CN106673040B - Aluminium polychloride method is recycled using the aluminium trichloride waste water of synthesis of triazine ultra-violet absorber - Google Patents
Aluminium polychloride method is recycled using the aluminium trichloride waste water of synthesis of triazine ultra-violet absorber Download PDFInfo
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- CN106673040B CN106673040B CN201611182801.XA CN201611182801A CN106673040B CN 106673040 B CN106673040 B CN 106673040B CN 201611182801 A CN201611182801 A CN 201611182801A CN 106673040 B CN106673040 B CN 106673040B
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Abstract
The present invention relates to a kind of aluminium trichloride waste waters using synthesis of triazine ultra-violet absorber to recycle aluminium polychloride method.Aluminium skimmings are added into aluminium trichloride waste water, stirring is warming up to 85 90 DEG C of heat preservations, obtains the liquid that pH value is 3.5 4.5；Liquid is cooled to 20 50 DEG C of addition activated carbons, is stirred, filtering removes the organic impurities of unreacted aluminium skimmings and insoluble impurity and activated carbon adsorption, obtains filtrate；Obtained filtrate is put into container, it is heated with stirring to 100 105 DEG C of reflux, withdrawing fluid continues to flow back full of water knockout drum, until sinking without chlorobenzene or o-dichlorohenzene, lower layer's solvent is collected, the water in water knockout drum is released, and continues to distill moisture content, density >=1.10g/ml, as liquid aluminium polychloride when detecting 20 DEG C of remaining liq.The present invention not only reduces the discharge of waste water, also turns waste into wealth, and reduces the manufacturing cost of triazine-based ultraviolet absorbent, has achieved the purpose that energy-saving and emission-reduction, environmentally protective.
Description
Technical field
The invention belongs to organic synthesis wastewater treating technology fields, and in particular to a kind of to be inhaled using synthesis of triazine ultraviolet light
The aluminium trichloride waste water for receiving agent recycles aluminium polychloride method.
Background technology
Triazine-based ultraviolet absorbent has the structure of structure formula (I)：
Wherein R is-H ,-CH3It is-H ,-C Deng, R18H17、-CH2CH(OH)OC12H25、-CH2CH(OH)OC13H27、-CH2CH
(OH)OC4H9Deng.When R is-H ,-CH3, when R1 is-H, structure formula (I) is 2- (2,4- dihydroxy phenyl)-diphenyl -1 4,6-,
3,5- triazines or bis- (2,4- the 3,5-dimethylphenyl) -1,3,5-triazines of 2- (2,4- dihydroxy phenyl) -4,6-, important is as in
Mesosome further synthesizes the ultra-violet absorber of the excellent unique energy of multiple performance, such as 2- (2,4- dihydroxy benzenes
Base) -4,6- diphenyl -1,3,5-triazines and bromohexane reaction synthesis UV1577；2- (2,4- dihydroxy phenyl) -4,6- it is bis- (2,
4- 3,5-dimethylphenyls) -1,3,5-triazines and bromooctane reaction synthesis UV1164；2- (2,4- dihydroxy phenyl) -4,6- bis- (2,4-
3,5-dimethylphenyl) -1,3,5-triazines and-CH2CH(OH)OC12H25、-CH2CH(OH)OC13H27Reaction synthesis UV400；UV1577
Favorable compatibility with low volatility and with multiple polymers, copolymer and synthetic resin is used in makrolon and polyester side
Face has better effect；UV1164 has the ultraviolet light inherent stability of height, does not react with metal, and durability is high,
For nylon, PVC, PET, PBT, ABS and PMMA etc.；UV400 has excellent thermal stability and environment durability, migration effect
Low, good light stability is used in the coating used under high-temperature baking and extreme harsh conditions, is additionally operable to amine catalysis or metal catalytic
Cured coating system and the cured coating system of ultraviolet light.
