CN108715578A - A kind of method that dimethyl carbonate substitutes toluene production DCB 3,3' dichlorobenzidine hydrochloride - Google Patents
A kind of method that dimethyl carbonate substitutes toluene production DCB 3,3' dichlorobenzidine hydrochloride Download PDFInfo
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- CN108715578A CN108715578A CN201810772246.9A CN201810772246A CN108715578A CN 108715578 A CN108715578 A CN 108715578A CN 201810772246 A CN201810772246 A CN 201810772246A CN 108715578 A CN108715578 A CN 108715578A
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- dimethyl carbonate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/54—Preparation of compounds containing amino groups bound to a carbon skeleton by rearrangement reactions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C241/00—Preparation of compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
- C07C241/02—Preparation of hydrazines
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Abstract
The invention discloses a kind of dimethyl carbonates to substitute the method that toluene produces 3,3 '-dichlorobenzidine hydrochlorides, belongs to technical field of dye.The present invention is prepared using following steps：S1：Reduction reaction；S2：Position rotaring rearrangement；S3：Purifying；S4：Decoloration；S5：Decrease temperature crystalline；S6：Centrifugation.The present invention is scientific and reasonable, technological process is simple, the solvent that toluene is used as ortho-nitrochlorobenzene catalytic hydrogenation is substituted by dimethyl carbonate, since dimethyl carbonate itself is colourless, tasteless, nontoxic, is avoided using safe and environment-friendly hidden danger caused by toluene, greatly reduce pollution, it is very environmentally friendly, it is a kind of process for cleanly preparing, and 3 after translocation reaction, 3 '-dichlorobenzidine hydrochlorides are easily detached with dimethyl carbonate, and product yield is high, quality is high.
Description
Technical field
The present invention relates to technical field of dye, specially a kind of dimethyl carbonate substitutes toluene and produces 3,3 '-dichlorobenzenes
The method of amine hydrochlorate.
Background technology
DCB 3,3' dichlorobenzidine hydrochloride (C12H10Cl2N22HCl) is the double chlordiphenyl amine system row organic pigments of production
A kind of important intermediate, using its as primary raw material prepare organic pigment yield account for about the 27% of organic pigment total amount, extensively
The production starched for the colorings such as ink, paint, rubber, plastics and textile printing pigment and pigment dyeing.
Now domestic and use two kinds of catalytic reduction methods to prepare 3,3 '-dichlorobenzidine hydrochlorides in the world, this two
Kind of method is all based on the basis of catalytic hydrogenation method, difference lies in one is carrying out translocation reaction with hydrochloric acid, one is with
Sulfuric acid+hydrochloric acid carries out translocation reaction.But two methods will inevitably use a large amount of toluene as solvent, because catalysis adds
There are noble metal catalysts in hydrogen reaction, it is necessary to recycle catalyst reuse, when recycling inevitably has a large amount of toluene
Volatilization, there is also the volatilizations of bigger toluene for subsequent processing process.Toluene is toxic, easily plays electrostatic, and flash-point is low, not environmentally, is easy
Occupational disease is caused to human body.
Invention content
Toluene, which is substituted, the purpose of the present invention is to provide a kind of dimethyl carbonate produces DCB 3,3' dichlorobenzidine hydrochloride
Method, to solve the problems mentioned in the above background technology.
