CN108976131A - A kind of method of water substitution toluene production DCB 3,3' dichlorobenzidine hydrochloride - Google Patents
A kind of method of water substitution toluene production DCB 3,3' dichlorobenzidine hydrochloride Download PDFInfo
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- CN108976131A CN108976131A CN201810770542.5A CN201810770542A CN108976131A CN 108976131 A CN108976131 A CN 108976131A CN 201810770542 A CN201810770542 A CN 201810770542A CN 108976131 A CN108976131 A CN 108976131A
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- dichlorobenzidine
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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
Abstract
The invention discloses the methods that a kind of water substitution toluene produces 3,3 '-dichlorobenzidine hydrochlorides, belong 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, process flow is simple, solvent of the toluene as ortho-nitrochlorobenzene catalytic hydrogenation is substituted by water to avoid since water itself is colourless, tasteless, nontoxic using safe and environment-friendly hidden danger brought 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 easy to recovery of applied, and product yield is high, quality is high.
Description
Technical field
The present invention relates to technical field of dye, specially a kind of water substitution toluene produces 3,3 '-dichlorobenzidine hydrochlorides
Method.
Background technique
DCB 3,3' dichlorobenzidine hydrochloride (C12H10Cl2N22HCl) is to produce double chlordiphenyl amine system column organic pigments
A kind of important intermediate, using its as primary raw material preparation 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 prepare 3,3 '-dichlorobenzidine hydrochlorides using two kinds of catalytic reduction methods in the world, this two
Kind of method is all based on the basis of catalytic hydrogenation method, and difference is 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.
Summary of the invention
The purpose of the present invention is to provide a kind of water to substitute the method that toluene produces 3,3 '-dichlorobenzidine hydrochlorides, with
Solve the problems mentioned above in the background art.
To achieve the above object, the invention provides the following technical scheme: a kind of water substitution toluene produces 3,3 '-dichlorobenzenes
The method of amine hydrochlorate, including be prepared using following steps:
S1: reduction reaction throws ortho-nitrochlorobenzene, water, sodium hydroxide, catalyst, co-catalyst and surfactant
Enter in autoclave, open stirring, control mixing speed is 160~220rpm, after 5~10h of sustained response, by reaction under high pressure
Material filtering in kettle, filter cake recycling catalyst is spare, and filtrate obtains 2,2 '-dichlorohydrazobenzenes and lye mixture；
S2: position rotaring rearrangement, 2,2 '-dichlorohydrazobenzenes and lye mixture are cooled to 40 DEG C hereinafter, 2,2 '-dichloro hydrogen
Change azobenzene crystallization, then filters, filtrate drains into sewage treatment, is ground to 2,2 '-dichlorohydrazobenzenes using grinder
Particle is sent into position rotaring rearrangement in 23% hydrochloric acid less than 60 mesh, and control temperature of reactor is 20~40 DEG C, while opening stirring, is controlled
Mixing speed processed 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, and filter cake is first washed with clear water, is then dissolved with hot mother liquor；
S4: active 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 being centrifuged
Hydrochloride.
Preferably, in step 1, the water uses light water or softened water.
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 the chloro- 1,4-naphthoquinone of 2,3- bis-, mass fraction 90%.
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 DEG C, grinding precision granularity is less than 60 mesh.
Preferably, in step 4, the active 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 revolving 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 present invention are:
1. the present invention is scientific and reasonable, process flow is simple, substitutes toluene as ortho-nitrochlorobenzene catalytic hydrogenation by water
Solvent avoid greatly reducing using safe and environment-friendly hidden danger brought by toluene since water itself is colourless, tasteless, nontoxic
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 and water
Separation, product yield is high, quality is high；
2. the present invention grind in dnockout to 2,2 '-dichlorohydrazobenzenes and water by grinding pump, material is made to exist
Hundreds of thousands time per minute or even up to a million high speed shears are born in working chamber, form strong aquashear and turbulent flow,
Material moment under the comprehensive functions power such as centrifugation, extruding, collision, grinding, crushing obtains fully dispersed, homogeneous and mixing, improves
2,2 '-dichlorohydrazobenzene position rotaring rearrangement effects improve 2,2 '-dichlorohydrazobenzene yields.
