CN106946712A - The method that fixed bed hydrogenation method produces 1 amino naphthalenes - Google Patents
The method that fixed bed hydrogenation method produces 1 amino naphthalenes Download PDFInfo
- Publication number
- CN106946712A CN106946712A CN201710141102.9A CN201710141102A CN106946712A CN 106946712 A CN106946712 A CN 106946712A CN 201710141102 A CN201710141102 A CN 201710141102A CN 106946712 A CN106946712 A CN 106946712A
- Authority
- CN
- China
- Prior art keywords
- fixed bed
- amino naphthalenes
- produces
- reaction
- bed hydrogenation
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 57
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical class C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- RJKGJBPXVHTNJL-UHFFFAOYSA-N 1-nitronaphthalene Chemical compound C1=CC=C2C([N+](=O)[O-])=CC=CC2=C1 RJKGJBPXVHTNJL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000000694 effects Effects 0.000 claims abstract description 8
- 238000004821 distillation Methods 0.000 claims abstract description 7
- 238000004807 desolvation Methods 0.000 claims abstract description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 238000001994 activation Methods 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 239000007868 Raney catalyst Substances 0.000 claims 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- 230000001988 toxicity Effects 0.000 abstract description 3
- 231100000419 toxicity Toxicity 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 208000012839 conversion disease Diseases 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 8
- 238000010924 continuous production Methods 0.000 description 8
- 230000009467 reduction Effects 0.000 description 5
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004434 industrial solvent Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 239000002351 wastewater Substances 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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 invention discloses a kind of method that fixed bed hydrogenation method produces 1 amino naphthalenes, comprise the following steps：It is seated in nickel catalyst carried in fixed bed reactors and activates, 1 nitronaphthalene solution is pumped into fixed bed reactors, and be passed through hydrogen and carry out hydrogenation reaction, 1 amino naphthalenes is produced after reaction solution, distillation desolvation are collected after the completion of reaction.Nickel catalyst carried to have very high hydrogenation activity and resistant to sulfur toxicity in fixed bed, activity stability was up to more than 5000 hours.It can be recycled, extend the service life of catalyst, reduce production cost.In addition, this method also has technique simple, easy to operate, economic security, production efficiency is high, reaction conversion ratio and the advantages of high income, meets industrialization production requirements.
Description
Technical field
1- amino naphthalenes are produced the present invention relates to fine chemistry industry preparing technical field, more particularly to a kind of fixed bed hydrogenation method
Method.
Background technology
Alpha naphthylamine also known as 1- amino naphthalenes, α-amino-naphthalene, alpha-naphthylamine or naphthalidine, are white needles, with niff.
Water is slightly soluble in, ethanol, ether is soluble in.The product are a variety of dyestuffs such as direct dyes, acid dyes, azoic dyes and disperse dyes
The intermediate of product, is the primary raw material of a variety of rubber antioxidants, is also used for organic synthesis.Alpha naphthylamine industrial production is mainly used
Crude naphthalene nitrification obtains nitronaphthalene and restores obtained alpha naphthylamine, and main restoring method has akali sulphide or iron powder reducing method and catalysis to add
Hydrogen reduction method, sodium sulfide reducing method, using sulphur and caustic soda producing alpha naphthylamine by reduction, exists as described in patent CN101973894A
Major defect have：Product yield is low, poor appearance, and produces a large amount of difficult waste water, waste residues, does not meet cleanly production
It is required that, high energy consumption does not meet the requirement of energy-saving and emission-reduction, is gradually replaced by catalytic hydrogenating reduction method.Catalytic hydrogenating reduction method has
The characteristics of having environment-friendly, can efficiently reduce three waste discharge, improve the yield of product.The catalysis of industrial applications is realized
Agent mainly has palladium carbon, Raney's nickel, but is due to that crude naphthalene brings catalyst in a small amount of sulfur compound impurities, actual hydrogenation process into
And easily poisoned by sulfur-containing compound, catalyst can not be recycled, and cause catalyst cost to remain high.Other catalyst are reported
There are ambrose alloy composite catalyst or nitrogen doped carbon nanotube, such as Chinese patent CN102304053A and CN105753717A, but at present all
Experimental stage is rested on, industrialization report is there are no.In addition, these in the prior art catalytic hydrogenation synthesis alpha naphthylamine generally use
Batch Process mode, inefficiency, catalyst activity is low, and yield is low, it is necessary to which continuous supplement, applies mechanically the few short life of number of times, behaviour
Make inconvenience, be now in experiment or lab scale stage, industrializing implementation is more difficult.
