CN109504120A - A kind of clean method for producing of high-purity copper phthalocyanine - Google Patents
A kind of clean method for producing of high-purity copper phthalocyanine Download PDFInfo
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- CN109504120A CN109504120A CN201910029391.2A CN201910029391A CN109504120A CN 109504120 A CN109504120 A CN 109504120A CN 201910029391 A CN201910029391 A CN 201910029391A CN 109504120 A CN109504120 A CN 109504120A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
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Abstract
The present invention provides the clean method for producing of high-purity copper phthalocyanine, include the following steps: that (1) synthesizes: alkylbenzene is put into condensation tank, after heating, continues to put into phthalic anhydride, urea, stannous chloride and ammonium molybdate are put into after phthalic anhydride dissolution, reacts and copper phthalocyanine crude product is made；(2) it refines: copper phthalocyanine slurry is made in copper phthalocyanine crude product, and it is added in the mixed liquor N of dilute sulfuric acid and cosolvent composition, heating stirring to copper phthalocyanine crude product is completely dissolved, water is added dropwise again, until copper phthalocyanine crystal is no longer precipitated, using filter, filter cake is washed through alcohol, washes, is filtered, and vacuum drying obtains high-purity copper phthalocyanine product；(3) devil liquor recovery: by a large amount of filtrates generated in reaction process through ion exchange resin absorption, neutralization, concentration and evaporation, centrifugation and etc. be made product ammonium sulfate.The made copper phthalocyanine purity is high of the present invention, crystal form is single, and coloring effect is good, and color stability is excellent, while the tail gas and waste water being effectively treated in production, the economic benefit with energy-saving and emission-reduction.
Description
Technical field
The invention belongs to dyestuff preparation technical fields, and in particular to a kind of production method of copper phthalocyanine, more particularly to it is a kind of
The clean method for producing of high-purity copper phthalocyanine.
Background technique
Copper phthalocyanine, molecular formula: C32H16CuN8, it is macrocyclic compound, the special construction containing four azaporphins.In 1907,
Copper phthalocyanine is chanced in one experiment by German chemist A.Braun and J.Tchemiac.Copper phthalocyanine has distinct indigo plant
Color has higher tinting strength, tinting power, energy acid and alkali-resistance, solvent resistant, and has good fast light and weatherability, is to have every excellent properties
A kind of pigment, therefore in organic pigment, it occupies an important position.Copper phthalocyanine is combined in a manner of covalent bond, is had good
Good stability.It can be distilled in 400-500 DEG C of vacuum or in inert gas without changing, even if for a long time and mineral
Acid contact will not slough metal.Copper phthalocyanine is generally not soluble in water, is slightly soluble in organic solvent, but can be dissolved in the concentrated sulfuric acid, chlorosulfonic acid,
Acid salt is formed in phosphoric acid.It can be destroyed by strong oxidizer such as nitric acid, potassium permanganate solution, and it is sub- to form phthalyl
Amine.
Benzene bitter wine-urea method is that industrial common copper phthalocyanine preparation method is reacted using enamel material under normal pressure
Solvent, phthalic anhydride, urea, cuprous, catalyst investment are wherein uniformly mixed, heat up, pressurize by device, pressure control 0.35 ~
0.4Mpa, temperature are 140 ~ 185 DEG C, and decrease temperature and pressure blowing obtains copper phthalocyanine after reaction.Made copper phthalocyanine purity is not high, and produces
Object is mixing crystal form, and coloring effect is bad, and color stability is not good enough.Therefore, the copper phthalocyanine of a kind of high-purity, single crystal form is developed
Clean method for producing becomes urgent problem to be solved.
Summary of the invention
The present invention provides a kind of clean method for producing of high-purity copper phthalocyanine, copper phthalocyanine purity is high produced, and
Crystal form is single, and coloring effect is good, and color stability is excellent, while the tail gas and waste water being effectively treated in production, has energy conservation
The economic benefit of emission reduction.
