CN109529826A - A kind of continuity method prepares the method and catalyst of cyclohexyl methylamine - Google Patents
A kind of continuity method prepares the method and catalyst of cyclohexyl methylamine Download PDFInfo
- Publication number
- CN109529826A CN109529826A CN201811307413.9A CN201811307413A CN109529826A CN 109529826 A CN109529826 A CN 109529826A CN 201811307413 A CN201811307413 A CN 201811307413A CN 109529826 A CN109529826 A CN 109529826A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carrier
- minutes
- solution
- ruthenium
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 21
- XTUVJUMINZSXGF-UHFFFAOYSA-N N-methylcyclohexylamine Chemical compound CNC1CCCCC1 XTUVJUMINZSXGF-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 14
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 22
- 239000012065 filter cake Substances 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 13
- 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 claims description 11
- 239000013078 crystal Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 11
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 229960000892 attapulgite Drugs 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 229910052625 palygorskite Inorganic materials 0.000 claims description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- -1 nitric acid aluminium salt Chemical class 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 claims description 2
- 238000009938 salting Methods 0.000 claims description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims 2
- 239000002689 soil Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 13
- 238000010924 continuous production Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 38
- 239000000243 solution Substances 0.000 description 23
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000001768 carboxy methyl cellulose Substances 0.000 description 9
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 9
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- 230000001404 mediated effect Effects 0.000 description 9
- 230000003472 neutralizing effect Effects 0.000 description 9
- 239000011265 semifinished product Substances 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 6
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- SWGXDLRCJNEEGZ-UHFFFAOYSA-N N-cyclohexylformamide Chemical compound O=CNC1CCCCC1 SWGXDLRCJNEEGZ-UHFFFAOYSA-N 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000012825 JNK inhibitor Substances 0.000 description 1
- 229940118135 JNK inhibitor Drugs 0.000 description 1
- 238000006000 Knoevenagel condensation reaction Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 230000000202 analgesic effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals 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
- 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
- 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
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
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 preparation methods of cyclohexyl methylamine, use benzene methanamine for raw material, under the conditions of Ru catalyst is existing, cyclohexyl methylamine is prepared using fixed bed hydrogenation technique, its react in benzene methanamine conversion ratio up to 99.9%, product selectivity is the preparation method simple process, at low cost up to 98.5%, is suitble to industrialization continuous production.Used catalyst has suitable duct, suitable auxiliary agents is added to, so that catalyst duct is not easy to plug, the service life is longer.
Description
Technical field
The invention belongs to organic hydrogenation fields, and in particular to a kind of continuity method prepares the method for cyclohexyl methylamine and used
Catalyst.
Background technique
Benzene methanamine is important the intermediate of medicine, surfactant, dyestuff, while being also organic synthesis raw material.For
Raw material, cationic surfactant of surfactant amine etc..Since it contains phenyl ring, there are certain toxicity, therefore certain
The application in field is subject to certain restrictions, and its structure of cyclohexyl methylamine is similar to benzene methanamine, and physical and chemical performance is also more similar, therefore
Cyclohexyl methylamine can substitute benzene methanamine in some application fields.
Cyclohexyl methylamine is important organic synthesis raw material, can be used for the synthesis of medicine, pesticide etc., such as synthesis analgestic H,
Jnk inhibitor etc..Its primary synthetic methods is as follows: 1) using cyclohexyl formamide as raw material, urging in heavy metal or its oxycarbide
Under change, the hydro-reduction under high-temperature and high-pressure conditions, yield 83%~92%.This method Recent study is more, but reaction condition
It is required that high, catalytic reagent is expensive.2) using cyclohexyl formamide as raw material, borane reduction, yield 77%, wherein restoring are used
Reagent borine poor selectivity, low boiling point, inflammable, unsuitable long-distance transportation limits using and being mass produced for this method.