To achieve the above object, the present invention provides the following technical solutions：A kind of dimethyl carbonate substitutes toluene production 3,3 '-
The method of dichlorobenzidine hydrochloride, including be prepared using following steps：
S1：Reduction reaction, by ortho-nitrochlorobenzene, dimethyl carbonate, sodium hydroxide, water, catalyst, co-catalyst and table
In face activating agent input autoclave, stirring is opened, control mixing speed is 160~220rpm, after 5~8h of sustained response,
By material filtering in autoclave, filter cake recycling catalyst is spare, and filtrate obtains 2,2 '-dichlorohydrazobenzenes and carbonic acid two
Mixtures of methyl esters；
S2：Position rotaring rearrangement, 2,2 '-dichlorohydrazobenzenes and dimethyl carbonate mixture are cooled to 40 DEG C hereinafter, 2, and 2 '-
Dichlorohydrazobenzene crystallizes, and then filters, and filtrate returns to reduction and applies mechanically, using grinder by 2,2 '-dichlorohydrazobenzenes
It is ground to particle and is less than 60 mesh, be sent into position rotaring rearrangement in 23% hydrochloric acid, control temperature of reactor is 20~40 DEG C, while opening and stirring
It mixes, control mixing speed is 60~100rpm, persistently stirs 2~8h；
S3：Material is sent into filter press with filter pressing pump and is separated by solid-liquid separation by purifying, reaction end, and liquid hydrochloric acid carries out dense
Contracting is applied mechanically.Filter cake is first washed with clear water, is then dissolved with hot mother liquor；
S4：Activated carbon is added into filtrate for decoloration, recycles waste active carbon after stirring 15min, and obtain clarified solution；
S5：Clarified solution is transferred to crystallization kettle by decrease temperature crystalline, and with circulating water cooling, temperature is down to 40 DEG C；
S6：Centrifugation after the crystallization of 3,3 '-dichlorobenzidine hydrochlorides, then obtains 3,3 '-dichloro-benzidine of finished product after centrifugation
Hydrochloride.
Preferably, in step 1, the dimethyl carbonate is technical grade.
Preferably, in step 1, the catalyst uses 0.3%Pt/C catalyst, 50% or more water capacity.
Preferably, in step 1, the co-catalyst uses 2,3-, bis- chloro- 1,4-naphthoquinones, technical grade.
Preferably, in step 1, the surfactant uses neopelex, technical grade.
Preferably, in step 2, when grinding reflux cycle of the grinding pump a length of 30min, grinding operating temperature is
24℃。
Preferably, in step 4, the activated carbon is fine-powder shape shell activated carbon, and granularity is 200~500 mesh,
Its specific surface area is 600~1500 ㎡/g.
Preferably, in step 6, the rotating speed of low speed centrifuge is 600rpm, the when a length of 5min or more of low-speed centrifugal.
Compared with prior art, the beneficial effects of the invention are as follows：
1. the present invention is scientific and reasonable, technological process is simple, and substituting toluene by dimethyl carbonate is used as ortho-nitrochlorobenzene
The solvent of catalytic hydrogenation is avoided since dimethyl carbonate itself is colourless, tasteless, nontoxic using safe and environment-friendly caused by toluene
Hidden danger greatly reduces pollution, very environmentally friendly, is a kind of process for cleanly preparing, and 3 after translocation reaction, 3 '-dichlorobenzenes
Amine hydrochlorate is easily detached with dimethyl carbonate, and product yield is high, quality is high；
2. the present invention by 2,2 '-dichlorohydrazobenzene of grinding pump pair and dimethyl carbonate grind in dnockout,
So that material is born hundreds of thousands per minute time or even up to a million high speed shears in working chamber, forms strong aquashear
And turbulent flow, material moment under the comprehensive functions power such as centrifugation, extruding, collision, grinding, crushing obtain fully dispersed, homogeneous and mix
It closes, improves 2,2 '-dichlorohydrazobenzene position rotaring rearrangement effects, improve 2,2 '-dichlorohydrazobenzene yields.
Specific implementation mode
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
The every other embodiment that art personnel are obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment one
The present invention provides a kind of technical solution：A kind of dimethyl carbonate replacement toluene production DCB 3,3' dichlorobenzidine hydrochloric acid
The method of salt, including be prepared using following steps：
S1：Reduction reaction, by ortho-nitrochlorobenzene, dimethyl carbonate, sodium hydroxide, water, catalyst, co-catalyst and table
In face activating agent input autoclave, stirring is opened, control mixing speed is 160rpm, after sustained response 5h, high pressure is anti-
Material filtering in kettle is answered, filter cake recycling catalyst is spare, and filtrate obtains 2,2 '-dichlorohydrazobenzenes and dimethyl carbonate mixing
Object；
S2：Position rotaring rearrangement, 2,2 '-dichlorohydrazobenzenes and dimethyl carbonate mixture are cooled to 40 DEG C, 2,2 '-dichloros
Hydrazobenzene crystallizes, and then filters, and filtrate returns to reduction and applies mechanically, and is ground 2,2 '-dichlorohydrazobenzenes using grinder
It is 60 mesh to particle, is sent into position rotaring rearrangement in 23% hydrochloric acid, control temperature of reactor is 20 DEG C, while opening stirring, and control is stirred
It is 60rpm to mix speed, persistently stirs 2h；
S3：Material is sent into filter press with filter pressing pump and is separated by solid-liquid separation by purifying, reaction end, and liquid hydrochloric acid carries out dense
Contracting is applied mechanically.Filter cake is first washed with clear water, is then dissolved with hot mother liquor；
S4：Activated carbon is added into filtrate for decoloration, recycles waste active carbon after stirring 15min, and obtain clarified solution；
S5：Clarified solution is transferred to crystallization kettle by decrease temperature crystalline, and with circulating water cooling, temperature is down to 40 DEG C；
S6：Centrifugation after the crystallization of 3,3 '-dichlorobenzidine hydrochlorides, then obtains 3,3 '-dichloro-benzidine of finished product after centrifugation
Hydrochloride.
