CN107721887A - A kind of preparation method of highly acid blue dyes - Google Patents
A kind of preparation method of highly acid blue dyes Download PDFInfo
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- CN107721887A CN107721887A CN201710970155.1A CN201710970155A CN107721887A CN 107721887 A CN107721887 A CN 107721887A CN 201710970155 A CN201710970155 A CN 201710970155A CN 107721887 A CN107721887 A CN 107721887A
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- blue dyes
- acid blue
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
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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
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/12—Amino derivatives of triarylmethanes without any OH group bound to an aryl nucleus
- C09B11/14—Preparation from aromatic aldehydes, aromatic carboxylic acids or derivatives thereof and aromatic amines
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation method of highly acid blue dyes, it is characterised in that：Comprise the following steps：Step 1：N ethyl ns（3` sulfonic group benzyls）Aniline and the condensation product aqueous solution of ortho-sulfonic acid sodium benzaldehyde generation, carry out oxidation reaction with the molten aqueous of hydrogen peroxide, add alkali, filter, obtain filtrate；Step 2：To filtrate made from step 1, purified, dry, obtain dye product.The present invention need not handle metal ion and inorganic salts by chemical deposition method, will not produce a large amount of solid waste, substantially reduce the risk of residual heavy metal ion, the quality of product is more stable, and the content of dyestuff is up to 96 ~ 97%（The staining power of dyestuff is 355 ~ 360%）；The catalytic activity of catalyst is handled by introducing dispersion technology, solves unstable due to catalytic activity, can not effectively control condensation material to make the oxidation Pureness control of product more than 88%, the quality and yield of product are more stable by the problem of peroxidating.
Description
Technical field
The present invention relates to a kind of preparation method of highly acid blue dyes, and in particular to a kind of highly acid blue dyes it is new
Type clean method for producing.
Background technology
Such as formula（Ⅰ）The production of dyestuff existing decades, show that this dyestuff mainly there are two kinds of synthesis from presently disclosed data
Route：First, N- ethyls-N-（3`- sulfonic group benzyls）Aniline and the condensation product aqueous solution of ortho-sulfonic acid sodium benzaldehyde reaction generation,
In acid condition, sodium dichromate is used（Potassium）Or brown lead oxide or manganese dioxide, oxidation reaction is carried out, after removing metal ion,
Saltout, dry, obtain product.For product 95% on sale at present above is being produced by such a route, the production cost of this route is relatively low
Honest and clean, the content for the high content product produced by this method also can only achieve 85 ~ 88%, while can be produced in production process a large amount of
" three wastes " problem, be currently that all enterprises all can problems faced.Second, N- ethyls-N-（3`- sulfonic group benzyls）Aniline with
The condensation product aqueous solution of ortho-sulfonic acid sodium benzaldehyde reaction generation, under catalyst action, is reacted with hydrogen peroxide oxidation, dries, obtain
Product.Because this technological principle is to use Fenton oxidation principle, macromolecular is fragmented into by small molecule by Strong oxdiative, so as to come
The effect in pollution degradation source, but want this principle using formula（Ⅰ）Product synthesis in, how to efficiently control Strong oxdiative and draw
The scission of link of the chemical structural formula risen and the problem of eventually affect the quality and conversion ratio of product, be that this current process route can not
Carry out the main contributor of large-scale production.
Such as formula（Ⅰ）Dyestuff is an important blue series dyes, because it has gay colours, excellent water solubility
And relatively low physiological-toxicity, not only a large amount of uses are in textile industry, and are widely used daily use chemicals, agrochemical, food, medicine etc.
Non-thermoplastic field.Its product is particularly allowed to meet in non-thermoplastic product, the content of its product must reach more than 85%, weight
Metal ion is necessarily less than 50ppm, in order to reach the two important indicators, although the product of both the above process route production is all
Can reach requirement, but desalination in second of art production process, removal of impurities process can relatively easy, understand caused by " three wastes " problem
Also can be fewer.