3) using cyclohexyl nitrile as raw material, use Raney Ni to restore as catalyst high-pressure hydrogenation, be most common synthesis side
One of method, this method is more mature, but selectivity and yield are lower, and purchase raw material cyanide formality is more loaded down with trivial details and expensive,
And condition of high voltage is needed, reduzate is often accompanied by the coupling by-products being not readily separated.4) using cyclohexanone as raw material, pass through
Knoevenagel reaction generates Nitromethylene cyclohexanone, and sodium borohydride/iodine reduction system obtains cyclohexyl methylamine, total recovery
83.6%, raw material, agents useful for same needed for this method are cheap and easy to get, and reaction condition is milder, but isolate and purify it is complex, together
When yield it is also not high.5) using benzene methanamine as raw material, under hydrogenation catalyst, it is hydrogenated to cyclohexyl methylamine, the process route raw material
Be easy to get, process route it is relatively easy, by-product is few, but the report of correlative study is less.
Summary of the invention
The technical problem to be solved by the present invention is to the prior art there are catalyst under the conditions of fixed bed continuously hydrogen adding because
It is the problems such as de- amido, knot carbon, not high so as to cause activity and selectivity, it is unfavorable for industrialization, the present invention uses suitable catalyst
And reaction process, reaction efficiency is improved, the production cost of product can be reduced.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows:
The preparation method of cyclohexyl methylamine of the present invention uses benzene methanamine for raw material in fixed bed reactors, deposits in ruthenium catalysis
In case plus hydrogen prepares cyclohexyl methylamine, the process conditions of hydrogenation reaction are as follows: 80~120 DEG C of temperature, 1~5MPa of pressure, liquid
0.5~2h of body air speed-1。
The group of ruthenium catalyst used in the present invention becomes, the mass content 0.1~0.3% of active element ruthenium, pH value
Auxiliary agent is adjusted, content is the 0.2~2% of quality of alumina, remaining is carrier, and the specific surface area of catalyst is 70~120m2/
G, 0.12~0.28mL/g of Kong Rong.
Carrier of the present invention is the mixture of aluminium oxide and attapulgite or diatomite.
Hydrogenation catalyst of the invention is prepared using following steps:
(A) it prepares acid aluminum nitrate solution to be added to being heated to 50~80 DEG C in the reaction kettle stirred, filler is added
It sufficiently stirs evenly, with sodium bicarbonate salting liquid, carries out neutralization precipitation, neutralize the time 15~30 minutes, adjusting endpoint pH 7.0~
8.0;
(B) it is aged 20~50 minutes at 60~80 DEG C, fixed crystal form obtains filter cake after washing, filtering;
(C) filter cake is dried to plasticity, and add-on type auxiliary agent extruded moulding carries out again at being then 600~800 DEG C in temperature
Roasting, obtains catalyst carrier for hydrgenating;
(D) with hydrate ruthenium trichloride and the solution for being configured to suitable concentration, solution B is uniformly sprayed onto carrier, material
It is first dried for the first time in constant temperature blast drying oven, then sample is moved in microwave oven and is heat-treated, obtain finished product
Catalyst;Catalyst activity element may be implemented using the drying means to migrate to catalyst surface, improve catalyst activity
The utilization rate at center reduces the usage amount of active element.
(E) activation of catalyst: catalyst is restored 4~8 hours at 200~300 DEG C with 5% hydrogen/nitrogen, is obtained
Catalyst prod.
Filler is one of attapulgite, diatomite in carrier preparation step (A) of the present invention.
Soluble salt pH value is incorporated in carrier preparation step (A) of the present invention in aluminium salt and adjusts auxiliary agent, soluble salt is selected from nitric acid
One or more of magnesium, zirconium nitrate, calcium nitrate.Carrier surface acid-base property can effectively be changed, while passing through several metals
The mutual synergistic effect of element and ruthenium element, it is suppressed that the generation that amine, knot carbon reaction are taken off in hydrogenation process, to improve
The yield of product cyclohexyl methylamine.
Specific embodiment
The method of the present invention is described in detail below with reference to embodiment, but the present invention is not limited to the embodiment.
