 2mm, which is put into diameter,
In fixed bed reactors, packing specific area 3700m2/m3, heap density is 576kg/m3；
Second step, with nitrogen replacement Treatment device and pipe-line system 8~12 minutes；
Third step, using chloroplatinic acid and water be hybridly prepared into 150L platinum concentration be 1.0ppm platinum acid chloride solution as treatment fluid
It is put into solution reservoir；
4th step, with pump by the treatment fluid in third step solution reservoir with air speed 100h-1Squeeze into preheater, the temperature of preheater
Degree is 80 DEG C, is then 800h with air speed-1, nitrogen hydrogen than for 10:1 nitrogen hydrogen mixeding gas mixing after enter the first step reactor
In, the temperature of reactor is 80 DEG C, pressure 0.15MPa, is vented after the gas condensation come out by reactor；The liquid of discharge returns
Solution reservoir to third step continues continuously to participate in the treatment process of this step as treatment fluid；Reactor passes through treatment fluid and nitrogen hydrogen
Behind continuous circular treatment 2 hours of gaseous mixture, Pt/ metal packing catalyst is obtained.Emit light using inductively coupled plasma body
Spectrometer carries out Pt constituent content analysis to catalyst, and Pt load capacity is 42.1mgkg-1；
5th step, uses N2Replace the tubular fixed-bed reactor and its pipe equipped with Pt/ metal packing catalyst of the 4th step
Reactor after 8~12 minutes, is warming up to reaction temperature, reaction temperature is 180 DEG C by road system.With pump by raw material nitrobenzene with
Flow is that 4.8L/h is squeezed into preheater and is preheated to 120 DEG C, and then autoreactor bottom enters reactor (i.e. liquid air speed is at this time
1.2h-1).It is 3600L/h (i.e. gas air speed 900h that 120 DEG C of flows, which will be equally warming up to,-1) hydrogen reacted device bed bottom
Gas-liquid distributor is dispersed in material liquid, and gas-liquid mixture carries out catalysis reaction in filler catalyst surface, converts nitrobenzene
For aniline.Reaction pressure is 1.2MPa.After condenser condenses, hydrogen is recycled the gas-liquid mixture come out from reactor,
Liquid phase is reaction product, and nitrobenzene conversion rate 100%, the yield of aniline is 99.7%, converts into the nitre in terms of unit mass Pt
Base benzene transformation frequency is 5.94 X 104gNB·(gPt·h)-1。
Embodiment 3
The first step, it is 100mm, the tubular fixed-bed reaction of a height of 600mm that 4L zirconium material perforated plate corrugated filler, which is put into diameter,
In device, packing specific area 501m2/m3, heap density is 325kg/m3；
Second step, with nitrogen replacement Treatment device and pipe-line system 8~12 minutes；
Third step, using chloroplatinic acid and water be hybridly prepared into 150L platinum concentration be 0.5ppm platinum acid chloride solution as treatment fluid
It is put into solution reservoir；
4th step, with pump by the treatment fluid in third step solution reservoir with air speed 100h-1Squeeze into preheater, the temperature of preheater
Degree is 150 DEG C, is then 800h with air speed-1, nitrogen hydrogen than for 10:1 nitrogen hydrogen mixeding gas mixing after enter the first step it is anti-
Filler surface is answered in device and acts on, the temperature of reactor is 150 DEG C, pressure 0.8MPa, comes out gas condensation by reactor
After be vented；The solution reservoir that the liquid of discharge returns to third step continues the treatment process for continuously participating in this step as treatment fluid；Instead
It answers device behind continuous circular treatment 2 hours for the treatment of fluid and nitrogen and hydrogen mixture, obtains Pt/ metal packing catalyst.Utilize electricity
Feel coupled plasma optical emission spectrometer and Pt constituent content analysis is carried out to catalyst, Pt load capacity is 38.1mgkg-1；
5th step, uses N2Replace the tubular fixed-bed reactor and its pipe equipped with Pt/ metal packing catalyst of the 4th step
Reactor after 8~12 minutes, is warming up to reaction temperature, reaction temperature is 200 DEG C by road system.With pump by raw material nitrobenzene with
4L/h, which is squeezed into preheater, is preheated to 120 DEG C, and then autoreactor bottom enters reactor (i.e. liquid air speed is 1.0h at this time-1)。