The content of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art there is provided a kind of catalyst to there is height to be hydrogenated with to live
Property and resistant to sulfur toxicity, production cost are low, production efficiency is high, technique is simple and convenient to operate, the fixed bed of conversion ratio and high income adds
The method that hydrogen method produces 1- amino naphthalenes.
In order to solve the above technical problems, the present invention uses following technical scheme：
A kind of method that fixed bed hydrogenation method produces 1- amino naphthalenes, comprises the following steps：
It is seated in nickel catalyst carried in fixed bed reactors, activates, 1- nitronaphthalene solution is pumped into fixed bed anti-
Answer in device, and be passed through hydrogen and carry out hydrogenation reaction, 1- amino is produced after reaction solution, distillation desolvation are collected after the completion of reaction
Naphthalene.
The method that above-mentioned fixed bed hydrogenation method produces 1- amino naphthalenes, it is preferred that it is described it is nickel catalyst carried in, Ni is
Active component, Ni is loaded on a catalyst support, and the catalyst carrier includes Al2O3Or MgAlO.
The method that above-mentioned fixed bed hydrogenation method produces 1- amino naphthalenes, it is preferred that the nickel catalyst carried preparation
Process is：Solvable nickel salt and nitrate react under precipitating reagent effect and precipitated, and dry and obtain after filtering distillation water washing
Loaded catalyst crude product is obtained, the solid controls to control under 200-600 DEG C of roasting 2-5h, switching atmosphere of hydrogen under nitrogen atmosphere
300-550 DEG C of roasting 2-4h, is produced nickel catalyst carried.
Wherein, nitrate includes the one or two in magnesium nitrate and aluminum nitrate；Precipitating reagent includes sodium metasilicate or sodium carbonate.
The method that above-mentioned fixed bed hydrogenation method produces 1- amino naphthalenes, it is preferred that the nickel catalyst carried activation
Process is：By nickel catalyst carried filling in the reactor, 170 DEG C are warming up under flowing hydrogen atmosphere, Phosphating Solution is passed through and starts
Phosphine, phosphine terminates rear hydrogen gas space velocity for 100-1000h-1, it is warming up to 300 DEG C and starts aging 1-8h.
Wherein, Phosphating Solution is mass concentration 1-15% triphenylphosphine solutions.
The method that above-mentioned fixed bed hydrogenation method produces 1- amino naphthalenes, it is preferred that the reaction temperature of the hydrogenation reaction is
100~300 DEG C, hydrogen pressure ＞ 1.0MPa, air speed is .0.1~1.0h-1(weight ratio at 25 DEG C).
The method that above-mentioned fixed bed hydrogenation method produces 1- amino naphthalenes, it is preferred that in the 1- nitronaphthalenes solution, 1- nitros
The weight ratio of naphthalene and solvent is 1: 0.3~5.
The method that above-mentioned fixed bed hydrogenation method produces 1- amino naphthalenes, it is preferred that the solvent includes alcohols, amine, virtue
Hydrocarbon or halogenated alkane.