Embodiment 1
Weighing nine water aluminum nitrate of 800g adds deionized water to be configured to 1L solution, pours into the 3L glass reaction with stirring and heating
It is warming up to 70 DEG C in kettle, attapulgite 300g is added, 6% sodium bicarbonate aqueous solution is added dropwise, carry out neutralization precipitation, neutralizing the time is
It 30 minutes, adjusts 7.2,70 DEG C of endpoint pH and is aged 40 minutes, fixed crystal form obtains filter cake after washing filtering;Filter cake is dried to
Water content 52%, addition pore-creating auxiliary agent carboxymethyl cellulose 2.2g are mediated 30 minutes, are then extruded intoBar shaped is cut after drying
At 3~5mm of length, then carries out roasting 2 hours at 750 DEG C again in Muffle furnace, obtain carrier.Weigh 0.77g RuCl3
3H2O is dissolved in 25g deionized water, after ultrasonic dissolution, solution is uniformly sprayed on 200g carrier, in 80 DEG C of thermostatic drying chambers
It places 1 hour, then sample is put into microwave oven, microwave frequency 300GHz, power 500W, handled 10 minutes
Afterwards, catalyst semi-finished product are obtained, then are restored 4 hours at 300 DEG C of 5% hydrogen/nitrogen of normal pressure, catalyst prod C1 is obtained.Catalysis
The Ru content of agent product is 0.15%, specific surface area 81.3m2/ g, Kong Rong 0.18mL/g.
Embodiment 2
It weighs nine water aluminum nitrate of 800g and 2.31g magnesium nitrate hexahydrate adds deionized water to be configured to 1L solution, pour into band stirring
Be warming up to 50 DEG C in the 3L glass reaction kettle of heating, attapulgite 250g is added, 8% sodium bicarbonate aqueous solution is added dropwise, carries out
Neutralization precipitation, neutralizing the time is 15 minutes, adjusts endpoint pH 7.2, is aged 35 minutes, and fixed crystal form obtains after washing filtering
Filter cake;Filter cake is dried to water content 48%, and addition pore-creating auxiliary agent carboxymethyl cellulose 2.8g is mediated 50 minutes, is then extruded intoBar shaped is cut into 3~5mm of length after drying, then carry out roasting 3 hours at 800 DEG C again in Muffle furnace, carried
Body.Weigh the RuCl33H of 0.77g2O is dissolved in 25g deionized water, and after ultrasonic dissolution, solution is uniformly sprayed onto 200g load
On body, it is placed at room temperature for 1 hour, then sample is put into microwave oven, microwave frequency 700GHz, power 600W, place
Reason after ten minutes, obtains catalyst semi-finished product, then restore 4 hours at 300 DEG C of 5% hydrogen/nitrogen of normal pressure, obtains catalyst prod
C2.The Ru content of catalyst prod is 0.15%, specific surface area 89.8m2/ g, Kong Rong 0.19mL/g.
Embodiment 3
It weighs nine water aluminum nitrate of 800g and five water zirconium nitrate of 2.56g adds deionized water to be configured to 1L solution, pour into band stirring
Be warming up to 80 DEG C in the 3L glass reaction kettle of heating, diatomite 300g is added, is added dropwise 7% sodium bicarbonate aqueous solution, in progress
And precipitating, neutralizing the time is 25 minutes, adjusts endpoint pH 7.2, is aged 30 minutes, and fixed crystal form is filtered after washing filtering
Cake;Filter cake is dried to water content 56%, and addition pore-creating auxiliary agent carboxymethyl cellulose 4.5g is mediated 60 minutes, is then extruded into
Bar shaped is cut into 3~5mm of length after drying, then carry out roasting 3 hours at 680 DEG C again in Muffle furnace, obtain carrier.It weighs
The RuCl33H of 0.51g2O is dissolved in 25g deionized water, after ultrasonic dissolution, solution is uniformly sprayed on 200g carrier, room
Temperature is placed 2 hours, then sample is put into microwave oven, microwave frequency 400GHz, power 600W, is handled 20 minutes
Afterwards, catalyst semi-finished product are obtained, then restored 7 hours at 250 DEG C of 5% hydrogen/nitrogen of normal pressure, obtain catalyst prod C3.Catalysis
The Ru content of agent product is 0.10%, specific surface area 103.5m2/ g, Kong Rong 0.28mL/g.