It is 2800L/h (i.e. gas air speed 700h that 120 DEG C of flows, which will be equally warming up to,-1) H2The gas-liquid distributor of reacted device bed bottom
It is dispersed in material liquid, gas-liquid mixture carries out catalysis reaction in filler catalyst surface, and nitrobenzene is made to be converted into aniline.Reaction
Pressure is 1.2MPa.After condenser condenses, hydrogen is recycled the gas-liquid mixture come out from reactor, and liquid phase is that reaction produces
Object, nitrobenzene conversion rate 100%, the yield of aniline are 99.7%, convert into the nitrobenzene transformation frequency in terms of unit mass Pt
For 9.69 X 104gNB·(gPt·h)-1。
Embodiment 4
The first step, it is 100mm that the screen waviness packings that 4L material is stainless steel, which are put into diameter, the drip of a height of 600mm
In bed reactor, packing specific area 700m2/m3, heap density is 415kg/m3；
Second step, with nitrogen replacement Treatment device 8~12 minutes；
Palladium chloride and water are hybridly prepared into the palladium chloride solution that 80L palladium concentration is 2ppm and put as treatment fluid by third step
Enter solution reservoir；
4th step, with the treatment fluid in pump third step solution reservoir with air speed 50h-1Squeeze into preheater, the temperature of preheater
It is 150 DEG C, subsequently into the reactor of the first step and filler surface is acted on, the temperature of reactor is 150 DEG C, and pressure is
0.3MPa；This step is continuously participated in as treatment fluid continuation by the solution reservoir that the liquid that reactor ejects returns to third step
Reason process；Reactor obtains Pd/ filler catalyst after the continuous circular treatment for the treatment of fluid 2 hours.Using inductive coupling etc. from
Daughter emission spectrometer carries out Pd constituent content analysis to catalyst, and Pd load capacity is 29.1mgkg-1；
5th step, uses N2Replace the trickle bed reactor and its pipe-line system equipped with Pd/ filler catalyst of the 4th step, 8
After~12 minutes, reactor is warming up to reaction temperature, reaction temperature is 60 DEG C.With pump by raw material nitrobenzene with 0.8L/h (i.e.
Liquid air speed 0.2h-1) squeeze into preheater and be preheated to 40 DEG C, then and being equally warming up to 40 DEG C of flows is 640L/h (i.e. gas air speed
160h-1) H2It mixes and enters reactor at the top of autoreactor.Gas-liquid mixture carries out catalysis reaction in filler catalyst surface,
Nitrobenzene is set to be converted into aniline.Reaction pressure is 2.0MPa.The gas-liquid mixture come out from reactor is after condenser condenses, hydrogen
Gas is recycled, and liquid phase is reaction product, and nitrobenzene conversion rate 95.0%, the yield of aniline is 99.9%, converts into unit
The nitrobenzene transformation frequency of quality Pd meter is 1.89 X 104gNB·(gPd·h)-1。
Embodiment 5
The first step, it is for 100mm, a height of 600mm that the net corrugated filling that 4L material is monel metal, which is put into diameter,
Tubular fixed-bed reactor in, packing specific area 643m2/m3, heap density is 508kg/m3；
Second step, with nitrogen replacement Treatment device and pipe-line system 8~12 minutes；
Third step, using rhodium chloride and water be hybridly prepared into 100L concentration be 1.5ppm rhodium chloride solution as handle
Liquid is put into solution reservoir；
4th step, with pump by the treatment fluid in third step solution reservoir with air speed 100h-1Squeeze into preheater, the temperature of preheater
Degree is 200 DEG C, is then 800h with air speed-1, nitrogen hydrogen than for 10:1 nitrogen hydrogen mixeding gas mixing after enter the first step reaction
In device and filler surface is acted on, the temperature of reactor is 200 DEG C, pressure 2.0MPa, is condensed by the gas that reactor comes out
After be vented；The solution reservoir that the liquid of discharge returns to third step continues the treatment process for continuously participating in this step as treatment fluid；Instead
It answers device behind continuous circular treatment 1 hour for the treatment of fluid and nitrogen and hydrogen mixture, obtains Rh/ metal packing catalyst.Utilize electricity
Feel coupled plasma optical emission spectrometer and Rh constituent content analysis is carried out to catalyst, Rh load capacity is 31.5mgkg-1；