The technical proposal for solving the technical problem of the invention are as follows:
A kind of clean method for producing of high-purity copper phthalocyanine, which is characterized in that the production method includes the following steps:
(1) it synthesizes: alkylbenzene being put into condensation tank, is warming up to 125 ~ 135 DEG C, continue to put into phthalic anhydride, at 125 ~ 135 DEG C
Insulated and stirred to phthalic anhydride is completely dissolved, then puts into urea, stannous chloride and catalyst ammonium molybdate, after feeding intake, sealing boosting
It is depressurized to normal pressure after the reaction was continued at 185 ~ 195 DEG C 6 ~ 8 hours to 0.4 ~ 0.5Mpa, room temperature is cooled to, after blowing is dry
Obtain copper phthalocyanine crude product；The tail gas generated in condensation reaction successively uses 25wt% dilute sulfuric acid and water spray to absorb, and gained absorbs twice
Liquid merges to be layered through sedimentation, and it is stand-by to obtain subnatant M；After phthalic anhydride is completely dissolved, then other raw materials are put into, so that reaction is completeer
Entirely, product yield is higher.
Copper phthalocyanine can generate the tail gas such as a large amount of ammonias and carbon dioxide in the synthesis process, use tail gas in preparation process
25wt% dilute sulfuric acid and water spray absorb, and harmful substance contents in tail gas can be effectively reduced, and liquid containing ammonium sulfate and a small amount of ammonium hydroxide is made
Absorbing liquid, i.e. subnatant M.
(2) it refines: copper phthalocyanine slurry is made in copper phthalocyanine crude product obtained by step (1), and dilute sulfuric acid and cosolvent group is added
At mixed liquor N in, after being heated to 90 ~ 95 DEG C, insulated and stirred 3 ~ 5 hours, copper phthalocyanine crude product is completely dissolved, then water is added dropwise, directly
It is no longer precipitated to copper phthalocyanine crystal, using filter, obtains that filtrate A is to be processed, and filter cake is washed through alcohol, washes, filtered, 60 ~ 70 DEG C of vacuum
Dry to obtain high-purity copper phthalocyanine product；
Cosolvent described in step (2) is certain herbaceous plants with big flowers base glucoside or Octyl glucoside.
Containing raw materials such as the complete phthalic anhydride of unreacted, urea in the made copper phthalocyanine crude product of step (1), simultaneously because copper phthalocyanine
With " more matter isomorphous " phenomenon, contains a variety of crystal form mixtures such as α, β in copper phthalocyanine crude product, lead to copper phthalocyanine crude product purity not
Height, product coloring effect and color stability be not good enough.Due to beta-type copper phthalocyanine dissolubility with higher in concentrated sulfuric acid, by it
It is dissolved in the concentrated sulfuric acid, then is diluted with water, the crystal being precipitated at this time is α type.Using this characteristic of copper phthalocyanine, can refine
Obtain the higher single crystal form of purity, i.e. α type copper phthalocyanine.But it usually requires to use a large amount of concentrated sulfuric acid in subtractive process, and uses
The eduction rate of crystal is lower when water dilutes, and copper phthalocyanine yield in subtractive process is caused to be declined.And the use recycling of concentrated acid
Environment protection emission and economic cost will be increased.
The present invention refines copper phthalocyanine crude product using the mixed liquor N that dilute sulfuric acid and cosolvent form, and cosolvent is selected
Certain herbaceous plants with big flowers base glucoside or Octyl glucoside.Cosolvent can with the N atom in copper phthalocyanine formed hydrogen bond structure, thus increase its
Dissolubility in acid is dissolved in it in mixed liquor N.The acid concentration of mixed liquor N is significantly less than concentrated sulfuric acid acid concentration, effectively reduces
Environmental pollution.Water is added thereto again, acid concentration continues to reduce, and α type copper phthalocyanine is gradually precipitated at this time.After filtering, contain in filter cake
There are raw materials and an acid solutions such as the complete phthalic anhydride of unreacted, urea, frequent alcohol washes, washes and successively removes, and obtains high-purity alpha type copper phthalein
Cyanines product.Copper phthalocyanine slurry is made in copper phthalocyanine crude product obtained by step (1) facilitates it in mixed liquor N and dissolves.