Embodiment 4
It weighs nine water aluminum nitrate of 800g and 8.91g calcium nitrate adds deionized water to be configured to 1L solution, pour into band stirring and add
It is warming up to 60 DEG C in the 3L glass reaction kettle of heat, diatomite 300g is added, 6% sodium bicarbonate aqueous solution is added dropwise, it is heavy neutralize
It forms sediment, neutralizing the time is 25 minutes, adjusts endpoint pH 7.4, is aged 40 minutes, and fixed crystal form obtains filter cake after washing filtering;Filter
Cake is dried to water content 48%, and addition pore-creating auxiliary agent carboxymethyl cellulose 2.8g is mediated 40 minutes, is then extruded intoBar shaped,
It is cut into 3~5mm of length after drying, then carries out roasting 4 hours at 650 DEG C again in Muffle furnace, obtains carrier.Weigh 1.08g
RuCl33H2O is dissolved in 25g deionized water, after ultrasonic dissolution, solution is uniformly sprayed on 200g carrier, is placed at room temperature for
1 hour, then sample is put into microwave oven, microwave frequency 500GHz, power 500W, after processing 30 minutes, is obtained
It is restored 6 hours to catalyst semi-finished product, then at 200 DEG C of 5% hydrogen/nitrogen of normal pressure, obtains catalyst prod C4.Catalyst prod
Ru content be 0.21%, specific surface area 96.5m2/ g, Kong Rong 0.22mL/g.
Embodiment 5
It weighs nine water aluminum nitrate of 800g and 11.57g magnesium nitrate hexahydrate adds deionized water to be configured to 1L solution, pour into band stirring
Be warming up to 50 DEG C in the 3L glass reaction kettle of heating, attapulgite 300g is added, 6% sodium bicarbonate aqueous solution is added dropwise, carries out
Neutralization precipitation, neutralizing the time is 12 minutes, adjusts endpoint pH 7.7, is aged 30 minutes, and fixed crystal form obtains after washing filtering
Filter cake;Filter cake is dried to water content 52%, and addition pore-creating auxiliary agent carboxymethyl cellulose 2.8g is mediated 40 minutes, is then extruded intoBar shaped is cut into 3~5mm of length after drying, then carry out roasting 3 hours at 680 DEG C again in Muffle furnace, carried
Body.Weigh the RuCl33H of 0.92g2O is dissolved in 25g deionized water, and after ultrasonic dissolution, solution is uniformly sprayed onto 200g load
On body, it is placed at room temperature for 1 hour, then sample is put into microwave oven, microwave frequency 400GHz, power 700W, place
Reason obtained catalyst semi-finished product after 30 minutes, then restored 3 hours at 300 DEG C of 5% hydrogen/nitrogen of normal pressure, obtained catalyst prod
C5.The Ru content of catalyst prod is 0.18%, specific surface area 79.3m2/ g, Kong Rong 0.13mL/g.
Embodiment 6
It weighs nine water aluminum nitrate of 800g and five water zirconium nitrate of 7.69g adds deionized water to be configured to 1L solution, pour into band stirring
Be warming up to 70 DEG C in the 3L glass reaction kettle of heating, diatomite 300g is added, is added dropwise 7% sodium bicarbonate aqueous solution, in progress
And precipitating, neutralizing the time is 20 minutes, adjusts endpoint pH 8.0, is aged 40 minutes, and fixed crystal form is filtered after washing filtering
Cake;Filter cake is dried to water content 54%, and addition pore-creating auxiliary agent carboxymethyl cellulose 2.8g is mediated 40 minutes, is then extruded into
Bar shaped is cut into 3~5mm of length after drying, then carry out roasting 3 hours at 800 DEG C again in Muffle furnace, obtain carrier.It weighs
1.28g RuCl33H2O is dissolved in 25g deionized water, after ultrasonic dissolution, solution is uniformly sprayed on 200g carrier, room
Temperature is placed 2 hours, then sample is put into microwave oven, microwave frequency 300GHz, power 800W, is handled 25 minutes
Afterwards, catalyst semi-finished product are obtained, then are restored 4 hours at 300 DEG C of 5% hydrogen/nitrogen of normal pressure, catalyst prod C6 is obtained.Catalysis
The Ru content of agent product is 0.25%, specific surface area 89.7m2/ g, Kong Rong 0.20mL/g.