5th step, uses N2Replace the tubular fixed-bed reactor and its pipe equipped with Rh/ metal packing catalyst of the 4th step
Reactor after 8~12 minutes, is warming up to reaction temperature, reaction temperature is 150 DEG C by road system.With pump by raw material nitrobenzene with
3.2L/h, which is squeezed into preheater, is preheated to 100 DEG C, and then autoreactor bottom enters reactor (i.e. at this time liquid air speed 0.8h-1)。
It is 2500L/h (i.e. gas air speed 625h that 100 DEG C of flows, which will be equally warming up to,-1) H2The gas-liquid distributor of reacted device bed bottom
It is dispersed in material liquid, gas-liquid mixture carries out catalysis reaction in filler catalyst surface, and nitrobenzene is made to be converted into aniline.Reaction
Pressure is 1.0MPa.After condenser condenses, hydrogen is recycled the gas-liquid mixture come out from reactor, and liquid phase is that reaction produces
Object, nitrobenzene conversion rate 100%, the yield of aniline are 99.7%, convert into the nitrobenzene transformation frequency in terms of unit mass Rh
For 6.0 X 104gNB·(gRh·h)-1。
Embodiment 6
The first step, it is 100mm, the tubular type of a height of 600mm that the stainless steel θ ring filler that 4L specification is 3 × 3mm, which is put into diameter,
In fixed bed reactors, packing specific area 2800m2/m3, heap density is 460kg/m3；；
Second step, with nitrogen replacement Treatment device and pipe-line system 8~12 minutes；
Third step, using ruthenium trichloride and water be hybridly prepared into 100L concentration be 1.5ppm solution of ruthenium trichloride as handle
Liquid is put into solution reservoir；
4th step, with pump by the treatment fluid in third step solution reservoir with air speed 100h-1Squeeze into preheater, the temperature of preheater
Degree is 100 DEG C, is then 800h with air speed-1, nitrogen hydrogen than for 10:1 nitrogen hydrogen mixeding gas mixing after enter the first step reaction
In device and filler surface is acted on, the temperature of reactor is 100 DEG C, pressure 0.3MPa, is condensed by the gas that reactor comes out
After be vented；The solution reservoir that the liquid of discharge returns to third step continues the treatment process for continuously participating in this step as treatment fluid；Instead
Device is answered to obtain Ru/ metal packing catalyst behind continuous circular treatment 1 hour for the treatment of fluid and nitrogen and hydrogen mixture.Utilize inductance
Coupled plasma optical emission spectrometer carries out Ru constituent content analysis to catalyst, and Ru load capacity is 51.3mgkg-1；
5th step, uses N2Replace the tubular fixed-bed reactor and its pipe equipped with Ru/ metal packing catalyst of the 4th step
Reactor after 8~12 minutes, is warming up to reaction temperature, reaction temperature is 120 DEG C by road system.With pump by raw material nitrobenzene with
1L/h, which is squeezed into preheater, is preheated to 80 DEG C, and then autoreactor bottom enters reactor (i.e. at this time liquid air speed 0.25h-1).It will
Equally being warming up to 80 DEG C of flows is 800L/h (i.e. gas air speed 200h-1) H2The vapor-liquid distributor of reacted device bed bottom disperses
Into material liquid, gas-liquid mixture carries out catalysis reaction in filler catalyst surface, and nitrobenzene is made to be converted into aniline.Reaction pressure
For 0.3MPa.The gas-liquid mixture come out from reactor is after condenser condenses, and hydrogen is recycled, and liquid phase is reaction product,
The yield of nitrobenzene conversion rate and aniline is 100%, and converting into the nitrobenzene transformation frequency in terms of unit mass Ru is 1.28 X
104gNB·(gRu·h)-1。
Embodiment 7
The reaction process of embodiment 2 is continuously run with 1000h, nitrobenzene conversion rate and aniline yield rate remain at
100% and 99.7%, the metal/metal filler catalyst performance stabilised invented.Emit light using inductively coupled plasma body
Spectrometer carries out Pt constituent content analysis to the catalyst after operating 1000h, and Pt load capacity is 42.1mgkg-1, preceding new with reacting
Fresh catalyst is compared there is no variation, and the loss problem of active metal is not present in reaction process.