。
The content of the invention
It is an object of the invention to provide a kind of preparation method of highly acid blue dyes.
The technical solution adopted by the present invention is：
A kind of preparation method of highly acid blue dyes, it is characterised in that：Comprise the following steps：
Step 1：N- ethyls-N-（3`- sulfonic group benzyls）Aniline and the condensation product aqueous solution of ortho-sulfonic acid sodium benzaldehyde generation, it is used
The molten aqueous of hydrogen oxide carries out oxidation reaction, and the catalyst of oxidation reaction is the scattered suspension of water, iron nitrogen complex compound, dispersant composition
Liquid, the weight ratio of three kinds of compositions is 3 ~ 6:0.5~1:0.5 ~ 1, add alkali, filter, obtain filtrate；
Step 2：To filtrate made from step 1, purified, dry, obtain dye product.
The temperature of the oxidation reaction of the step 1 is 5 ~ 20 DEG C.
The pH value control of step 1 oxidation reaction is pH=1.5 ~ 2.0, is controlled by alkaline solution.
Described alkaline solution is sodium hydroxide, potassium hydroxide, sodium carbonate, sodium acid carbonate, tertiary sodium phosphate, biphosphate
The aqueous solution that one kind or any combination in sodium, disodium hydrogen phosphate, sodium citrate, sodium acetate are made into.
The purification of the step 2 is to use milipore filter, NF membrane, multi-effect evaporating device composition combination unit carry out major-minor into
The separation of part.
Dye product described in the step 2 is the liquid and 45 ~ 97% pulvis that content is 35 ~ 50%.
Advantages of the present invention：Metal ion and inorganic salts need not be handled by chemical deposition method, will not produced a large amount of solid
Body discarded object, the risk of residual heavy metal ion is substantially reduced, the quality of product is more stable, and the content of dyestuff is up to 96 ~ 97%
（The staining power of dyestuff is 355 ~ 360%）；By introduce dispersion technology handle catalyst catalytic activity, solve due to
Catalytic activity it is unstable, can not effectively control condensation material the oxidation Pureness control of product can be made to exist by the problem of peroxidating
More than 88%, the quality and yield of product are more stable.
Brief description of the drawings
The present invention is described in further detail with reference to the accompanying drawings and detailed description.
Fig. 1 is the preparation method flow chart of the present invention.
Embodiment
As shown in Figure 1：
Embodiment 1
Into 500L reactors, 400 ㎏ are put into（80 moles）By N- ethyls-N-（3`- sulfonic group benzyls）Aniline and ortho-sulfonic acid sodium
The condensation product of benzaldehyde generation, is warming up to 60 DEG C, adds the fresh catalyst dispersions of 0.2 ㎏（Catalyst dispersion reclaimed water：
Iron nitrogen complex compound：Weight ratio=4 of three kinds of compositions of dispersant:1:1）, stir 0.5 hour, be cooled to 8 DEG C, be added dropwise to 1 hour
50 ㎏ mass fractions are 13% aqueous hydrogen peroxide solution, at the same with mass fraction be 32% sodium hydrate aqueous solution control pH=
1.5 by liquid chromatographic detection terminal, after terminal arrives, with pure adjusting PH with base=7.5, add 0.1kg diatomite, stir 0.5 hour,
Filtering, filter residue about 0.5kg, obtains filtrate.Filtrate is transferred in another 500L reactors, is first diluted with 0.5 times of pure water constant volume,
Most of accessory substance is first removed with GE device for ultrafiltration membrane, caused highly concentrated clear liquid is collected.It is dilute with 0.5 times of pure water constant again
Release, caused low dense clear liquid collects the industrial water as lower batch, after the accessory substance basic handling remained after testing is qualified, leads to
The nano-filtration membrane equipment for crossing GE carries out concentrate, and caused permeate is dehydrated into triple effect with highly concentrated clear liquid, is dry that low content produces
The filler of product.Concentrate terminates, and obtains the liquid 120.8kg of 45% content（Yield is 2.15）Or dry 96% content dry powder
56.1kg（Yield is 2.13）.