Aluminium trichloride waste water is in synthesis 2- (2,4- dihydroxy phenyl) -4,6- diphenyl -1,3,5-triazines or 2- (2,4-
Dihydroxy phenyl) -4,6- bis- both intermediates of (2,4- 3,5-dimethylphenyl) -1,3,5-triazines production process in generate,
There are magnesium powder method, alchlor process, since the condition of magnesium powder method is harsher, so most of use trichlorine both at home and abroad at present
Change aluminium method, i.e., Cyanuric Chloride, chlorobenzene or o-dichlorohenzene, the alchlor of 3 times of molal quantitys of Cyanuric Chloride are added in the reactor and stirs
It mixes, the benzene or meta-xylene of 2 times of molal quantitys of Cyanuric Chloride is slowly added dropwise at 0-5 DEG C, 1 times of molal quantity of Cyanuric Chloride is then added
Resorcinol, react and triazine diphenols ultra-violet absorber be made, i.e. 2- (2,4- dihydroxy phenyl)-diphenyl -1 4,6-,
3,5- triazines or bis- (2,4- the 3,5-dimethylphenyl) -1,3,5-triazines of 2- (2,4- dihydroxy phenyl) -4,6-, reaction are finished material
It pours into 0-5 DEG C of dilute hydrochloric acid, hydrolyzes alchlor, hydrolysis formula of the alchlor in dilute hydrochloric acid is：
AlCl3+H2O→Al2(OH)nCl6-n+ HCl, wherein n are 1-5.
Then solid product is filtered out, filtrate standing separation organic phase, inorganic phase, that is, aluminium trichloride waste water and minimal amount of
Organic matter and solvent chlorobenzene or o-dichlorohenzene, due to a large amount of generations of aluminium trichloride waste water, to constrain triazine-based ultraviolet
The production of absorbent, aluminium trichloride waste water are generally the diluted hydrochloric acid aqueous solution of the 4-8% of mass concentration containing alchlor, therefore trichlorine
The waste water that the recycling of change aluminium waste water solves triazine-based ultraviolet absorbent can not emission problem.
Finding a kind of method recycling aluminium trichloride waste water is particularly important, currently, general method is to be added
The lye such as sodium hydroxide or quick lime generate aluminium chloride (aluminium polychloride), or aluminium chloride heat drying is formed
Solid basic aluminium chloride, or by aluminium chloride pyrolysis reduction, by the hydrogen chloride supplement chlorine of pyrolysis, chlorination is anhydrous trichlorine again
Change aluminium.Because lye, which is added, introduces new substance again, salt is produced, so as to cause new treatment of wastes produced, and due to
Part salt removal is not clean, influences its flocculating effect as water purification agent.The invention avoids the generation of new waste, generation
Aluminium polychloride flocculating effect is good, efficient.
Invention content
It is an object of the invention to solve the production bottleneck of the prior art, a kind of utilization synthesis of triazine ultraviolet light suction is provided
The aluminium trichloride waste water for receiving agent recycles aluminium polychloride method, it is intended to reduce discharge of wastewater, turn waste into wealth, recycle.
To achieve the above object, the technical solution used in the present invention is：
A kind of aluminium trichloride waste water recycling aluminium polychloride method using synthesis of triazine ultra-violet absorber, including with
Lower step：
(1) aluminium skimmings are added into aluminium trichloride waste water, stirring is warming up to 85-90 DEG C of heat preservation, and it is 3.5-4.5's to obtain pH value
Liquid；
(2) liquid that step (1) obtains is cooled to 20-50 DEG C of addition activated carbon, stirred, filtering removes unreacted
The organic impurities of aluminium skimmings and insoluble impurity and activated carbon adsorption, obtains filtrate；
(3) filtrate that step (2) obtains is put into container, is heated with stirring to 100-105 DEG C of reflux, withdrawing fluid fills
Full marks hydrophone continues to flow back, until sinking without chlorobenzene or o-dichlorohenzene, lower layer's solvent is collected, and releases the water in water knockout drum,
And continue to distill moisture content, density >=1.10g/ml, as liquid aluminium polychloride when 20 DEG C of remaining liq of detection.