Embodiment 7
It weighs nine water aluminum nitrate of 800g and 20.83g magnesium nitrate hexahydrate adds deionized water to be configured to 1L solution, pour into band stirring
Be warming up to 80 DEG C in the 3L glass reaction kettle of heating, diatomite 300g is added, is added dropwise 6% sodium bicarbonate aqueous solution, in progress
And precipitating, neutralizing the time is 25 minutes, adjusts endpoint pH 7.4, is aged 40 minutes, and fixed crystal form is filtered after washing filtering
Cake;Filter cake is dried to water content 55%, and addition pore-creating auxiliary agent carboxymethyl cellulose 6.7g is mediated 50 minutes, is then extruded into
Bar shaped is cut into 3~5mm of length after drying, then carry out roasting 4 hours at 750 DEG C again in Muffle furnace, obtain carrier.It weighs
The RuCl33H of 0.67g2O is dissolved in 25g deionized water, after ultrasonic dissolution, solution is uniformly sprayed on 200g carrier, room
Temperature is placed 1.5 hours, then sample is put into microwave oven, microwave frequency 500GHz, power 600W, handles 25 points
Zhong Hou obtains catalyst semi-finished product, then restores 6 hours at 250 DEG C of 5% hydrogen/nitrogen of normal pressure, obtains catalyst prod C7.It urges
The Ru content of agent product is 0.13%, specific surface area 119.4m2/ g, Kong Rong 0.26mL/g.
Embodiment 8
It weighs nine water aluminum nitrate of 800g and 3.57g calcium nitrate adds deionized water to be configured to 1L solution, pour into band stirring and add
It is warming up to 60 DEG C in the 3L glass reaction kettle of heat, attapulgite 300g is added, 7% sodium bicarbonate aqueous solution is added dropwise, is neutralized
Precipitating, neutralizing the time is 25 minutes, adjusts endpoint pH 7.0, is aged 50 minutes, and fixed crystal form obtains filter cake after washing filtering;
Filter cake is dried to water content 50%, and addition pore-creating auxiliary agent carboxymethyl cellulose 4.0g is mediated 50 minutes, is then extruded intoItem
Shape is cut into 3~5mm of length after drying, then carry out roasting 3 hours again at 700 DEG C of Muffle furnace, obtain carrier.Weigh 1.54g
RuCl33H2O is dissolved in 25g deionized water, after ultrasonic dissolution, solution is uniformly sprayed on 200g carrier, is placed at room temperature for
1 hour, then sample is put into microwave oven, microwave frequency 500GHz, power 500W, processing after twenty minutes, obtains
It is restored 5 hours to catalyst semi-finished product, then at 300 DEG C of 5% hydrogen/nitrogen of normal pressure, obtains catalyst prod C8.Catalyst prod
Ru content be 0.30%, specific surface area 97.9m2/ g, Kong Rong 0.25mL/g.
Embodiment 9
It weighs nine water aluminum nitrate of 800g and 3.57g calcium nitrate adds deionized water to be configured to 1L solution, pour into band stirring and add
It is warming up to 60 DEG C in the 3L glass reaction kettle of heat, attapulgite 300g is added, 7% sodium bicarbonate aqueous solution is added dropwise, is neutralized
Precipitating, neutralizing the time is 25 minutes, adjusts endpoint pH 7.0, is aged 50 minutes, and fixed crystal form obtains filter cake after washing filtering;
Filter cake is dried to water content 50%, and addition pore-creating auxiliary agent carboxymethyl cellulose 4.0g is mediated 50 minutes, is then extruded intoItem
Shape is cut into 3~5mm of length after drying, then carry out roasting 3 hours again at 700 DEG C of Muffle furnace, obtain carrier.Weigh 1.54g
RuCl33H2O is dissolved in 25g deionized water, after ultrasonic dissolution, solution is uniformly sprayed on 200g carrier, is placed at room temperature for
1 hour, 400 roasting 4 hours in Muffle furnace are placed on, obtain catalyst semi-finished product, then restore at 300 DEG C of 5% hydrogen/nitrogen of normal pressure
5 hours, obtain catalyst prod C9.The Ru content of catalyst prod is 0.30%, specific surface area 90.1m2/ g, Kong Rong
0.22mL/g。
Application Example
The reactor reacted in the embodiment of the present invention is fixed bed reactors, and reactor specification is
Catalyst C1~the C9 measured in 20~50ml above-described embodiment 1~9 is loaded into configured benzene methanamine solution in reactor
Preheating enters hydrogenator progress catalytic hydrogenation after being mixed by metering pump with hydrogen, and hydrogen is controlled by mass flowmenter,
Product is after condensing and separating, hydrogen gas automatic blow down, and liquid product collection is analyzed, and product before and after hydrogen is added to be divided using gas-chromatography
Analysis, calculates conversion ratio and selectivity.