Embodiment 2
Into 500L reactors, 400 ㎏ are put into（80 moles）By N- ethyls-N-（3`- sulfonic group benzyls）Aniline and ortho-sulfonic acid sodium
The condensation product of benzaldehyde generation, is warming up to 65 DEG C, adds the fresh catalyst dispersions of 0.2 ㎏（Catalyst dispersion reclaimed water：
Iron nitrogen complex compound：Weight ratio=4 of three kinds of compositions of dispersant:1:1）, stir 0.5 hour, be cooled to 10 DEG C, be added dropwise to 2 hours
50 ㎏ mass fractions are 13% aqueous hydrogen peroxide solution, at the same with mass fraction be 32% sodium hydrate aqueous solution control pH=
2.0, by liquid chromatographic detection terminal, after terminal arrives, with pure adjusting PH with base=8.5, add 0.1kg diatomite, stir 0.5 hour,
Filtering, filter residue about 0.5kg, filtrate is obtained, filtrate readjustment pH value, dries, obtains the product 71.7kg of 79% content（Yield is 2.24）.
Embodiment 3
Into 500L reactors, 400 ㎏ are put into（80 moles）By N- ethyls-N-（3`- sulfonic group benzyls）Aniline and ortho-sulfonic acid sodium
The condensation product of benzaldehyde generation, is warming up to 60 DEG C, adds the fresh catalyst dispersions of 0.2 ㎏（Catalyst dispersion reclaimed water：
Iron nitrogen complex compound：Weight ratio=4 of three kinds of compositions of dispersant:1:1）, stir 0.5 hour, be cooled to 9 DEG C, be added dropwise with 1.5 hours
It is 13% aqueous hydrogen peroxide solution to enter 50 ㎏ mass fractions, at the same with mass fraction be 32% sodium hydrate aqueous solution control pH=
1.7, by liquid chromatographic detection terminal, after terminal arrives, with pure adjusting PH with base=8, add 0.1kg diatomite, stir 0.5 hour, mistake
Filter, filter residue about 0.5kg, obtains filtrate.Filtrate is transferred in another 500L reactors, is first diluted, used with 0.5 times of pure water constant volume
GE device for ultrafiltration membrane first removes most of accessory substance, and caused highly concentrated clear liquid is collected.It is dilute with 0.5 times of pure water constant again
To release, caused low dense clear liquid collects the industrial water as lower batch, after the accessory substance basic handling remained after testing is qualified, after
The continuous device for ultrafiltration membrane by GE carries out concentrate, and caused permeate is dehydrated with highly concentrated clear liquid into triple effect, dry low contains
The filler of volume production product.Concentrate terminates, and obtains the liquid 112.3kg of 45% content（Yield is 2.0）Or dry 96% content it is dry
Powder 52.6kg（Yield is 1.98）.
Embodiment 4
Into 500L reactors, 400 ㎏ are put into（80 moles）By N- ethyls-N-（3`- sulfonic group benzyls）Aniline and ortho-sulfonic acid sodium
The condensation product of benzaldehyde generation, is warming up to 60 DEG C, adds the fresh catalyst dispersions of 0.2 ㎏（Catalyst dispersion reclaimed water：
Iron nitrogen complex compound：Weight ratio=4 of three kinds of compositions of dispersant:1:1）, stir 0.5 hour, be cooled to 8 DEG C, be added dropwise to 1 hour
50 ㎏ mass fractions are 13% aqueous hydrogen peroxide solution, at the same with mass fraction be 32% sodium hydrate aqueous solution control pH=
1.5, by liquid chromatographic detection terminal, after terminal arrives, with pure adjusting PH with base=7.5, add 0.1kg diatomite, stir 0.5 hour,
Filtering, filter residue about 0.5kg, obtains filtrate.Filtrate is transferred in another 500L reactors, is first diluted with 0.5 times of pure water constant volume,
Most of accessory substance is first removed with GE device for ultrafiltration membrane, caused highly concentrated clear liquid is collected.It is dilute with 0.5 times of pure water constant again
Release, caused low dense clear liquid collects the industrial water as lower batch, after the accessory substance basic handling remained after testing is qualified, leads to
The device for ultrafiltration membrane for crossing GE is purified, after the accessory substance basic handling remained after testing is qualified, be directly standardized 35%
The liquid 156.7kg of content（Yield is 2.17）Or dry 93% content dry powder 58.4kg（Yield is 2.15）.