(3) devil liquor recovery: filtrate A obtained by step (2) is handled through anionic ion-exchange resins and removes organic matter, is obtained
Liquor B, liquor B mix neutralization with subnatant M, and adjustment mixed liquor PH is 4, are filtered, then through anion exchange resin process
Organic matter is removed, then through activated carbon adsorption, is filtered, filter residue obtains liquor C and enters MVR evaporator evaporation and concentration as fixed-end forces,
Gained concentrate dries to obtain wet product ammonium sulfate by centrifuge.
Contain a large amount of dilute sulfuric acids in filtrate A, a small amount of complete organic matter of unreacted is removed through anion exchange resin process
Organic matter, gained liquor B are dilute acid soln, and neutralization is mixed with the subnatant M containing a small amount of ammonium hydroxide, and neutralized reaction generates sulfur-bearing
The waste liquid of sour ammonium.Organic matter is removed through anion exchange resin process again, then filter further removal through activated carbon adsorption to have
Machine object, filtering, gained liquor C is ammonium sulfate solution at this time, is concentrated by evaporation, is centrifuged to obtain ammonium sulfate wet product.
(4) resin regeneration: the resin of adsorption saturation is regenerated with the ammonium hydroxide that mass concentration is 2-5%, and 5wt% is added in desorbed solution
Sulfuric acid is neutralized to PH as 2-3 filtering, and filter residue returns to ammonium sulfate system as solid waste, filtrate.
Preferably, alkylbenzene described in step (1) is toluene, ortho-xylene or meta-xylene.
Preferably, alkylbenzene described in step (1), phthalic anhydride, urea, stannous chloride and catalyst ammonium molybdate mass ratio
For 480 ~ 520:200 ~ 250:200 ~ 250:40 ~ 45:1.
Preferably, the mass concentration of dilute sulfuric acid described in step (2) is 30 ~ 45%, the copper phthalocyanine slurry, dilute sulfuric acid
Mass ratio with cosolvent is 1 ~ 2:1:0.3 ~ 0.5.The concentration of dilute sulfuric acid and cosolvent is to copper phthalocyanine crude product dissolved with larger
It influences, concentration is too low, cannot dissolve copper phthalocyanine crude product；Excessive concentration can generate a large amount of acid waste waters.
Preferably, the rate of addition of water described in step (2) is 15 ~ 20mL/min.The rate of addition of water will affect α type
The precipitation rate and granularity of copper phthalocyanine, water droplet acceleration is too fast, then α type copper phthalocyanine speed of separating out is too fast, and particle is excessive, causes
Product content is too low in mother liquor, to stop crystallization too early, so that product yield is too low.
Preferably, anionic ion-exchange resins described in step (3) are the absorption of macropore Hypercrosslinked polystyrene
The aperture of resin, the macropore Hypercrosslinked polystyrene absorption resin is 6 ~ 30nm.
Preferably, copper phthalocyanine slurry described in step (2) the preparation method comprises the following steps: copper phthalocyanine crude product add water mashing mixing
It after uniformly, then emulsifies and is made through colloid mill, the mass ratio of the copper phthalocyanine crude product and water is 1:15 ~ 20.
The invention has the benefit that
1, the present invention refines copper phthalocyanine crude product using the mixed liquor N that dilute sulfuric acid and cosolvent form, and improves product purity, obtains
The α type copper phthalocyanine of single crystal form is obtained, the partially red phase of product form and aspect, bright in color light, tinting strength, tinting power is good, and color stability.
2, the tail gas that condensation reaction generates is effectively treated copper phthalocyanine production method provided by the present invention, and by with essence
In waste liquid during system and ammonium sulfate is obtained, environmental pollution is on the one hand reduced, has on the other hand reached resource reutilization
Purpose, the economic benefit with energy-saving and emission-reduction.
3, the present invention joined a small amount of cosolvent in copper phthalocyanine subtractive process, help speed up the dissolution of copper phthalocyanine crude product,
It avoids using the concentrated sulfuric acid, greatly reduces operation difficulty, reduce acid waste water discharge.