Unaccomplished matter of the present invention is well-known technique.
Claims (6)
1. a kind of method of nitrobenzene continuous liquid phase hydrogenation synthesis aniline, it is characterized in that method includes the following steps:
With nitrogen displacement equipped with after active metal/metal packing catalyst reactor 8~12 minutes, reactor is warming up to
60~200oThen C will be preheating to 40~120 respectivelyoThe nitrobenzene and hydrogen of C is continuously added to be reacted in reactor, nitro
0.01~3h of liquid air speed of benzene-1, the gas air speed of hydrogen is 100~2000 h-1, the pressure in reactor is 0.3~2.0MPa；
The gas-liquid mixture come out from reactor is after condenser condenses, and hydrogen is back to reactor, and liquid phase obtains reaction product aniline；
The reactor is tubular fixed-bed reactor or trickle bed reactor；
The active metal/metal packing catalyst, is prepared by following methods, comprising the following steps:
Metal packing is fitted into reactor by the first step, and the admission space of filler is the 80%~90% of reactor volume；Then it uses
Nitrogen replacement Treatment device and pipe-line system；Final reactor is warming up to 80~200oC ；
Treatment fluid in solution reservoir is squeezed into preheater with pump, then into the reactor of the first step, reacted by second step
0.15~2.0MPa of device pressure；It is vented after the gas condensation ejected by reactor, the liquid of discharge is collected into the solution
In storage tank, processing is continued to participate in as treatment fluid；After 1~2 h of reactor continuous processing, obtains active metal/metal packing and urge
Agent；
Wherein, the temperature of the preheater is 80~200oC, the mode that the treatment fluid enters the first stage reactor are
It enters directly into the reactor of the first step, or enters in the reactor of the first step after being mixed with nitrogen hydrogen mixeding gas；Nitrogen hydrogen
The air speed of gaseous mixture is 500~800h-1, nitrogen hydrogen ratio is 10:0.01~1；
The treatment fluid is the metal salt of active component and the mixed liquor that water is hybridly prepared into, the metal salt in terms of active component
Concentration be 0.1~10ppm；
The metal packing is stainless steel, filler made of zirconium or alloy, and the specific surface area of filler is 200~5000m2/m3；
The metal salt of the active component is chloroplatinic acid, palladium chloride, ruthenium trichloride or radium chloride.
2. the method for nitrobenzene continuous liquid phase hydrogenation synthesis aniline as described in claim 1, it is characterized in that the first step
In metal packing be specific surface area be 501~3700 m2/m3θ ring filler or ripple packing.
3. the method for nitrobenzene continuous liquid phase hydrogenation synthesis aniline as described in claim 1, it is characterized in that the second step
In, metal salt solution liquid air speed is 50~100 h-1。
4. the method for nitrobenzene continuous liquid phase hydrogenation synthesis aniline as described in claim 1, it is characterized in that the second step
In, nitrogen hydrogen ratio is 10:1 in nitrogen hydrogen mixeding gas.
5. the method for nitrobenzene continuous liquid phase hydrogenation synthesis aniline as described in claim 1, it is characterized in that the second step
In, the concentration of the metal salt in treatment fluid in terms of active component is 0.5~3ppm.