Compared with prior art, the advantage of the invention is that：
1st, the method that fixed bed hydrogenation method of the invention produces 1- amino naphthalenes, fixed bed is used as using nickel catalyst carried
The catalyst of catalytic hydrogenation method production 1- amino naphthalenes, high mechanical strength (>20N/cm), physical table area height (100-300m2/g)、
Active metal nickel surface area height (>50m2/ g), aperture can modulation (6-12nm), have in fixed bed very high hydrogenation activity and
Resistant to sulfur toxicity, activity stability was up to more than 5000 hours.Catalyst can be recycled, and extend the service life of catalyst, reduction
Production cost.
2nd, the method that fixed bed hydrogenation method of the invention produces 1- amino naphthalenes, catalytic hydrogenation is carried out using fixed bed reactors
Reaction, technique is simple, easy to operate, economic security, production efficiency height, reaction conversion ratio and high income, meets industrialized production
It is required that.
3rd, further, the method that fixed bed hydrogenation method of the invention produces 1- amino naphthalenes, can be used conven-tional industrial solvent
Dissolve raw material 1- nitronaphthalenes, do not influence hydrogenation reaction to carry out, solvent is cheap and easily-available, and it is recyclable apply mechanically, recovery method is simply just
Victory, with commercial viability.
Embodiment
Below in conjunction with specific preferred embodiment, the invention will be further described, but not thereby limiting the invention
Protection domain.
Nickel catalyst carried in following examples, using Ni as active component, Ni is loaded on a catalyst support, catalysis
Agent carrier includes Al2O3Or MgAlO.
The nickel catalyst carried preparation process is：The nickel catalyst carried preparation process is：Solvable nickel salt
React and precipitated under precipitating reagent effect with nitrate, drying acquisition loaded catalyst is thick after filtering distillation water washing
Product, the solid controls 300-550 DEG C of roasting 2- of control under 200-600 DEG C of roasting 2-5h, switching atmosphere of hydrogen under nitrogen atmosphere
4h, is produced nickel catalyst carried.
Wherein, nitrate includes the one or two in magnesium nitrate and aluminum nitrate；Precipitating reagent includes sodium metasilicate or sodium carbonate.
The nickel catalyst carried of gained is cloverleaf pattern.Feature mainly have it is following some：First, high mechanical strength (>20N/
cm)；2nd, physical table area height (100~300m2/g)；3rd, aperture can modulation (6~12nm), to adapt to different molecule chis
It is very little；4th, active metal nickel surface area it is high (>50m2/g).Use packing method：Take 10g catalyst and 10g quartz sands mixed when using
Caliber 10mm is seated in after closing uniformly, length 60cm reaction tube stage casing, the upper-lower section of reaction tube fills quartz sand, and insertion is carried
In thermocouple thermometer warm sleeve.It can be used after activated.
Embodiment 1：
1- nitronaphthalenes are dissolved in standby during ethanol turns, the weight ratio of 1- nitronaphthalenes and ethanol is 1: 2.Ni/MgAlO is urged
Agent load in the reactor, 170 DEG C are warming up under flowing hydrogen atmosphere, be passed through Phosphating Solution start phosphine (Phosphating Solution be quality it is dense
Spend 7.5% triphenylphosphine solution), phosphine terminates rear hydrogen gas space velocity for 500h-1, it is warming up to 300 DEG C and starts aging 4h.
1- nitronaphthalene solution is pumped into fixed bed reactors by fixed bed feed pump, and is passed through hydrogen, controls fixed bed temperature
200 DEG C of degree, hydrogen pressure 3.0MPa, air speed 0.25h-1, hydrogenation reaction is carried out, while the reaction that will be flowed out again with reflux pump from fixed bed
Liquid pump goes out, and the flow velocity of feed pump is 40ml/h, and 1- amino naphthalenes are produced after collecting reaction solution, distillation desolvation.Continuous production
4000 hours, conversion rate of products 99.8%, yield 99.6%；More than the conversion ratio 98.3% after 5000 hours, yield 98%.