Specific embodiment
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
Art personnel every other embodiment 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 method that water substitution toluene produces 3,3 '-dichlorobenzidine hydrochlorides,
Including being prepared using following steps:
S1: reduction reaction throws ortho-nitrochlorobenzene, water, sodium hydroxide, catalyst, co-catalyst and surfactant
Enter in autoclave, open stirring, control mixing speed is 160rpm, after sustained response 5h, by material in autoclave
Filtering, filter cake recycling catalyst is spare, and filtrate obtains 2,2 '-dichlorohydrazobenzenes and lye mixture；
S2: position rotaring rearrangement, 2,2 '-dichlorohydrazobenzenes and lye mixture are cooled to 40 DEG C, and the hydrogenation of 2,2 '-dichloros is even
Pyridine crystallization, is then filtered, filtrate drains into sewage treatment, and 2,2 '-dichlorohydrazobenzenes are ground to particle using grinder
Less than 60 mesh, it is sent into position rotaring rearrangement in 23% hydrochloric acid, control temperature of reactor is 20 DEG C, while opening stirring, control stirring speed
Degree is 60rpm, 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, and filter cake is first washed with clear water, is then dissolved with hot mother liquor；
S4: active 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 being centrifuged
Hydrochloride.
Wherein, water uses light water or softened water；Catalyst uses 0.3%Pt/C catalyst, water capacity 50%；It helps and urges
Agent uses the chloro- 1,4-naphthoquinone of 2,3- bis-, mass fraction 90%；In step 1, surfactant uses detergent alkylate sulphur
Sour sodium, technical grade；A length of 30min when the grinding reflux cycle of grinding pump, grinding operating temperature are 24 DEG C, grinding precision particle
Degree is less than 60 mesh；Active carbon be fine-powder shape shell activated carbon, granularity be 200~500 mesh, specific surface area be 600~
1500㎡/g；The revolving speed of low speed centrifuge is 600rpm, the when a length of 5min of low-speed centrifugal.
Embodiment two
The present invention provides a kind of technical solution: a kind of method that water substitution toluene produces 3,3 '-dichlorobenzidine hydrochlorides,
Including being prepared using following steps:
S1: reduction reaction throws ortho-nitrochlorobenzene, water, sodium hydroxide, catalyst, co-catalyst and surfactant
Enter in autoclave, open stirring, control mixing speed is 180rpm, after sustained response 7h, by material in autoclave
Filtering, filter cake recycling catalyst is spare, and filtrate obtains 2,2 '-dichlorohydrazobenzenes and lye mixture；
S2: position rotaring rearrangement, 2,2 '-dichlorohydrazobenzenes and lye mixture are cooled to 38 DEG C, and the hydrogenation of 2,2 '-dichloros is even
Pyridine crystallization, is then filtered, filtrate drains into sewage treatment, and 2,2 '-dichlorohydrazobenzenes are ground to particle using grinder
For 60 mesh, it is sent into position rotaring rearrangement in 23% hydrochloric acid, control temperature of reactor is 22 DEG C, while opening stirring, controls mixing speed
For 75rpm, 4h is persistently stirred；
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, and filter cake is first washed with clear water, is then dissolved with hot mother liquor；
S4: active 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 being centrifuged
Hydrochloride.
Wherein, water uses light water or softened water；Catalyst uses 0.3%Pt/C catalyst, water capacity 50%；It helps and urges
Agent uses the chloro- 1,4-naphthoquinone of 2,3- bis-, mass fraction 90%；In step 1, surfactant uses detergent alkylate sulphur
Sour sodium, technical grade；A length of 30min when the grinding reflux cycle of grinding pump, grinding operating temperature are 24 DEG C；Active carbon is subtle
Powdered shell activated carbon, granularity are 200~500 mesh, and specific surface area is 600~1500 ㎡/g；Low speed centrifuge turns
Speed is 600rpm, the when a length of 5min of low-speed centrifugal.