Embodiment 5
Into 500L reactors, 320 ㎏ are put into（80 moles）By N- ethyls-N-（3`- sulfonic group benzyls）Aniline and ortho-sulfonic acid sodium
The condensation product of benzaldehyde generation, is warming up to 62 DEG C, adds the fresh catalyst dispersions of 0.2 ㎏（Catalyst dispersion reclaimed water：
Iron nitrogen complex compound：Weight ratio=4 of three kinds of compositions of dispersant:1:1）, stir 0.5 hour, be cooled to 9 DEG C, be added dropwise with 2.5 hours
It is 13% aqueous hydrogen peroxide solution to enter 54 ㎏ mass fractions, at the same with mass fraction be 32% sodium hydrate aqueous solution control pH=
1.7, by liquid chromatographic detection terminal, after terminal arrives, with sodium bicarbonate and pure adjusting PH with base=8, add 0.1kg diatomite, stirring 0.5
Hour, filtering, filter residue about 0.4kg, filtrate is transferred in another 500L reactors, is first diluted, used with 0.6 times of pure water constant volume
GE device for ultrafiltration membrane first removes most of accessory substance, and caused highly concentrated clear liquid is collected.It is dilute with 0.7 times of pure water constant again
Release, caused low dense clear liquid reclaims the industrial water as lower batch, after the accessory substance basic handling remained after testing is qualified, leads to
The nano-filtration membrane equipment for crossing GE carries out concentrate, and caused permeate is dehydrated into triple effect with highly concentrated clear liquid, is dry that low content produces
The filler of product.Concentrate terminates, be standardized 35% content liquid 153.1kg（Yield is 2.12）Or dry 93% to contain
The dry powder 56.8kg of amount（Yield is 2.09）.
Comparison example 1
Into 300L reactors, 120 ㎏ are put into（80 moles）By N- ethyls-N-（3`- sulfonic group benzyls）Aniline and ortho-sulfonic acid sodium
The condensation product of benzaldehyde generation, is cooled to 20 DEG C, and it is 90% manganese dioxide to add 13 ㎏ mass fractions with 0.5 hour, uses matter
Measure the hydrochloric acid that fraction is 31% and control pH=2.0, by liquid chromatographic detection terminal, after terminal arrives, add weight than for 10% it is pure
After alkali stirs 2 hours, filtering, filter residue about 35kg, filtrate is transferred in another 300L reactors, adds weight than for 1%
After diatomite stirs 0.5 hour, refilter, filter residue about 8kg, filtrate readjustment pH value, drying, obtain the product 77.6kg of 70% content
（Yield is 2.15）.