Wherein, dimethyl carbonate is technical grade；Catalyst uses 0.3%Pt/C catalyst, water capacity 50%；Co-catalyst
Using 2,3-, bis- chloro- 1,4-naphthoquinones, technical grade；Surfactant uses neopelex, technical grade；Grinding pump is ground
A length of 30min when reflux cycle is ground, grinding operating temperature is 24 DEG C；Activated carbon is fine-powder shape shell activated carbon, grain
Degree is 200~500 mesh, and specific surface area is 600~1500 ㎡/g；The rotating speed of low speed centrifuge is 600rpm, low-speed centrifugal
Shi Changwei 5min.
Embodiment two
The present invention provides a kind of technical solution：A kind of dimethyl carbonate replacement toluene production DCB 3,3' dichlorobenzidine hydrochloric acid
The method of salt, including be prepared using following steps：
S1：Reduction reaction, by ortho-nitrochlorobenzene, dimethyl carbonate, sodium hydroxide, water, catalyst, co-catalyst and table
In face activating agent input autoclave, stirring is opened, control mixing speed is 180rpm, after sustained response 6h, high pressure is anti-
Material filtering in kettle is answered, filter cake recycling catalyst is spare, and filtrate obtains 2,2 '-dichlorohydrazobenzenes and dimethyl carbonate mixing
Object；
S2：Position rotaring rearrangement, 2,2 '-dichlorohydrazobenzenes and dimethyl carbonate mixture are cooled to 36 DEG C, 2,2 '-dichloros
Hydrazobenzene crystallizes, and then filters, and filtrate returns to reduction and applies mechanically, and is ground 2,2 '-dichlorohydrazobenzenes using grinder
It is 60 mesh to particle, is sent into position rotaring rearrangement in 23% hydrochloric acid, control temperature of reactor is 25 DEG C, while opening stirring, and control is stirred
It is 75rpm to mix speed, persistently stirs 4h；
S3：Material is sent into filter press with filter pressing pump and is separated by solid-liquid separation by purifying, reaction end, and liquid hydrochloric acid carries out dense
Contracting is applied mechanically.Filter cake is first washed with clear water, is then dissolved with hot mother liquor；
S4：Activated carbon is added into filtrate for decoloration, recycles waste active carbon after stirring 15min, and obtain clarified solution；
S5：Clarified solution is transferred to crystallization kettle by decrease temperature crystalline, and with circulating water cooling, temperature is down to 40 DEG C；
S6：Centrifugation after the crystallization of 3,3 '-dichlorobenzidine hydrochlorides, then obtains 3,3 '-dichloro-benzidine of finished product after centrifugation
Hydrochloride.
Wherein, dimethyl carbonate is technical grade；Catalyst uses 0.3%Pt/C catalyst, water capacity 50%；Co-catalyst
Using 2,3-, bis- chloro- 1,4-naphthoquinones, technical grade；Surfactant uses neopelex, technical grade；Grinding pump is ground
A length of 30min when reflux cycle is ground, grinding operating temperature is 24 DEG C；Activated carbon is fine-powder shape shell activated carbon, grain
Degree is 200~500 mesh, and specific surface area is 600~1500 ㎡/g；The rotating speed of low speed centrifuge is 600rpm, low-speed centrifugal
Shi Changwei 5min.