Embodiment three
The present invention provides a kind of technical solution: a kind of method that water substitution toluene produces 3,3 '-dichlorobenzidine hydrochlorides,
Including being prepared using following steps:
S1: reduction reaction throws ortho-nitrochlorobenzene, water, sodium hydroxide, catalyst, co-catalyst and surfactant
Enter in autoclave, open stirring, control mixing speed is 200rpm, after sustained response 8h, by material in autoclave
Filtering, filter cake recycling catalyst is spare, and filtrate obtains 2,2 '-dichlorohydrazobenzenes and lye mixture；
S2: position rotaring rearrangement, 2,2 '-dichlorohydrazobenzenes and lye mixture are cooled to 36 DEG C, and the hydrogenation of 2,2 '-dichloros is even
Pyridine crystallization, is then filtered, filtrate drains into sewage treatment, and 2,2 '-dichlorohydrazobenzenes are ground to particle using grinder
For 60 mesh, it is sent into position rotaring rearrangement in 23% hydrochloric acid, control temperature of reactor is 36 DEG C, while opening stirring, controls mixing speed
For 90rpm, 6h is persistently stirred；
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, and filter cake is first washed with clear water, is then dissolved with hot mother liquor；
S4: active 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 being centrifuged
Hydrochloride.
Wherein, water uses light water or softened water；Catalyst uses 0.3%Pt/C catalyst, water capacity 50%；It helps and urges
Agent uses the chloro- 1,4-naphthoquinone of 2,3- bis-, mass fraction 90%；In step 1, surfactant uses detergent alkylate sulphur
Sour sodium, technical grade；A length of 30min when the grinding reflux cycle of grinding pump, grinding operating temperature are 24 DEG C, grinding precision particle
Degree is less than 60 mesh；Active carbon be fine-powder shape shell activated carbon, granularity be 200~500 mesh, specific surface area be 600~
1500㎡/g；The revolving speed of low speed centrifuge is 600rpm, the when a length of 5min of low-speed centrifugal.
Example IV
The present invention provides a kind of technical solution: a kind of method that water substitution toluene produces 3,3 '-dichlorobenzidine hydrochlorides,
Including being prepared using following steps:
S1: reduction reaction throws ortho-nitrochlorobenzene, water, sodium hydroxide, catalyst, co-catalyst and surfactant
Enter in autoclave, open stirring, control mixing speed is 220rpm, after sustained response 10h, by material in autoclave
Filtering, filter cake recycling catalyst is spare, and filtrate obtains 2,2 '-dichlorohydrazobenzenes and lye mixture；
S2: position rotaring rearrangement, 2,2 '-dichlorohydrazobenzenes and lye mixture are cooled to 34 DEG C, and the hydrogenation of 2,2 '-dichloros is even
Pyridine crystallization, is then filtered, filtrate drains into sewage treatment, and 2,2 '-dichlorohydrazobenzenes are ground to particle using grinder
For 60 mesh, it is sent into position rotaring rearrangement in 23% hydrochloric acid, control temperature of reactor is 40 DEG C, while opening stirring, controls mixing speed
For 100rpm, 8h is persistently stirred；
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, and filter cake is first washed with clear water, is then dissolved with hot mother liquor；
S4: active 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 being centrifuged
Hydrochloride.
Wherein, water uses light water or softened water；Catalyst uses 0.3%Pt/C catalyst, water capacity 50%；It helps and urges
Agent uses the chloro- 1,4-naphthoquinone of 2,3- bis-, mass fraction 90%；In step 1, surfactant uses detergent alkylate sulphur
Sour sodium, technical grade；A length of 30min when the grinding reflux cycle of grinding pump, grinding operating temperature are 24 DEG C；Active carbon is subtle
Powdered shell activated carbon, granularity are 200~500 mesh, and specific surface area is 600~1500 ㎡/g；Low speed centrifuge turns
Speed is 600rpm, the when a length of 5min of low-speed centrifugal.