Specific embodiment
Next combined with specific embodiments below the present invention is further described, but it is specific real not limit the invention to these
Apply mode.
Embodiment 1
(1) it synthesizes: 500g toluene being put into condensation tank, is warming up to 130 DEG C, continue to put into 220g phthalic anhydride, be protected at 130 DEG C
Temperature stirring to phthalic anhydride is completely dissolved, then puts into 220g urea, 40g stannous chloride and 1g catalyst ammonium molybdate, close after feeding intake
Envelope boosts to 0.5Mpa, after the reaction was continued at 185 DEG C 7 hours, is depressurized to normal pressure, is cooled to room temperature, after blowing is dry
302g copper phthalocyanine crude product；The tail gas generated in condensation reaction successively uses 25wt% dilute sulfuric acid and water spray to absorb, and gained is inhaled twice
It receives liquid to merge through sedimentation layering, it is stand-by to obtain subnatant M；
(2) it refines: adding the mashing of 450g water after mixing, then through colloid mill to emulsify 30g copper phthalocyanine crude product obtained by step (1)
480g copper phthalocyanine slurry is made, and is added in the mixed liquor N of 240g 25wt% dilute sulfuric acid and 96g certain herbaceous plants with big flowers base glucoside composition,
After being heated to 90 DEG C, insulated and stirred 5 hours, copper phthalocyanine crude product is completely dissolved, then water is added dropwise, until copper phthalocyanine crystal is no longer analysed
Out, using filter, obtain that filtrate A is to be processed, and filter cake is washed through alcohol, washes, filtered, 65 DEG C of vacuum dry purity is 95.7%
17.5g copper phthalocyanine product, the content that gained copper phthalocyanine product measures α type copper phthalocyanine through x-ray diffractometer are 99.7%.
(3) devil liquor recovery: filtrate A obtained by step (2) is handled through anionic ion-exchange resins and removes organic matter, is obtained
Liquor B, liquor B mix neutralization with subnatant M, and adjustment mixed liquor PH is 4, are filtered, then through anion exchange resin process
Organic matter is removed, then through activated carbon adsorption, is filtered, filter residue obtains liquor C and enters MVR evaporator evaporation and concentration as fixed-end forces,
Gained concentrate dries to obtain wet product ammonium sulfate by centrifuge.
(4) resin regeneration: the ammonium hydroxide that the resin mass concentration of adsorption saturation is 35% regenerates, and 5wt% sulphur is added in desorbed solution
It is 2.5 filterings that acid, which is neutralized to PH, and filter residue returns to ammonium sulfate system as solid waste, filtrate.
Embodiment 2
(1) it synthesizes: 480g ortho-xylene being put into condensation tank, is warming up to 125 DEG C, continue to put into 250g phthalic anhydride, in 125 DEG C
Lower insulated and stirred to phthalic anhydride is completely dissolved, then puts into 250g urea, 45g stannous chloride and 1g catalyst ammonium molybdate, is fed intake and is finished
Afterwards, sealing boosts to 0.45Mpa, after the reaction was continued at 195 DEG C 8 hours, is depressurized to normal pressure, is cooled to room temperature, and blowing is dry
328g copper phthalocyanine crude product is obtained afterwards；The tail gas generated in condensation reaction successively uses 25wt% dilute sulfuric acid and water spray to absorb, gained two
Secondary absorbing liquid merges to be layered through sedimentation, and it is stand-by to obtain subnatant M；
(2) it refines: adding the mashing of 540g water after mixing, then through colloid mill to emulsify 30g copper phthalocyanine crude product obtained by step (1)
570g copper phthalocyanine slurry is made, and is added in the mixed liquor N of 570g 25wt% dilute sulfuric acid and 228g Octyl glucoside composition,
After being heated to 95 DEG C, insulated and stirred 3 hours, copper phthalocyanine crude product is completely dissolved, then water is added dropwise, until copper phthalocyanine crystal is no longer analysed
Out, using filter, obtain that filtrate A is to be processed, and filter cake is washed through alcohol, washes, filtered, 60 DEG C of vacuum dry purity is 96.3%
18.2g copper phthalocyanine product, the content that gained copper phthalocyanine product measures α type copper phthalocyanine through x-ray diffractometer are 99.5%.