Embodiment 2：
The present embodiment is substantially the same manner as Example 1, and it only difference is that：Control 130 DEG C of fixed bed temperature.Continuous production
4000 hours, conversion rate of products 99.6%, yield 99.2%；More than the conversion ratio 98% after 5000 hours, yield 97.8%.
Embodiment 3：
The present embodiment is substantially the same manner as Example 1, and it only difference is that：Control 250 DEG C of fixed bed temperature.Continuous production
4000 hours, conversion rate of products 99.6%, yield 99.2%；More than the conversion ratio 97% after 5000 hours, yield 96.5%.
Embodiment 4：
The present embodiment is substantially the same manner as Example 1, and it only difference is that：Control hydrogen pressure 2.0Mpa.Continuous production 4000
Hour, conversion rate of products 99.0%, yield 98.8% does not change, more than the conversion ratio 98.8% after 5000 hours, yield
98.2%.
Embodiment 5：
The present embodiment is substantially the same manner as Example 1, and it only difference is that：Control air speed 0.35h-1.Continuous production 3000
Hour obtains conversion rate of products 99.0%, yield 99.2%, more than the conversion ratio 96% after 4000 hours, yield 94.60%.
Embodiment 6：
The present embodiment is substantially the same manner as Example 1, and it only difference is that：Control air speed 0.5h-1(woulding you please supplementary unit).
Continuous produce obtains conversion rate of products 98.2% for 3000 hours, yield 97.6%, more than the conversion ratio 94.5% after 4000 hours,
Yield 93.2%.
Embodiment 7：
The present embodiment is substantially the same manner as Example 1, and it only difference is that：Piperidines is replaced into the ethanol in embodiment 1.Even
Continuous production 3000 hours, conversion rate of products 99.6%, yield 99.2% does not change, more than the conversion ratio 98% after 5000 hours,
Yield 96.8%.
Embodiment 8：
The present embodiment is substantially the same manner as Example 1, and it only difference is that：Toluene is replaced into the ethanol in embodiment 1.Even
Continuous production 3000 hours, conversion rate of products 99.6%, yield 99.2%, more than the conversion ratio 96% after 5000 hours, yield
94.7%.
Embodiment 9：
The present embodiment is substantially the same manner as Example 1, and it only difference is that：1,2- dichloroethanes is replaced in embodiment 1
Ethanol.Continuous production 3000 hours, obtains conversion rate of products 99.8%, yield 99.2%.More than the conversion after 5000 hours
Rate 97%, yield 95.6%.
The above is only the preferred embodiment of the present invention, and protection scope of the present invention is not limited merely to above-mentioned implementation
Example.All technical schemes belonged under thinking of the present invention belong to protection scope of the present invention.It is noted that for the art
Those of ordinary skill for, improvements and modifications under the premise without departing from the principles of the invention, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (7)
1. a kind of method that fixed bed hydrogenation method produces 1- amino naphthalenes, comprises the following steps：
It is seated in nickel catalyst carried in fixed bed reactors, activates, 1- nitronaphthalene solution is pumped into fixed bed reactors
In, and hydrogen progress hydrogenation reaction is passed through, produce 1- amino naphthalenes after reaction solution, distillation desolvation are collected after the completion of reaction.
2. the method that fixed bed hydrogenation method according to claim 1 produces 1- amino naphthalenes, it is characterised in that the support type
In Raney nickel, Ni is active component, and Ni is loaded on a catalyst support, and the catalyst carrier includes Al2O3Or MgAlO.
3. the method that fixed bed hydrogenation method according to claim 2 produces 1- amino naphthalenes, it is characterised in that the support type
The preparation process of Raney nickel is：Solvable nickel salt and nitrate react under precipitating reagent effect and precipitated, filtering distillation
Drying obtains loaded catalyst crude product after water washing, and the solid controls 200-600 DEG C of roasting 2-5h, switching under nitrogen atmosphere
300-550 DEG C of roasting 2-4h is controlled under atmosphere of hydrogen, is produced nickel catalyst carried.