The invention has the following beneficial effects:
The present invention is scientific and reasonable, and process flow is simple, substitutes toluene as ortho-nitrochlorobenzene catalytic hydrogenation by water
Solvent avoids greatly reducing dirt using safe and environment-friendly hidden danger brought by toluene since water itself is colourless, tasteless, nontoxic
Dye, it is very environmentally friendly, it is a kind of process for cleanly preparing, and 3 after translocation reaction, 3 '-dichlorobenzidine hydrochlorides are easily and moisture
From product yield is high, quality is high；The present invention grind in dnockout to 2,2 '-dichlorohydrazobenzenes and water by grinding pump
Mill makes material bear the high speed shear of hundreds of thousands per minute time or even up to a million times in working chamber, forms strong fluid power
Shearing and turbulent flow, material moment under the comprehensive functions power such as centrifugation, extruding, collision, grinding, crushing obtain fully dispersed, homogeneous
And mixing, 2,2 '-dichlorohydrazobenzene position rotaring rearrangement effects are improved, 2,2 '-dichlorohydrazobenzene yields are improved.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (8)
1. a kind of method that water substitution toluene produces 3,3 '-dichlorobenzidine hydrochlorides, it is characterised in that: use following steps system
It is standby to form:
S1: reduction reaction puts into ortho-nitrochlorobenzene, water, sodium hydroxide, catalyst, co-catalyst and surfactant high
It presses in reaction kettle, opens stirring, control mixing speed is 160~220rpm, will be in autoclave after 5~10h of sustained response
Material filtering, filter cake recycling catalyst is spare, and filtrate obtains 2,2 '-dichlorohydrazobenzenes and lye mixture；
S2: position rotaring rearrangement, 2,2 '-dichlorohydrazobenzenes and lye mixture are cooled to 40 DEG C hereinafter, 2, and the hydrogenation of 2 '-dichloros is even
Pyridine crystallization, is then filtered, filtrate drains into sewage treatment, and 2,2 '-dichlorohydrazobenzenes are ground to particle using grinder
Less than 60 mesh, it is sent into position rotaring rearrangement in 23% hydrochloric acid, control temperature of reactor is 20~40 DEG C, while opening stirring, and control is stirred
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: active 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 being centrifuged
Salt.
2. the method that a kind of water substitution toluene according to claim 1 produces 3,3 '-dichlorobenzidine hydrochlorides, feature
Be: in step 1, the water uses light water or softened water.
3. the method that a kind of water substitution toluene according to claim 1 produces 3,3 '-dichlorobenzidine hydrochlorides, feature
Be: in step 1, the catalyst uses 0.3%Pt/C catalyst, 50% or more water capacity.
4. the method that a kind of water substitution toluene according to claim 1 produces 3,3 '-dichlorobenzidine hydrochlorides, feature
Be: in step 1, the co-catalyst uses the chloro- 1,4-naphthoquinone of 2,3- bis-, mass fraction 90%.
5. the method that a kind of water substitution toluene according to claim 1 produces 3,3 '-dichlorobenzidine hydrochlorides, feature
Be: in step 1, the surfactant uses neopelex, technical grade.
6. the method that a kind of water substitution toluene according to claim 1 produces 3,3 '-dichlorobenzidine hydrochlorides, feature
Be: in step 2, when grinding reflux cycle of the grinding pump a length of 30min, grinding operating temperature is 24 DEG C, grinding essence
Granularity is spent less than 60 mesh.
7. the method that a kind of water substitution toluene according to claim 1 produces 3,3 '-dichlorobenzidine hydrochlorides, feature
Be: in step 4, the active carbon is fine-powder shape shell activated carbon, and granularity is 200~500 mesh, specific surface area
For 600~1500 ㎡/g.
8. the method that a kind of water substitution toluene according to claim 1 produces 3,3 '-dichlorobenzidine hydrochlorides, feature
Be: in step 6, the revolving speed of low speed centrifuge is 600rpm, the when a length of 5min or more of low-speed centrifugal.
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|---|---|---|---|
| CN201810770542.5A CN108976131A (en) | 2018-07-13 | 2018-07-13 | A kind of method of water substitution toluene production DCB 3,3' dichlorobenzidine hydrochloride |
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| CN101225054A (en) * | 2008-01-25 | 2008-07-23 | 山西大学 | Method for preparing 2,2'-dichlorohydrazobenzene |
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| CN104610072A (en) * | 2015-02-17 | 2015-05-13 | 宁夏蓝丰精细化工有限公司 | Method for preparing 3,3'-dichlorobenzidine hydrochloride through rearrangement |
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| US4550207A (en) * | 1976-03-08 | 1985-10-29 | Bayer Aktiengesellschaft | Process for the preparation of benzene compounds |
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Application publication date: 20181211 |