Comparison example 2
Into 300L reactors, 120 ㎏ are put into（80 moles）By N- ethyls-N-（3`- sulfonic group benzyls）Aniline and ortho-sulfonic acid sodium
The condensation product of benzaldehyde generation, is cooled to 25 DEG C, and it is 90% manganese dioxide to add 13 ㎏ mass fractions with 1 hour, uses quality
The hydrochloric acid that fraction is 31% controls pH=3.0, by liquid chromatographic detection terminal, after terminal arrives, adds weight than the soda ash for 10%
After stirring 2 hours, filtering, filter residue about 35kg, filtrate is transferred in another 300L reactors, adds weight than the silicon for 1%
After diatomaceous earth stirs 0.5 hour, refilter, filter residue about 8kg, filtrate readjustment pH value, diluted with 2.5 times of pure water constant volumes, first use GE
Device for ultrafiltration membrane first remove most of accessory substance, then diluted with 1.7 times of pure water constant, the accessory substance remained after testing is basic
Handle it is qualified after, drying, obtain the product 53.3kg of 91% content（Yield is 1.92）.
Claims (6)
- A kind of 1. preparation method of highly acid blue dyes, it is characterised in that：Comprise the following steps：Step 1：N- ethyls-N-（3`- sulfonic group benzyls）Aniline and the condensation product aqueous solution of ortho-sulfonic acid sodium benzaldehyde generation, it is used The molten aqueous of hydrogen oxide carries out oxidation reaction, and the catalyst of oxidation reaction is the scattered suspension of water, iron nitrogen complex compound, dispersant composition Liquid, the weight ratio of three kinds of compositions is 3 ~ 6:0.5~1:0.5 ~ 1, add alkali, filter, obtain filtrate；Step 2：To filtrate made from step 1, purified, dry, obtain dye product.
- A kind of 2. preparation method of highly acid blue dyes according to claim 1, it is characterised in that：The step 1 The temperature of oxidation reaction is 5 ~ 20 DEG C.
- A kind of 3. preparation method of highly acid blue dyes according to claim 1, it is characterised in that：Step 1 oxygen The pH value control for changing reaction is pH=1.5 ~ 2.0, is controlled by alkaline solution.
- A kind of 4. preparation method of highly acid blue dyes according to claim 1 or 3, it is characterised in that：Described alkali Property solution be sodium hydroxide, potassium hydroxide, sodium carbonate, sodium acid carbonate, tertiary sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, lemon The aqueous solution that one kind or any combination in sour sodium, sodium acetate are made into.
- A kind of 5. preparation method of highly acid blue dyes according to claim 1, it is characterised in that：The step 2 Purification is to use milipore filter, NF membrane, and the combination unit of multi-effect evaporating device composition carries out the separation of major-minor composition.
- A kind of 6. preparation method of highly acid blue dyes according to claim 1, it is characterised in that：Step 2 institute It is the liquid and 45 ~ 97% pulvis that content is 35 ~ 50% to state dye product.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111007059A (en) * | 2019-11-05 | 2020-04-14 | 北京海洋海泰科技有限公司 | Blood stain color developing agent and preparation and use methods thereof |
| CN114958026A (en) * | 2022-05-30 | 2022-08-30 | 金华双宏化工有限公司 | Improved trisazo red acid dye and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327533A (en) * | 2014-09-04 | 2015-02-04 | 恒升化工有限公司 | Clean production technology of acid blue 9 dye |
| US20170247557A1 (en) * | 2016-02-29 | 2017-08-31 | Canon Kabushiki Kaisha | Compound, ink, ink cartridge and ink jet recording method |
-
2017
- 2017-10-18 CN CN201710970155.1A patent/CN107721887A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327533A (en) * | 2014-09-04 | 2015-02-04 | 恒升化工有限公司 | Clean production technology of acid blue 9 dye |
| US20170247557A1 (en) * | 2016-02-29 | 2017-08-31 | Canon Kabushiki Kaisha | Compound, ink, ink cartridge and ink jet recording method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111007059A (en) * | 2019-11-05 | 2020-04-14 | 北京海洋海泰科技有限公司 | Blood stain color developing agent and preparation and use methods thereof |
| CN114958026A (en) * | 2022-05-30 | 2022-08-30 | 金华双宏化工有限公司 | Improved trisazo red acid dye and preparation method thereof |
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