Obtained liquid aluminium polychloride is dried, and obtains solid polyaluminium chloride.
The addition of aluminium skimmings is aluminium trichloride waste water quality 1.6-2.2% in the step (1).
In the step (1) 85-90 DEG C of heat preservation 3-6h is warming up to using 2-3h stirrings.
Activated carbon addition is the 0.5-1% of aluminium trichloride waste water quality in the step (2).
It is filtered after stirring 2-4h at 20-50 DEG C in the step (2).
The activated carbon being added in the step (2) is the sawdust charcoal of 220 mesh.
The hydrolysis formula of the aluminium trichloride waste water of the step (1) is：
AlCl3+H2O→Al2(OH)nCl6-n+ HCl, wherein n are 1-5.
Aluminium skimmings (aluminium content 85-90%, alundum (Al2O3) content 10-5%) dissolving reaction equation be：
Al+H2O+HCl→Al2(OH)nCl6-n+H2, Al2O3+H2O+HCl→Al2(OH)nCl6-n, wherein n is 1-5.
With the dissolving of aluminium skimmings, pH value gradually increases, Al2(OH)nCl6-nGradually polymerization, reaction equation are：
mAl2(OH)n Cl6-n→[Al2(OH)n Cl6-n]m, m 1-10, n 1-5.
The present invention reduces the losses of solvent, and by it is every production 1 ton 2- (2,4- dihydroxy phenyl) -4,6- it is bis- (2,
4- 3,5-dimethylphenyls) -1,3,5-triazines (or 0.85 ton of 2- (2,4- dihydroxy phenyl) -4,6- diphenyl -1,3,5-triazines)
About 18 tons of aluminium trichloride waste waters of generation are transformed into 2.1 tons of solid polyaluminium chloride；The chlorobenzene or o-dichlorohenzene of recycling simultaneously
Recovery, the moisture steamed, which is added hydrochloric acid and is tuned into, needs the dilute hydrochloric acid of concentration to hydrolyze alchlor for lower batch.The present invention is not
The discharge for only reducing waste water, also turns waste into wealth, and produces great economic benefit and social benefit.In the method for the present invention
Not only intra-company uses the polyaluminium chloride water purification agent arrived, can also sell as product.Present invention reduces triazines
The manufacturing cost of class ultra-violet absorber has achieved the purpose that energy-saving and emission-reduction, environmentally protective, waste make full use of.It can be used for making
The processing of the industrial wastewaters such as paper industry, mining industry and the processing of sanitary sewage etc. are solved and are limited because aluminium trichloride waste water is too many
The problem of production capacity.