Embodiment three
The present invention provides a kind of technical solution：A kind of dimethyl carbonate replacement toluene production DCB 3,3' dichlorobenzidine hydrochloric acid
The method of salt, including be prepared using following steps：
S1：Reduction reaction, by ortho-nitrochlorobenzene, dimethyl carbonate, sodium hydroxide, water, catalyst, co-catalyst and table
In face activating agent input autoclave, stirring is opened, control mixing speed is 200rpm, after sustained response 7h, high pressure is anti-
Material filtering in kettle is answered, filter cake recycling catalyst is spare, and filtrate obtains 2,2 '-dichlorohydrazobenzenes and dimethyl carbonate mixing
Object；
S2：Position rotaring rearrangement, 2,2 '-dichlorohydrazobenzenes and dimethyl carbonate mixture are cooled to 32 DEG C, 2,2 '-dichloros
Hydrazobenzene crystallizes, and then filters, and filtrate returns to reduction and applies mechanically, and is ground 2,2 '-dichlorohydrazobenzenes using grinder
It is 60 mesh to particle, is sent into position rotaring rearrangement in 23% hydrochloric acid, control temperature of reactor is 35 DEG C, while opening stirring, and control is stirred
It is 90rpm to mix speed, persistently stirs 6h；
S3：Material is sent into filter press with filter pressing pump and is separated by solid-liquid separation by purifying, reaction end, and liquid hydrochloric acid carries out dense
Contracting is applied mechanically.Filter cake is first washed with clear water, is then dissolved with hot mother liquor；
S4：Activated carbon is added into filtrate for decoloration, recycles waste active carbon after stirring 15min, and obtain clarified solution；
S5：Clarified solution is transferred to crystallization kettle by decrease temperature crystalline, and with circulating water cooling, temperature is down to 40 DEG C；
S6：Centrifugation after the crystallization of 3,3 '-dichlorobenzidine hydrochlorides, then obtains 3,3 '-dichloro-benzidine of finished product after centrifugation
Hydrochloride.
Wherein, dimethyl carbonate is technical grade；Catalyst uses 0.3%Pt/C catalyst, water capacity 50%；Co-catalyst
Using 2,3-, bis- chloro- 1,4-naphthoquinones, technical grade；Surfactant uses neopelex, technical grade；Grinding pump is ground
A length of 30min when reflux cycle is ground, grinding operating temperature is 24 DEG C；Activated carbon is fine-powder shape shell activated carbon, grain
Degree is 200~500 mesh, and specific surface area is 600~1500 ㎡/g；The rotating speed of low speed centrifuge is 600rpm, low-speed centrifugal
Shi Changwei 5min.
Example IV
The present invention provides a kind of technical solution：A kind of dimethyl carbonate replacement toluene production DCB 3,3' dichlorobenzidine hydrochloric acid
The method of salt, including be prepared using following steps：
S1：Reduction reaction, by ortho-nitrochlorobenzene, dimethyl carbonate, sodium hydroxide, water, catalyst, co-catalyst and table
In face activating agent input autoclave, stirring is opened, control mixing speed is 220rpm, after sustained response 8h, high pressure is anti-
Material filtering in kettle is answered, filter cake recycling catalyst is spare, and filtrate obtains 2,2 '-dichlorohydrazobenzenes and dimethyl carbonate mixing
Object；
S2：Position rotaring rearrangement, 2,2 '-dichlorohydrazobenzenes and dimethyl carbonate mixture are cooled to 28 DEG C, 2,2 '-dichloros
Hydrazobenzene crystallizes, and then filters, and filtrate returns to reduction and applies mechanically, and is ground 2,2 '-dichlorohydrazobenzenes using grinder
It is 60 mesh to particle, is sent into position rotaring rearrangement in 23% hydrochloric acid, control temperature of reactor is 40 DEG C, while opening stirring, and control is stirred
It is 100rpm to mix speed, persistently stirs 8h；
S3：Material is sent into filter press with filter pressing pump and is separated by solid-liquid separation by purifying, reaction end, and liquid hydrochloric acid carries out dense
Contracting is applied mechanically.Filter cake is first washed with clear water, is then dissolved with hot mother liquor；
S4：Activated carbon is added into filtrate for decoloration, recycles waste active carbon after stirring 15min, and obtain clarified solution；
S5：Clarified solution is transferred to crystallization kettle by decrease temperature crystalline, and with circulating water cooling, temperature is down to 40 DEG C；
S6：Centrifugation after the crystallization of 3,3 '-dichlorobenzidine hydrochlorides, then obtains 3,3 '-dichloro-benzidine of finished product after centrifugation
Hydrochloride.