6. the method for nitrobenzene continuous liquid phase hydrogenation synthesis aniline as described in claim 1, it is characterized in that the nitrobenzene
The liquid air speed of charging is preferably 0.2~1.2h-1, the gas air speed of hydrogen is preferably 160~900 h-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710803255.5A CN107382745B (en) | 2017-09-08 | 2017-09-08 | A kind of method of nitrobenzene continuous liquid phase hydrogenation synthesis aniline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710803255.5A CN107382745B (en) | 2017-09-08 | 2017-09-08 | A kind of method of nitrobenzene continuous liquid phase hydrogenation synthesis aniline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107382745A CN107382745A (en) | 2017-11-24 |
| CN107382745B true CN107382745B (en) | 2019-09-06 |
Family
ID=60352002
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710803255.5A Expired - Fee Related CN107382745B (en) | 2017-09-08 | 2017-09-08 | A kind of method of nitrobenzene continuous liquid phase hydrogenation synthesis aniline |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107382745B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107721804B (en) * | 2017-10-16 | 2020-09-18 | 绍兴贝斯美化工股份有限公司 | Method for preparing o-xylene through 3-nitro-o-xylene |
| CN110721646A (en) * | 2019-12-02 | 2020-01-24 | 河北工业大学 | Active micro-reactor |
| CN113429295B (en) * | 2021-07-12 | 2022-12-20 | 浙江迪邦化工有限公司 | Method for preparing m-phenylenediamine by continuous catalytic hydrogenation based on fixed bed microreactor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769164A (en) * | 2014-01-10 | 2014-05-07 | 浙江工业大学 | Stainless steel wire gauze platinum-loaded catalyst and application thereof |
| CN104311433A (en) * | 2014-10-09 | 2015-01-28 | 河北工业大学 | Process for synthesizing aniline by nitrobenzene hydrogenation |
-
2017
- 2017-09-08 CN CN201710803255.5A patent/CN107382745B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769164A (en) * | 2014-01-10 | 2014-05-07 | 浙江工业大学 | Stainless steel wire gauze platinum-loaded catalyst and application thereof |
| CN104311433A (en) * | 2014-10-09 | 2015-01-28 | 河北工业大学 | Process for synthesizing aniline by nitrobenzene hydrogenation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107382745A (en) | 2017-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107382745B (en) | A kind of method of nitrobenzene continuous liquid phase hydrogenation synthesis aniline | |
| US6676919B1 (en) | Method for producing platinum metal catalysts | |
| CN106699611B (en) | A kind of continuously hydrogen adding reduction prepares the production method of sodium m-aminobenzene sulfonate | |
| CN101658788B (en) | Catalyst for greenly synthesizing halogenated arylamine by means of high-efficiency catalytic hydrogenation of halogenated aromatic nitro compound and preparation method thereof | |
| CN101844976B (en) | Method for preparing butanedioic acid under catalytic hydrogenation | |
| CN110105223A (en) | A kind of method that continuity method prepares 1,3- hexamethylene dimethylamine | |
| CN102029199A (en) | Method for preparing load-type noble metal nanometer catalyst by solvent-free microwave-assisted pyrolysis method | |
| CN113620813B (en) | Preparation method of N, N-dimethyl-1, 3-propanediamine | |
| CN107473954A (en) | A kind of greenization production method of succinic acid | |
| CN113563201A (en) | Method for continuously and efficiently synthesizing 3, 4-dichloroaniline based on fixed bed microreactor | |
| CN107570146B (en) | Catalyst for directly loading active metal on metal filler | |
| CN108863738A (en) | A method of preparing cyclopentanone | |
| CN103214437A (en) | Continuous production method of 2-methyl tetrahydrofuran | |
| CN111689846B (en) | Process for producing succinic acid by aqueous phase hydrogenation | |
| CN102056879B (en) | Continuous process to produce hexafluoroisopropanol | |
| CN113563213B (en) | Preparation method of 3, 5-diaminobenzoic acid | |
| CN107570147B (en) | Application method of active metal/metal filler catalyst in reaction for synthesizing toluenediamine by hydrogenating dinitrotoluene | |
| CN102430404A (en) | Catalytic agent for synthesizing succinic acid through maleic acid hydrogenation and preparation method thereof | |
| CN103664586A (en) | Method for preparing cyclohexyl acetate and method for preparing cyclohexanol ethanol | |
| CN109096121A (en) | A kind of catalysis preparation method of trifluoroethylamine compound | |
| CN113307713A (en) | Method for preparing long-chain alkane by micro-channel-photocatalysis coupling | |
| CN106631819A (en) | Preparation method of 1,2-cyclohexyldiamine | |
| CN202506390U (en) | Reactor for producing hexanediamine through adiponitrile hydrogenation | |
| WO2018048320A1 (en) | Method for producing n-methyl-para-anisidine | |
| CN113797929A (en) | Solid catalyst for catalyzing synthesis of butanediamine, method for preparing butanediamine by using solid catalyst and system device |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190906 |