Specific implementation mode
Embodiment 1
Take aluminium trichloride waste water (concentration about 8%) 800kg of synthesis of triazine ultra-violet absorber that 17.6kg aluminium skimmings are added,
It is warming up to 85-90 DEG C of heat preservation 6h with 3h stirrings, is gradually risen with the dissolving pH value of aluminium skimmings, detection pH value is 3.8, is then cooled down
It is stirred in 20-50 DEG C of stirring 3h, the enamel still of press filtration to other 1000L to the sawdust charcoal of 20-50 DEG C of addition 8kg220 mesh
It mixes and is heated to 100-105 DEG C of reflux, withdrawing fluid continues to flow back full of water knockout drum, until sink without chlorobenzene or o-dichlorohenzene,
Lower layer solvent is collected into recovery, continues to distill moisture content, when steaming moisture content about 465kg, when detecting 20 DEG C of liquid in kettle
Density is 1.13g/ml, stops distillation, and the water steamed is tuned into diluted hydrochloric acid aqueous solution for lower batch of hydrolysis tri-chlorination after hydrochloric acid is added
Aluminium, liquid is released in kettle, obtains liquid aluminium polychloride, detects Al2O3Content 10.1%, basicity 49.2%, pH value are
3.9。
Embodiment 2
Take aluminium trichloride waste water (concentration about 4%) 800kg of synthesis of triazine ultra-violet absorber that 12.8kg aluminium skimmings are added,
It is warming up to 85-90 DEG C of heat preservation 3h with 2h stirrings, is gradually risen with the dissolving pH value of aluminium skimmings, detection pH value is 3.5, is then cooled down
It is stirred in 20-50 DEG C of stirring 2h, the enamel still of press filtration to other 1000L to the sawdust charcoal of 20-50 DEG C of addition 4kg220 mesh
It mixes and is heated to 100-105 DEG C of reflux, withdrawing fluid continues to flow back full of water knockout drum, until sink without chlorobenzene or o-dichlorohenzene,
Lower layer solvent is collected into recovery, continues to distill moisture content, when steaming moisture content about 590kg, when detecting 20 DEG C of liquid in kettle
Density is 1.11g/ml, stops distillation, and the water steamed is tuned into diluted hydrochloric acid aqueous solution for lower batch of hydrolysis tri-chlorination after hydrochloric acid is added
Aluminium, liquid is released in kettle, obtains liquid aluminium polychloride, detects Al2O3Content 8.6%, basicity 45.0%, pH value are
3.7。
Embodiment 3
Take aluminium trichloride waste water (concentration about 6%) 800kg of synthesis of triazine ultra-violet absorber that 15.2kg aluminium skimmings are added,
It is warming up to 85-90 DEG C of heat preservation 4.5h with 2.5h stirrings, is gradually risen with the dissolving pH value of aluminium skimmings, detection pH value is 4.0, then
It is cooled to the sawdust charcoal of 20-50 DEG C of addition 6kg220 mesh, 4h, the enamel still of press filtration to other 1000L are stirred in 20-50 DEG C
In, it is heated with stirring to 100-105 DEG C of reflux, withdrawing fluid continues to flow back full of water knockout drum, until not having chlorobenzene or o-dichlorohenzene
Sink, lower layer's solvent is collected into recovery, continue to distill moisture content, when steaming moisture content about 535kg, detects 20 DEG C of liquid in kettle
When density be 1.12g/ml, stop distillation, the water that steams is tuned into diluted hydrochloric acid aqueous solution for lower batch of hydrolysis three after hydrochloric acid is added
Aluminium chloride, liquid is released in kettle, obtains liquid aluminium polychloride, detects Al2O3Content 9.5%, basicity 51.9%, pH value
It is 4.1.
Embodiment 4
It takes aluminium trichloride waste water (concentration about 5%) 800kg of synthesis of triazine ultra-violet absorber that 15kg aluminium skimmings are added, uses
3h stirrings are warming up to 85-90 DEG C of heat preservation 5h, are gradually risen with the dissolving pH value of aluminium skimmings, and detection pH value is 4.5, is then cooled to
The sawdust charcoal of 20-50 DEG C of addition 6kg220 mesh, in 20-50 DEG C of stirring 3h, the enamel still of press filtration to other 1000L, stirring
It is heated to 100-105 DEG C of reflux, withdrawing fluid continues to flow back full of water knockout drum, until sink without chlorobenzene or o-dichlorohenzene, it will
Lower layer solvent collects recovery, continues to distill moisture content, close when detecting 20 DEG C of liquid in kettle when steaming moisture content about 550kg
Degree is 1.12g/ml, stops distillation, and be tuned into diluted hydrochloric acid aqueous solution after the water addition hydrochloric acid steamed hydrolyzes alchlor for lower batch,
Liquid is released in kettle, obtains liquid aluminium polychloride, detects Al2O3Content 10.3%, basicity 53.8%, pH value 4.5.