(3) devil liquor recovery: filtrate A obtained by step (2) is handled through anionic ion-exchange resins and removes organic matter, is obtained
Liquor B, liquor B mix neutralization with subnatant M, and adjustment mixed liquor PH is 4, are filtered, then through anion exchange resin process
Organic matter is removed, then through activated carbon adsorption, is filtered, filter residue obtains liquor C and enters MVR evaporator evaporation and concentration as fixed-end forces,
Gained concentrate dries to obtain wet product ammonium sulfate by centrifuge.
(4) resin regeneration: the ammonium hydroxide that the resin mass concentration of adsorption saturation is 35% regenerates, and 5wt% sulphur is added in desorbed solution
It is 2.5 filterings that acid, which is neutralized to PH, and filter residue returns to ammonium sulfate system as solid waste, filtrate.
Embodiment 3
(1) it synthesizes: 520g meta-xylene being put into condensation tank, is warming up to 135 DEG C, continue to put into 200g phthalic anhydride, in 135 DEG C
Lower insulated and stirred to phthalic anhydride is completely dissolved, then puts into 200g urea, 42g stannous chloride and 1g catalyst ammonium molybdate, is fed intake and is finished
Afterwards, sealing boosts to 0.4Mpa, after the reaction was continued at 190 DEG C 6 hours, is depressurized to normal pressure, room temperature is cooled to, after blowing is dry
Obtain 278g copper phthalocyanine crude product；The tail gas generated in condensation reaction successively uses 25wt% dilute sulfuric acid and water spray to absorb, and gained is twice
Absorbing liquid merges to be layered through sedimentation, and it is stand-by to obtain subnatant M；
(2) it refines: adding the mashing of 600g water after mixing, then through colloid mill to emulsify 30g copper phthalocyanine crude product obtained by step (1)
630g copper phthalocyanine slurry is made, and is added in the mixed liquor N of 240g 25wt% dilute sulfuric acid and 120g certain herbaceous plants with big flowers base glucoside composition,
After being heated to 92 DEG C, insulated and stirred 4 hours, copper phthalocyanine crude product is completely dissolved, then water is added dropwise, until copper phthalocyanine crystal is no longer analysed
Out, using filter, obtain that filtrate A is to be processed, and filter cake is washed through alcohol, washes, filtered, 70 DEG C of vacuum dry purity is 95.3%
18.4g copper phthalocyanine product, the content that gained copper phthalocyanine product measures α type copper phthalocyanine through x-ray diffractometer are 99.6%.
(3) devil liquor recovery: filtrate A obtained by step (2) is handled through anionic ion-exchange resins and removes organic matter, is obtained
Liquor B, liquor B mix neutralization with subnatant M, and adjustment mixed liquor PH is 4, are filtered, then through anion exchange resin process
Organic matter is removed, then through activated carbon adsorption, is filtered, filter residue obtains liquor C and enters MVR evaporator evaporation and concentration as fixed-end forces,
Gained concentrate dries to obtain wet product ammonium sulfate by centrifuge.
(4) resin regeneration: the ammonium hydroxide that the resin mass concentration of adsorption saturation is 35% regenerates, and 5wt% sulphur is added in desorbed solution
It is 2.5 filterings that acid, which is neutralized to PH, and filter residue returns to ammonium sulfate system as solid waste, filtrate.