Specific catalyst and process conditions and test result is as follows:
Data can be seen that from table, a series of catalyst of preparation, the benzene first with higher under suitable process conditions
Amine conversion ratio, while the selectivity of cyclohexyl methylamine with higher, prospects for commercial application are fine.
Claims (5)
1. a kind of preparation method of cyclohexyl methylamine, it is characterised in that benzene methanamine squeezes into the fixed bed equipped with ruthenium catalyst with metering pump
In reactor plus hydrogen prepares cyclohexyl methylamine, the process conditions of hydrogenation reaction are as follows: 80~120 DEG C of temperature, 1~5MPa of pressure, liquid
0.5~2h of air speed-1, ruthenium catalyst mainly forms are as follows: active element ruthenium, mass content 0.1~0.3%, pH value adjusting help
Agent, content are 0.2~2% of quality of alumina in carrier, remaining is carrier, and the specific surface area of catalyst is 70~120m2/
G, 0.12~0.28mL/g of Kong Rong.
2. ruthenium catalyst according to claim 1, it is characterised in that the catalyst carrier be aluminium oxide and attapulgite or
The mixture of diatomite.
3. ruthenium catalyst according to claim 1, it is characterised in that the catalyst is prepared using following steps:
(A) it prepares acid aluminum nitrate solution to be added to being heated to 50~80 DEG C in the reaction kettle stirred, it is abundant that filler is added
It stirs evenly, is pressed with sodium bicarbonate salting liquid, carry out neutralization precipitation, neutralize the time 15~30 minutes, adjust endpoint pH 7.0~8.0;
(B) it is aged 20~50 minutes at 60~80 DEG C, fixed crystal form obtains filter cake after washing, filtering;
(C) filter cake is dried to plasticity, and adding assistant extruded moulding is roasted again at being then 600~800 DEG C in temperature, obtained
To catalyst carrier for hydrgenating;
(D) with hydrate ruthenium trichloride and the solution for being configured to suitable concentration, solution B is uniformly sprayed onto carrier, material first exists
It is dried for the first time in constant temperature blast drying oven, then sample is moved in microwave oven and is heat-treated, obtain finished product catalysis
Agent;
(E) activation of catalyst: catalyst is restored 4~8 hours at 200~300 DEG C with 5% hydrogen/nitrogen, is catalyzed
Agent product.
4. the preparation method of hydrogenation catalyst as claimed in claim 3, it is characterised in that filler is concave convex rod in step (A)
One of soil, diatomite.
5. the preparation method of hydrogenation catalyst as claimed in claim 4, it is characterised in that be incorporated in its nitric acid aluminium salt in step (A)
Soluble salt pH value adjusts auxiliary agent, and soluble salt is selected from one or more of magnesium nitrate, zirconium nitrate, calcium nitrate.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811307413.9A CN109529826A (en) | 2018-11-05 | 2018-11-05 | A kind of continuity method prepares the method and catalyst of cyclohexyl methylamine |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811307413.9A CN109529826A (en) | 2018-11-05 | 2018-11-05 | A kind of continuity method prepares the method and catalyst of cyclohexyl methylamine |
Publications (1)
Publication Number | Publication Date |
---|---|
CN109529826A true CN109529826A (en) | 2019-03-29 |
Family
ID=65846148
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811307413.9A Pending CN109529826A (en) | 2018-11-05 | 2018-11-05 | A kind of continuity method prepares the method and catalyst of cyclohexyl methylamine |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109529826A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110090641A (en) * | 2019-05-21 | 2019-08-06 | 常州大学 | A kind of catalyst and preparation method and application adding hydrogen 1,3- hexamethylene dimethylamine for m-xylene diamine |