Embodiment 5
For the ease of transport, liquid aluminium polychloride is prepared into solid polyaluminium chloride.By the liquid polymeric of embodiment 3
Aluminium chloride 278kg is spray-dried, and 91kg solid polyaluminium chlorides are obtained, and buff powder detects Al2O3Content 30.5%,
Basicity is 51.8%, and the pH value of 1% aqueous solution is 4.2.
Embodiment 6
The liquid aluminium polychloride 256kg of embodiment 4 is spray-dried, 83kg solid polyaluminium chlorides are obtained, it is shallow
Yellow powder detects Al2O3The pH value of content 30.9%, basicity 54.0%, 1% aqueous solution is 4.8.
The present invention discloses and proposes a kind of poly- using the aluminium trichloride waste water recycling of synthesis of triazine ultra-violet absorber
Aluminium chloride method is closed, those skilled in the art can be by using for reference present disclosure, and the appropriate links such as condition route that change are realized, although
The method and technology of preparing of the present invention is described by preferred embodiment, and related technical personnel can obviously not depart from
Methods and techniques described herein route is modified or is reconfigured in the content of present invention, spirit and scope, to realize most
Whole technology of preparing.In particular, it should be pointed out that all similar replacements and change are aobvious for a person skilled in the art
And be clear to, they are considered as being included in spirit of that invention, range and content.
Claims (5)
1. a kind of aluminium trichloride waste water using synthesis of triazine ultra-violet absorber recycles aluminium polychloride method, feature
It is：Include the following steps：
(1) aluminium content 85-90%, the aluminium skimmings of alundum (Al2O3) content 10-5%, stirring heating are added into aluminium trichloride waste water
It is kept the temperature to 85-90 DEG C, obtains the liquid that pH value is 3.5-4.5；
(2) liquid that step (1) obtains is cooled to the sawdust charcoal of 20-50 DEG C of 220 mesh of addition, is stirred, filtering removes unreacted
Aluminium skimmings and insoluble impurity and activated carbon adsorption organic impurities, obtain filtrate；
(3) filtrate that step (2) obtains is put into container, is heated with stirring to 100-105 DEG C of reflux, withdrawing fluid, which is full of, to be divided
Hydrophone continues to flow back, until sinking without chlorobenzene or o-dichlorohenzene, lower layer's solvent is collected, the water in releasing water knockout drum, and after
Continuous distillation moisture content, density >=1.10g/ml, as liquid aluminium polychloride when 20 DEG C of detection remaining liq；
The addition of aluminium skimmings is the 1.6-2.2% of aluminium trichloride waste water quality in the step (1).
2. the method as described in claim 1 obtains solid polymerization chlorination it is characterized in that liquid aluminium polychloride is dried
Aluminium.
3. the method as described in claim 1, it is characterized in that being warming up to 85-90 DEG C of guarantor using 2-3h stirrings in the step (1)
Warm 3-6h.
4. the method as described in claim 1, it is characterized in that activated carbon addition is aluminium trichloride waste water matter in the step (2)
The 0.5-1% of amount.
5. the method as described in claim 1, it is characterized in that being filtered after stirring 2-4h at 20-50 DEG C in the step (2).
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| CN114133058B (en) * | 2021-10-29 | 2024-02-20 | 山东京博农化科技股份有限公司 | Friedel-crafts reaction aluminum-containing wastewater recycling method |
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| CN1253386C (en) * | 2003-11-19 | 2006-04-26 | 南京大学 | Polymeric aluminum chloride flocculant preparation method using phthalocyanine green waste water |
| US12054400B2 (en) * | 2014-06-13 | 2024-08-06 | G2O Technologies Llc | Method for making sulfated polyaluminum chloride (PACS) or polyaluminum chloride (PAC) and PACs or PAC made by same |
| CN104591248A (en) * | 2014-12-04 | 2015-05-06 | 常州大学 | Method for producing polyaluminum chloride by utilizing aluminium-containing waste hydrochloric acid |
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