Comparative example 1
(1) it synthesizes: 500g toluene being put into condensation tank, is warming up to 130 DEG C, continue to put into 220g phthalic anhydride, be protected at 130 DEG C
Temperature stirring to phthalic anhydride is completely dissolved, then puts into 220g urea, 40g stannous chloride and 1g catalyst ammonium molybdate, close after feeding intake
Envelope boosts to 0.5Mpa, after the reaction was continued at 185 DEG C 7 hours, is depressurized to normal pressure, is cooled to room temperature, after blowing is dry
302g copper phthalocyanine crude product；The tail gas generated in condensation reaction successively uses 25wt% dilute sulfuric acid and water spray to absorb, and gained is inhaled twice
It receives liquid to merge through sedimentation layering, it is stand-by to obtain subnatant M；
(2) it refines: 30g copper phthalocyanine crude product obtained by step (1) is added in the 50g concentrated sulfuric acid, until stirring to no longer dissolution, then
It is poured slowly into 1000g water, after stirring half an hour, refines 6 ~ 8 hours, filtering, filtration cakes torrefaction obtain copper phthalocyanine product, through X-ray
The content that diffractometer measures α type copper phthalocyanine is 63.8%.
It is obtained by comparative example 1 and comparative example 1, copper phthalocyanine refining methd provided by the present invention can obtain height
Purity α type copper phthalocyanine, avoids using the concentrated sulfuric acid, greatly reduces operation difficulty, reduces acid waste water discharge.
Comparative example 2
(1) it synthesizes: 500g toluene being put into condensation tank, is warming up to 130 DEG C, continue to put into 220g phthalic anhydride, be protected at 130 DEG C
Temperature stirring to phthalic anhydride is completely dissolved, then puts into 220g urea, 40g stannous chloride and 1g catalyst ammonium molybdate, close after feeding intake
Envelope boosts to 0.5Mpa, after the reaction was continued at 185 DEG C 7 hours, is depressurized to normal pressure, is cooled to room temperature, after blowing is dry
302g copper phthalocyanine crude product；The tail gas generated in condensation reaction successively uses 25wt% dilute sulfuric acid and water spray to absorb, and gained is inhaled twice
It receives liquid to merge through sedimentation layering, it is stand-by to obtain subnatant M；
(2) it refines: adding the mashing of 450g water after mixing, then through colloid mill to emulsify 30g copper phthalocyanine crude product obtained by step (1)
480g copper phthalocyanine slurry is made, and is added in 240g 25wt% dilute sulfuric acid, after being heated to 90 DEG C, insulated and stirred 20 hours, copper
Phthalocyanine crude still has a large amount of insoluble, filtering, and water is added dropwise again in filtrate, until copper phthalocyanine crystal is no longer precipitated, using filter, filter
Cake is washed through alcohol, washes, is filtered, 65 DEG C of vacuum dry purity be 47.3% 3.5g copper phthalocyanine product, gained copper phthalocyanine product warp
The content that x-ray diffractometer measures α type copper phthalocyanine is 72.3%.
It is obtained by comparative example 1 and comparative example 2, cosolvent helps speed up the dissolution of copper phthalocyanine crude product, improves product
Purity and α type copper phthalocyanine content.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (8)
1. a kind of clean method for producing of high-purity copper phthalocyanine, which is characterized in that the production method includes the following steps:
(1) it synthesizes: alkylbenzene being put into condensation tank, is warming up to 125 ~ 135 DEG C, continue to put into phthalic anhydride, at 125 ~ 135 DEG C
Insulated and stirred to phthalic anhydride is completely dissolved, then puts into urea, stannous chloride and catalyst ammonium molybdate, after feeding intake, sealing boosting
It is depressurized to normal pressure after the reaction was continued at 185 ~ 195 DEG C 6 ~ 8 hours to 0.4 ~ 0.5Mpa, room temperature is cooled to, after blowing is dry
Obtain copper phthalocyanine crude product；The tail gas generated in condensation reaction successively uses 25wt% dilute sulfuric acid and water spray to absorb, and gained absorbs twice
Liquid merges to be layered through sedimentation, and it is stand-by to obtain subnatant M；
(2) it refines: copper phthalocyanine slurry is made in copper phthalocyanine crude product obtained by step (1), and dilute sulfuric acid and cosolvent composition is added
In mixed liquor N, after being heated to 90 ~ 95 DEG C, insulated and stirred 3 ~ 5 hours, copper phthalocyanine crude product is completely dissolved, then water is added dropwise, until copper
Phthalocyanine crystal is no longer precipitated, and using filter, obtains that filtrate A is to be processed, and filter cake is washed through alcohol, washes, filtered, 60 ~ 70 DEG C of vacuum drying
Obtain high-purity copper phthalocyanine product；
(3) devil liquor recovery: filtrate A obtained by step (2) is handled through anionic ion-exchange resins and removes organic matter, obtains filtrate
B, liquor B mix neutralization with subnatant M, and adjustment mixed liquor PH is 4, are filtered, then remove through anion exchange resin process
Organic matter, then through activated carbon adsorption, filter, filter residue obtains liquor C and enters MVR evaporator evaporation and concentration, gained as fixed-end forces
Concentrate dries to obtain wet product ammonium sulfate by centrifuge.