CN110152642A (en) * | 2019-05-24 | 2019-08-23 | 常州大学 | A kind of catalyst being used to prepare m-xylene diamine and application |
CN113471366A (en) * | 2021-06-24 | 2021-10-01 | 华侨大学 | Preparation method of 2D/3D perovskite solar cell based on cyclohexylmethylamine iodide salt |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0796839A1 (en) * | 1996-03-18 | 1997-09-24 | Bayer Ag | Process for the preparation of a mixture of amino-methyl-cyclohexanes and diamino-methyl-cyclohexanes |
CN1424293A (en) * | 2002-12-12 | 2003-06-18 | 复旦大学 | Benzene selective hydrogenation carried ruthenium based catalyst and its preparation |
CN1915494A (en) * | 2005-08-17 | 2007-02-21 | 中国石化上海石油化工股份有限公司 | Catalyst for benzene ring hydrogenation of terephthalic acid or dimethyl terephthalate |
CN101161631A (en) * | 2006-10-10 | 2008-04-16 | 汉能科技有限公司 | Preparation method of cyclohexylamine |
CN102247896A (en) * | 2011-05-23 | 2011-11-23 | 中国石油天然气股份有限公司 | Alumina-zirconia composite carrier and preparation method thereof |
CN102294242A (en) * | 2011-05-23 | 2011-12-28 | 中国石油天然气股份有限公司 | C2 front-end hydrogenation catalyst and preparation method thereof |
CN102476052A (en) * | 2010-11-29 | 2012-05-30 | 中国石油化工股份有限公司 | Supported ruthenium catalyst and preparation method thereof |
CN102688757A (en) * | 2011-03-22 | 2012-09-26 | 中国科学院大连化学物理研究所 | Catalyst for preparing cyclohexanediamine by phenylenediamine hydrogenation under ammonia reaction conditions |
CN105561997A (en) * | 2014-10-11 | 2016-05-11 | 中国石油化工股份有限公司 | Preparation method of nickel liquid phase hydrogenation catalyst |
CN106994344A (en) * | 2017-03-31 | 2017-08-01 | 江苏清泉化学股份有限公司 | The method and catalyst of toluenediamine selection Hydrogenation methyl cyclohexane diamines |
-
2018
- 2018-11-05 CN CN201811307413.9A patent/CN109529826A/en active Pending
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0796839A1 (en) * | 1996-03-18 | 1997-09-24 | Bayer Ag | Process for the preparation of a mixture of amino-methyl-cyclohexanes and diamino-methyl-cyclohexanes |
US5741929A (en) * | 1996-03-18 | 1998-04-21 | Bayer Aktiengesellschaft | Process for preparing a mixture of amino-methyl-cyclohexanes and diamino-methyl-cyclohexanes |
CN1424293A (en) * | 2002-12-12 | 2003-06-18 | 复旦大学 | Benzene selective hydrogenation carried ruthenium based catalyst and its preparation |
CN1915494A (en) * | 2005-08-17 | 2007-02-21 | 中国石化上海石油化工股份有限公司 | Catalyst for benzene ring hydrogenation of terephthalic acid or dimethyl terephthalate |
CN101161631A (en) * | 2006-10-10 | 2008-04-16 | 汉能科技有限公司 | Preparation method of cyclohexylamine |
CN102476052A (en) * | 2010-11-29 | 2012-05-30 | 中国石油化工股份有限公司 | Supported ruthenium catalyst and preparation method thereof |
CN102688757A (en) * | 2011-03-22 | 2012-09-26 | 中国科学院大连化学物理研究所 | Catalyst for preparing cyclohexanediamine by phenylenediamine hydrogenation under ammonia reaction conditions |
CN102247896A (en) * | 2011-05-23 | 2011-11-23 | 中国石油天然气股份有限公司 | Alumina-zirconia composite carrier and preparation method thereof |
CN102294242A (en) * | 2011-05-23 | 2011-12-28 | 中国石油天然气股份有限公司 | C2 front-end hydrogenation catalyst and preparation method thereof |
CN105561997A (en) * | 2014-10-11 | 2016-05-11 | 中国石油化工股份有限公司 | Preparation method of nickel liquid phase hydrogenation catalyst |
CN106994344A (en) * | 2017-03-31 | 2017-08-01 | 江苏清泉化学股份有限公司 | The method and catalyst of toluenediamine selection Hydrogenation methyl cyclohexane diamines |
Non-Patent Citations (3)
Title |
---|
HONGXIAN MA ET AL.: ""Catalytic hydrogenation of 1,4-phenylenediamine to 1,4-cyclohexanediamine"", 《RUSSIAN JOURNAL OF APPLIED CHEMISTRY》 * |
曹芮等: ""Ru/Al2O3催化剂的制备及其对邻苯二甲酸酯催化加氢的工艺研究"", 《常州大学学报(自然科学版)》 * |