4. the method that fixed bed hydrogenation method according to claim 1 produces 1- amino naphthalenes, it is characterised in that the support type
The activation process of Raney nickel is：By nickel catalyst carried filling in the reactor, 170 DEG C are warming up under flowing hydrogen atmosphere,
It is passed through Phosphating Solution and starts phosphine, phosphine terminates rear hydrogen gas space velocity for 100-1000h-1, it is warming up to 300 DEG C and starts aging 1-8h.
5. the method that the fixed bed hydrogenation method according to any one of Claims 1 to 4 produces 1- amino naphthalenes, it is characterised in that
The reaction temperature of the hydrogenation reaction is 100~300 DEG C, hydrogen pressure ＞ 1.0MPa, and air speed is .0.1~1.0h-1。
6. the method that the fixed bed hydrogenation method according to any one of Claims 1 to 4 produces 1- amino naphthalenes, it is characterised in that
In the 1- nitronaphthalenes solution, the weight ratio of 1- nitronaphthalenes and solvent is 1: 0.3~5.
7. the method that fixed bed hydrogenation method according to claim 6 produces 1- amino naphthalenes, it is characterised in that the solvent bag
Include alcohols, amine, aromatic hydrocarbons or halogenated alkane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710141102.9A CN106946712A (en) | 2017-03-10 | 2017-03-10 | The method that fixed bed hydrogenation method produces 1 amino naphthalenes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710141102.9A CN106946712A (en) | 2017-03-10 | 2017-03-10 | The method that fixed bed hydrogenation method produces 1 amino naphthalenes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106946712A true CN106946712A (en) | 2017-07-14 |
Family
ID=59468317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710141102.9A Pending CN106946712A (en) | 2017-03-10 | 2017-03-10 | The method that fixed bed hydrogenation method produces 1 amino naphthalenes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106946712A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109928883A (en) * | 2017-12-19 | 2019-06-25 | 南京大学 | A kind of method of catalytic hydrogenation naphthalidine |
| CN109926051A (en) * | 2017-12-19 | 2019-06-25 | 南京大学 | A kind of preparation method of the Raney nickel for 1- nitronaphthalene catalytic hydrogenation |
| CN110407709A (en) * | 2018-04-26 | 2019-11-05 | 南京大学 | A kind of method that catalytic hydrogenation prepares p-aminoanisole |
| CN110407707A (en) * | 2018-04-26 | 2019-11-05 | 南京大学 | A kind of method that catalytic hydrogenation prepares aniline |
| CN116396173A (en) * | 2023-03-20 | 2023-07-07 | 郑州大学 | A kind of method for preparing 1-naphthylamine by continuous catalytic hydrogenation of nitronaphthalene |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101434550A (en) * | 2008-11-07 | 2009-05-20 | 甘肃中科药源生物工程有限公司 | Method for preparing 1-naphthylamine from 1-nitronaphthalene |
| CN101733106A (en) * | 2009-12-16 | 2010-06-16 | 南京大学 | Preparation method of supported nickel catalyst |
| CN105312071A (en) * | 2014-07-28 | 2016-02-10 | 南京大学 | A kind of preparation method of Ni2P catalyst supported by composite oxide |
| CN107540533A (en) * | 2016-06-29 | 2018-01-05 | 姜桂萍 | L lactic acid Full-automatic constant-temperature continuous acidolysis process methods |
-
2017
- 2017-03-10 CN CN201710141102.9A patent/CN106946712A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101434550A (en) * | 2008-11-07 | 2009-05-20 | 甘肃中科药源生物工程有限公司 | Method for preparing 1-naphthylamine from 1-nitronaphthalene |
| CN101733106A (en) * | 2009-12-16 | 2010-06-16 | 南京大学 | Preparation method of supported nickel catalyst |
| CN105312071A (en) * | 2014-07-28 | 2016-02-10 | 南京大学 | A kind of preparation method of Ni2P catalyst supported by composite oxide |
