CN1148344C - Process for preparation of 4.4' diaminophenylacyl substituted aniline - Google Patents
Process for preparation of 4.4' diaminophenylacyl substituted aniline Download PDFInfo
- Publication number
- CN1148344C CN1148344C CNB001125141A CN00112514A CN1148344C CN 1148344 C CN1148344 C CN 1148344C CN B001125141 A CNB001125141 A CN B001125141A CN 00112514 A CN00112514 A CN 00112514A CN 1148344 C CN1148344 C CN 1148344C
- Authority
- CN
- China
- Prior art keywords
- preparation
- anilide
- catalyzer
- water
- 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.)
- Expired - Lifetime
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title abstract description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title 1
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 13
- 229910000564 Raney nickel Inorganic materials 0.000 claims abstract description 11
- 239000007868 Raney catalyst Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 230000018044 dehydration Effects 0.000 claims abstract description 5
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims abstract 2
- -1 diaminobenzene anilide Chemical class 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 6
- 238000006073 displacement reaction Methods 0.000 claims description 5
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000013019 agitation Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000000843 powder Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 150000003931 anilides Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012257 stirred material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention discloses a preparation method of 4.4'-diaminobenzanilide, which uses 4.4'-dinitrobenzoylanilide as a raw material and comprises the steps of preparation, agitation, replacement, hydrogenation, separation, cooling, dehydration and desiccation in the condition of the existence of water and a catalyst called raney nickel or palladium-charcoal. The present invention has the characteristics of simple and feasible process, low product preparation cost, high yield, no impurity basically, no environmental pollution, etc.
Description
Technical field
The invention belongs to the chemical industry technical field, be specifically related to a kind of with 4,4 '-the dinitrobenzene anilide is a raw material, in the presence of water and catalyzer, prepare 4,4 through hydrotreatment '-a kind of industrialized preparing process of diaminobenzene anilide.
Background technology
4,4 '-the diaminobenzene anilide is a kind of important dyestuff intermediate.Present the dying factory in cities such as the Suzhou in numerous dye chemical industry factory such as the Jiangsu Province of China, Kunshan, Jiangyin all adopts its alternative serious O-Phenylene Diamine of contaminate environment in succession and prepares high-grade car and paint.The a tree name information material shows, existing 4,4 '-preparation method of diaminobenzene anilide, the mother liquor that the hydrogenation reaction operation is produced, be to adopt acid-base method, or adopt solvent method (organic solvents such as ethanol or methyl alcohol), and make its mother liquor be separated into finished product stoste and catalyzer filter cake.Undoubtedly, the complex process of prior art, the preparation cost height, yield is also lower.
Summary of the invention
The object of the present invention is to provide that a kind of technology is simple, preparation cost is lower, yield is higher relatively, and the preparation method of substantially free of impurities and environmental issue is to overcome the deficiencies in the prior art.
Realize that the object of the invention taked following technical scheme, it with 4,4 '-the dinitrobenzene anilide is a main raw material, in the presence of water and catalyzer, it comprises batching, stirring, displacement, hydrogenation, separation, cooling, dehydration and baking step successively.
And the proportioning raw materials of said batching (weight) is: 4,4 '-the dinitrobenzene anilide: water: catalyzer=1: 6～8: 0.05～0.08.
And said stirring is three kinds of materials of weighing by proportioning together preceding, drops into container in the lump and does and fully stir.
And the hydrogenation reaction temperature of said hydrogenation step is 90 ℃～130 ℃, and pressure is 0.2～0.6MPa, and the reaction times is 2～4 hours.
And said separation is to adopt to filter the mother liquor separation that the last road of decree hydrogenation reaction is produced, and produces finished product stoste and catalyzer filter cake.
And said cooling step, be treat to be cooled in the temperature of preceding one step through separating the finished product stoste produced≤30 ℃ the time, promptly cooling step finishes.
And the temperature of said oven dry is 105 ℃～115 ℃, and drying time is 4～5 hours.
The used catalyzer of the present invention is Raney nickel (Ni) or palladium carbon (Pd/C).And the present invention's Raney nickel (also claiming Raney's nickel) preferably.
The present invention has positive effect: by preparation method described above, prepared 4,4 '-diaminobenzene anilide final product, have that preparation technology is easy, preparation cost is lower, characteristics such as higher relatively and substantially free of impurities of yield and environmental pollution problem, according to test, its content can reach＞and 99.5%, its water content then is≤0.5%, yield can reach 〉=and 98%.
Embodiment
One of embodiment described in the invention is to be that 1000 liter reactors are container with volume.And carry out according to following steps successively:
Batching.By the weight ratio that is provided in the technical scheme, weigh respectively and get 4,4 '-dinitrobenzene anilide 100kg, water 700kg, catalyst powder attitude Raney nickel 6kg.
Stir.With three kinds of materials that the first step proportioning is weighed, drop into stirring tank in the lump and stir.Till abundant stirring, churning time is 1～2 hour.
Displacement.Press usual method, the second step stirred materials is led injected reactor with heating or cooling water spacer.And with nitrogen (N
2) displacement twice, promptly be evacuated to-0.09MPa, fill nitrogen again to 0.2MPa, be evacuated to again-0.09MPa, fill nitrogen again to 0.2MPa, so repeat twice.