李芳等: ""用作催化剂载体的纳米氧化铝的制备及改性"", 《山东理工大学学报(自然科学版)》 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110090641A (en) * | 2019-05-21 | 2019-08-06 | 常州大学 | A kind of catalyst and preparation method and application adding hydrogen 1,3- hexamethylene dimethylamine for m-xylene diamine |
CN110090641B (en) * | 2019-05-21 | 2022-03-25 | 常州大学 | Catalyst for preparing 1, 3-cyclohexyldimethylamine by m-xylylenediamine hydrogenation, preparation method and application |
CN110152642A (en) * | 2019-05-24 | 2019-08-23 | 常州大学 | A kind of catalyst being used to prepare m-xylene diamine and application |
CN113471366A (en) * | 2021-06-24 | 2021-10-01 | 华侨大学 | Preparation method of 2D/3D perovskite solar cell based on cyclohexylmethylamine iodide salt |
CN113471366B (en) * | 2021-06-24 | 2023-05-09 | 华侨大学 | Preparation method of 2D/3D perovskite solar cell based on cyclohexylmethylamine iodized salt |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109529826A (en) | A kind of continuity method prepares the method and catalyst of cyclohexyl methylamine | |
CN106391028B (en) | A kind of methanation catalyst and preparation method thereof for fluidized bed | |
CN105032428B (en) | A kind of preparation method of microwave heating synthetic catalyst and the method that catalyst one-step synthesis method cyclohexylamine is made based on the preparation method | |
CN103816934B (en) | The C5/C6 alkane isomerization catalyst of load nickel borides and preparation and application thereof | |
JP2013514296A (en) | Method for producing higher ethanolamine | |
CN106890662B (en) | A kind of catalyst, preparation method and its application | |
CN109550501A (en) | A kind of preparation method and applications of nitrobenzene liquid-phase hydrogenatin catalyst in aniline | |
CN110801841A (en) | Catalyst for preparing 2, 2' -bipyridine by coupling synthesis of pyridine and preparation method and application thereof | |
CN110090641A (en) | A kind of catalyst and preparation method and application adding hydrogen 1,3- hexamethylene dimethylamine for m-xylene diamine | |
CN103394348A (en) | Method for preparing catalyst for hydrogenating pyridine compound and application thereof | |
CN103357423B (en) | Preparation method of modified palladium-carbon catalyst for aromatic amine preparation, and application of catalyst | |
CN105833863A (en) | Catalyst for preparing succinic anhydride from maleic anhydride through low-temperature hydrogenation and preparation method and application of catalyst | |
CN103880590A (en) | Process for preparing 1,3,3,3-tetrafluoropropene | |
CN107008255B (en) | Nano diamond platinum catalyst and its preparation method and application for normal butane direct dehydrogenation butylene | |
CN110551278A (en) | Supported catalyst and preparation method and application thereof | |
WO2018133196A1 (en) | Phosphor-doped carbon material hydrogenation catalyst, preparation method therefor and use thereof | |
CN107999089A (en) | Catalyst for producing diethyl toluene diamine and preparation method thereof, application | |
CN104588089A (en) | Reformate olefin-removal catalyst preparation method by ammonium fluoride modification | |
CN109304175A (en) | A kind of nickel Pd/carbon catalyst, preparation method and applications | |
CN103450026B (en) | Synthesis method of N, N-diethylpropargylamine as electroplating additive | |
CN106366055A (en) | Ethyl tetrahydrofurfuryl ether preparation process | |
Muller et al. | Raney cobalt: an effective and recyclable catalyst for the Pauson–Khand reaction | |
CN109096121A (en) | A kind of catalysis preparation method of trifluoroethylamine compound | |
CN101475515B (en) | Method for preparing 5-amino-2-chloro-N-(2,4-xylyl)-benzene sulfonic amide in water phase | |
CN106582636B (en) | Composite catalyst bed |
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 | ||
WD01 | Invention patent application deemed withdrawn after publication | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190329 |