Wherein, dimethyl carbonate is technical grade；Catalyst uses 0.3%Pt/C catalyst, water capacity 50%；Co-catalyst
Using 2,3-, bis- chloro- 1,4-naphthoquinones, technical grade；Surfactant uses neopelex, technical grade；Grinding pump is ground
A length of 30min when reflux cycle is ground, grinding operating temperature is 24 DEG C；Activated carbon is fine-powder shape shell activated carbon, grain
Degree is 200~500 mesh, and specific surface area is 600~1500 ㎡/g；The rotating speed of low speed centrifuge is 600rpm, low-speed centrifugal
Shi Changwei 5min.
Yield can be obtained by four groups of above-mentioned embodiments up to 83% or more 3,3 '-dichlorobenzidine hydrochlorides,
The product yield highest for 3, the 3 '-dichlorobenzidine hydrochlorides that wherein embodiment two obtains, it is good in economic efficiency up to 91.6%, have
Conducive to promoting the use of.
The present invention has the advantages that：
The present invention is scientific and reasonable, and technological process is simple, and being used as ortho-nitrochlorobenzene by dimethyl carbonate replacement toluene urges
The solvent for changing hydrogenation is avoided since dimethyl carbonate itself is colourless, tasteless, nontoxic using safe and environment-friendly hidden caused by toluene
Suffer from, greatly reduces pollution, it is very environmentally friendly, it is a kind of process for cleanly preparing, and 3 after translocation reaction, 3 '-dichloro-benzidine
Hydrochloride is easily detached with dimethyl carbonate, and product yield is high, quality is high；The present invention is hydrogenated even by grinding pump pair 2,2 '-dichloro
Pyridine and dimethyl carbonate progress are ground in dnockout, so that material is born hundreds of thousands per minute in working chamber secondary or even up to a million
Secondary high speed shear, forms strong aquashear and turbulent flow, and material is comprehensive in centrifugation, extruding, collision, grinding, crushing etc.
Active force lower moment obtains fully dispersed, homogeneous and mixing, improves 2,2 '-dichlorohydrazobenzene position rotaring rearrangement effects, improves
2,2 '-dichlorohydrazobenzene yields.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understanding without departing from the principles and spirit of the present invention can carry out these embodiments a variety of variations, modification, replace
And modification, the scope of the present invention is defined by the appended.
Claims (8)
1. a kind of dimethyl carbonate substitutes the method that toluene produces 3,3 '-dichlorobenzidine hydrochlorides, it is characterised in that：Use with
Lower step is prepared：
S1：Reduction reaction lives ortho-nitrochlorobenzene, dimethyl carbonate, sodium hydroxide, water, catalyst, co-catalyst and surface
Property agent input autoclave in, open stirring, control mixing speed is 160~220rpm, will be high after 5~8h of sustained response
Material in reactor filtering is pressed, filter cake recycling catalyst is spare, and filtrate obtains 2,2 '-dichlorohydrazobenzenes and dimethyl carbonate
Mixture；
S2：Position rotaring rearrangement, 2,2 '-dichlorohydrazobenzenes and dimethyl carbonate mixture are cooled to 40 DEG C hereinafter, 2,2 '-dichloros
Hydrazobenzene crystallizes, and then filters, and filtrate returns to reduction and applies mechanically, and is ground 2,2 '-dichlorohydrazobenzenes using grinder
It is less than 60 mesh to particle, is sent into position rotaring rearrangement in 23% hydrochloric acid, control temperature of reactor is 20~40 DEG C, while opening stirring,
Control mixing speed is 60~100rpm, persistently stirs 2~8h；
S3：Material is sent into filter press with filter pressing pump and is separated by solid-liquid separation by purifying, reaction end, and liquid hydrochloric acid carries out concentration set
With.Filter cake is first washed with clear water, is then dissolved with hot mother liquor；
S4：Activated carbon is added into filtrate for decoloration, recycles waste active carbon after stirring 15min, and obtain clarified solution；
S5：Clarified solution is transferred to crystallization kettle by decrease temperature crystalline, and with circulating water cooling, temperature is down to 40 DEG C；
S6：Centrifugation after the crystallization of 3,3 '-dichlorobenzidine hydrochlorides, then obtains 3,3 '-dichloro-benzidine hydrochloric acid of finished product after centrifugation
Salt.