2. the clean method for producing of high-purity copper phthalocyanine as described in claim 1, which is characterized in that described in step (1)
Alkylbenzene be toluene, ortho-xylene or meta-xylene.
3. the clean method for producing of high-purity copper phthalocyanine as claimed in claim 1 or 2, which is characterized in that
Alkylbenzene described in step (1), phthalic anhydride, urea, stannous chloride and catalyst ammonium molybdate mass ratio be 480 ~ 520:200
~ 250:200 ~ 250:40 ~ 45:1.
4. the clean method for producing of high-purity copper phthalocyanine as described in claim 1, which is characterized in that described in step (2)
The mass concentration of dilute sulfuric acid is 30 ~ 45%, the mass ratio of the copper phthalocyanine slurry, dilute sulfuric acid and cosolvent be 1 ~ 2:1:0.3 ~
0.5。
5. the clean method for producing of high-purity alpha type copper phthalocyanine as described in claim 1, which is characterized in that institute in step (2)
The rate of addition for stating water is 15 ~ 20mL/min.
6. the clean method for producing of high-purity copper phthalocyanine as described in claim 1, which is characterized in that described in step (2)
Cosolvent be certain herbaceous plants with big flowers base glucoside or Octyl glucoside.
7. the clean method for producing of high-purity copper phthalocyanine as described in claim 1, which is characterized in that described in step (3)
Anionic ion-exchange resins be that macropore Hypercrosslinked polystyrene adsorbs resin, the macropore Hypercrosslinked polystyrene is inhaled
The aperture of attached resin is 6 ~ 30nm.
8. the clean method for producing of high-purity copper phthalocyanine as described in claim 1, which is characterized in that described in step (2)
Copper phthalocyanine slurry the preparation method comprises the following steps: copper phthalocyanine crude product add water mashing after mixing, then through colloid mill emulsify be made, it is described
The mass ratio of copper phthalocyanine crude product and water is 1:15 ~ 20.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110229164A (en) * | 2019-07-01 | 2019-09-13 | 双乐颜料股份有限公司 | Heatproof α type phthalocyanine blue production technology |
| CN112657326A (en) * | 2020-12-03 | 2021-04-16 | 宣城亚邦化工有限公司 | Purification system and purification method for tail gas generated in copper phthalocyanine production process |
| CN114133762A (en) * | 2021-10-22 | 2022-03-04 | 双乐颜料泰兴市有限公司 | Method and related device for synthesizing copper phthalocyanine |
| CN115960473A (en) * | 2022-12-28 | 2023-04-14 | 江苏丽王科技股份有限公司 | Method for preparing metal phthalocyanine pigment by solvent method |
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| CN112657326A (en) * | 2020-12-03 | 2021-04-16 | 宣城亚邦化工有限公司 | Purification system and purification method for tail gas generated in copper phthalocyanine production process |
| CN114133762A (en) * | 2021-10-22 | 2022-03-04 | 双乐颜料泰兴市有限公司 | Method and related device for synthesizing copper phthalocyanine |
| CN115960473A (en) * | 2022-12-28 | 2023-04-14 | 江苏丽王科技股份有限公司 | Method for preparing metal phthalocyanine pigment by solvent method |
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