Hydrogenation.And then to injecting high-temperature water in the water spacer of reactor that has the material of third step after displacement,, in reactor, inject hydrogen (H simultaneously with 0.4MPa pressure to the material heating
2).Because hydrogenation reaction is thermopositive reaction, thus should note the still interior reaction temperature, and regulated control by the temperature of in the water spacer, injecting water, control reaction temperature is between 120 ℃～125 ℃.Reaction times is 3 hours.The chemical expression formula of hydrogenation reaction is as follows:
Separate.With the mother liquor that preceding road hydrogenation reaction step is produced, import filter-paper filter and filter, and the catalyzer Raney nickel powder that order is present in the mother liquor separates with finished product stoste.Catalyzer Raney nickel powder exists with the filter cake state, after treatment can reuse.
Cooling.Press usual method, the finished product stoste that will produce after separating is cooled to＜and 30 ℃, final product is then separated out with solid phase, promptly gets the compound of final product and water.
Dehydration.Press usual method, the final product water mixture with preceding road cooling step is produced dries with centrifuge, and produces wet goods.
Oven dry.The wet goods that preceding road is produced are inserted in the Hotaircirculatingoven and are dried.Storing temperature is 110 ℃ ± 2 ℃, 4 hours time, treat that sample presentation detects its water content≤0.5% o'clock, and baking step finishes.
Thereafter, with the packing of fiber can inner lining plastic bag, every barrel of 40kg, export trade can appear on the market.
Two of embodiment described in the invention, in the weight ratio that when batching provided in by technical scheme, weigh respectively and get 4,4 '-dinitrobenzene anilide 100kg, water 700kg, containing the palladium amount is the palladium catalyst carbon 0.6kg of 3%-10%.Other step is as one of embodiment.
The used catalyzer of the present invention is the Raney nickel powder preferably, also contains palladium (Pd) amount and is the palladium carbon of 3%-10% (can by Russian, Taiwan import).And catalyzer Raney nickel powder can be added liquid phase sodium hydroxide (NaOH) and be produced after reaction by the al-ni alloy powder of ni content＞45%.There is confession in catalyzer Raney nickel powder market.
The raffinate that is become through the centrifuge dehydration of the present invention, qualified discharge after recycling.There is not environmental issue in the present invention.
Claims (2)
1, a kind of 4,4 '-preparation method of diaminobenzene anilide, it is with 4,4 '-the dinitrobenzene anilide is a raw material, in the presence of water and catalyzer, comprise batching, stirring, displacement, hydrogenation, separation, cooling, dehydration and baking step successively, it is characterized in that:
Proportioning raw materials (weight) at said batching step is: 4,4 '-the dinitrobenzene anilide: water: catalyzer=1: 6～8: 0.05～0.08;
At said whipping step, be three kinds of materials that preceding one step weighed by proportioning, drop in the container in the lump and do and fully stir;
Hydrogenation reaction temperature at said hydrogenation step is 90 ℃～130 ℃, and pressure is 0.2～0.6MPa, and the reaction times is 2-4 hour;
At said cooling step, be that the temperature of the finished product stoste produced together before treating is chilled to≤cooling step finishes 30 ℃ the time;
Bake out temperature at said baking step is 105 ℃～115 ℃, and drying time is 4～5 hours.
2, according to claim 14,4 '-preparation method of diaminobenzene anilide, it is characterized in that said catalyzer is Raney nickel or palladium carbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001125141A CN1148344C (en) | 2000-09-06 | 2000-09-06 | Process for preparation of 4.4' diaminophenylacyl substituted aniline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001125141A CN1148344C (en) | 2000-09-06 | 2000-09-06 | Process for preparation of 4.4' diaminophenylacyl substituted aniline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1285346A CN1285346A (en) | 2001-02-28 |
| CN1148344C true CN1148344C (en) | 2004-05-05 |
Family
ID=4582368
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001125141A Expired - Lifetime CN1148344C (en) | 2000-09-06 | 2000-09-06 | Process for preparation of 4.4' diaminophenylacyl substituted aniline |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1148344C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HU229858B1 (en) * | 2008-12-17 | 2014-10-28 | Richter Gedeon Nyrt | Process for the preparation of trans 4-amino-cyclohexyl acetic acid ethyl ester hcl |
| CN105294473B (en) * | 2015-11-12 | 2017-10-17 | 常州市阳光药业有限公司 | The preparation method of the diaminobenzene anilid of 2 chlorine 4,4 ' |
| CN106242990B (en) * | 2016-07-28 | 2020-04-28 | 浙江闰土研究院有限公司 | Preparation method of 2-amino-4-acetamino anisole |
-
2000
- 2000-09-06 CN CNB001125141A patent/CN1148344C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1285346A (en) | 2001-02-28 |
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| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Yangguang Fined Chemical Co., Ltd., Changzhou City Assignor: Hu Guoyi Contract fulfillment period: 2005.9.7 to 2020.9.6 Contract record no.: 2008320001064 Denomination of invention: Process for the preparation of 4, 4 '- two' - aniline Granted publication date: 20040505 License type: Exclusive license Record date: 20081027 |
|
| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2005.9.7 TO 2020.9.6; CHANGE OF CONTRACT Name of requester: CHANGZHOU CITY YANGGUANG FINE CHEMICAL CO., LTD. Effective date: 20081027 |
|
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20040505 |