| CN107540533A (en) * | 2016-06-29 | 2018-01-05 | 姜桂萍 | L lactic acid Full-automatic constant-temperature continuous acidolysis process methods |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109928883A (en) * | 2017-12-19 | 2019-06-25 | 南京大学 | A kind of method of catalytic hydrogenation naphthalidine |
| CN109926051A (en) * | 2017-12-19 | 2019-06-25 | 南京大学 | A kind of preparation method of the Raney nickel for 1- nitronaphthalene catalytic hydrogenation |
| CN110407709A (en) * | 2018-04-26 | 2019-11-05 | 南京大学 | A kind of method that catalytic hydrogenation prepares p-aminoanisole |
| CN110407707A (en) * | 2018-04-26 | 2019-11-05 | 南京大学 | A kind of method that catalytic hydrogenation prepares aniline |
| CN116396173A (en) * | 2023-03-20 | 2023-07-07 | 郑州大学 | A kind of method for preparing 1-naphthylamine by continuous catalytic hydrogenation of nitronaphthalene |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106946712A (en) | The method that fixed bed hydrogenation method produces 1 amino naphthalenes | |
| CN101733104B (en) | Catalyst for methanation of carbon dioxide-containing synthesis gas, preparation method and application | |
| CN106753549B (en) | A kind of method that the phenolic product hydrotreating of lignin depolymerization lightweight prepares HC fuel | |
| CN106179421B (en) | The preparation of sulfide catalyst and its application in lignin conversion | |
| CN101007275B (en) | Catalyst for hydrogenation of p-nitrophenol and preparation method thereof | |
| CN100575339C (en) | Method for preparing m-(β-hydroxyethylsulfone) aniline by hydrogenation of m-(β-hydroxyethylsulfone) nitrobenzene catalyzed by amorphous nickel alloy | |
| CN100354239C (en) | Method for preparing cyclohexyl bezene through highly-selectively catalytic hydrogenation for biphenyl | |
| CN106810683B (en) | A kind of method and device preparing polyetheramine | |
| CN110551278B (en) | Supported catalyst and preparation method and application thereof | |
| CN101157622A (en) | Process for synthesizing p-aminophenol from nitrobenzene by catalytic hydrogenation | |
| CN105566126A (en) | Method for preparing 2-amino-4-nitrophenol through liquid catalytic hydrogenation | |
| CN103772207B (en) | A kind of nitrobenzene one step catalytic hydrogenation high selectivity is prepared the method for cyclohexylamine | |
| CN101880242B (en) | Method for preparing 3-amino-4-methoxyacetanilide by taking Raney nickel as catalyst | |
| CN101474568B (en) | Selective hydrogenation olefin-removing bimetallic phosphide catalyst and preparation method thereof | |
| CN104744203B (en) | Method for preparing decahydronaphthalene by virtue of industrial naphthalene hydrogenation | |
| CN106977406A (en) | The method of continuous autoclave catalytic hydrogenation synthesizing amino naphthalene | |
| CN102050746A (en) | Method for preparing o-chloroaniline | |
| CN103694124A (en) | Method for high-selectivity preparation of 3,4-dichloroaniline | |
| CN102701905A (en) | Process for preparing cyclohexanone and cyclohexanol by cyclohexane selective oxidation | |
| CN104326875A (en) | Method for preparing bio-oil through hydrogenation degradation of lignin | |
| CN102212314A (en) | Method for preparing water-white highly-hydrogenated rosin | |
| CN100453525C (en) | The method for preparing 4-aminodiphenylamine | |
| CN101143323A (en) | Preparation and Application of Supported Nano-nickel Catalyst | |
| CN103450010B (en) | Method for preparing cyclohexanecarboxylic acid | |
| CN107488457B (en) | A kind of biomass liquid fuel and its preparation method and application |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170714 |