2. a kind of dimethyl carbonate according to claim 1 substitutes the side of toluene production DCB 3,3' dichlorobenzidine hydrochloride
Method, it is characterised in that：In step 1, the dimethyl carbonate is technical grade.
3. a kind of dimethyl carbonate according to claim 1 substitutes the side of toluene production DCB 3,3' dichlorobenzidine hydrochloride
Method, it is characterised in that：In step 1, the catalyst uses 0.3%Pt/C catalyst, 50% or more water capacity.
4. a kind of dimethyl carbonate according to claim 1 substitutes the side of toluene production DCB 3,3' dichlorobenzidine hydrochloride
Method, it is characterised in that：In step 1, the co-catalyst uses 2,3-, bis- chloro- 1,4-naphthoquinones, technical grade.
5. a kind of dimethyl carbonate according to claim 1 substitutes the side of toluene production DCB 3,3' dichlorobenzidine hydrochloride
Method, it is characterised in that：In step 1, the surfactant uses neopelex, technical grade.
6. a kind of dimethyl carbonate according to claim 1 substitutes the side of toluene production DCB 3,3' dichlorobenzidine hydrochloride
Method, it is characterised in that：In step 2, when grinding reflux cycle of the grinding pump a length of 30min, grinding operating temperature is 24
℃。
7. a kind of dimethyl carbonate according to claim 1 substitutes the side of toluene production DCB 3,3' dichlorobenzidine hydrochloride
Method, it is characterised in that：In step 4, the activated carbon is fine-powder shape shell activated carbon, and granularity is 200~500 mesh,
Specific surface area is 600~1500 ㎡/g.
8. a kind of dimethyl carbonate according to claim 1 substitutes the side of toluene production DCB 3,3' dichlorobenzidine hydrochloride
Method, it is characterised in that：In step 6, the rotating speed of low speed centrifuge is 600rpm, the when a length of 5min or more of low-speed centrifugal.
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| CN201810772246.9A CN108715578A (en) | 2018-07-13 | 2018-07-13 | A kind of method that dimethyl carbonate substitutes toluene production DCB 3,3' dichlorobenzidine hydrochloride |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH637919A5 (en) * | 1979-01-04 | 1983-08-31 | Lonza Ag | Process for the preparation of 2,2'-dichlorohydrazobenzene |
| EP0391606A1 (en) * | 1989-04-05 | 1990-10-10 | Toyo Ink Manufacturing Co., Ltd. | Process for the production of an aromatic hydrazo compound |
-
2018
- 2018-07-13 CN CN201810772246.9A patent/CN108715578A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH637919A5 (en) * | 1979-01-04 | 1983-08-31 | Lonza Ag | Process for the preparation of 2,2'-dichlorohydrazobenzene |
| EP0391606A1 (en) * | 1989-04-05 | 1990-10-10 | Toyo Ink Manufacturing Co., Ltd. | Process for the production of an aromatic hydrazo compound |
Non-Patent Citations (4)
| Title |
|---|
| HAIYANG CHENG等: "The effect of water on the hydrogenation of o-chloronitrobenzene in ethanol, n-heptane and compressed carbon dioxide", 《APPLIED CATALYSIS A: GENERAL》 * |
| 刘宇芳等: "水介质中2, 2" -二氯氢化偶氮苯的绿色合成", 《山西大学学报（自然科学版）》 * |
| 李进军，吴峰: "《绿色化学导论》", 31 August 2015 * |
| 石明泉等: "水介质中催化加氢制备2，2’-二氯氢化偶氮苯的研究", 《染料与染色》 * |
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Application publication date: 20181030 |