CN109942434A - A kind of production method of large red-based g - Google Patents
A kind of production method of large red-based g Download PDFInfo
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- CN109942434A CN109942434A CN201910232379.1A CN201910232379A CN109942434A CN 109942434 A CN109942434 A CN 109942434A CN 201910232379 A CN201910232379 A CN 201910232379A CN 109942434 A CN109942434 A CN 109942434A
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Abstract
The present invention provides a kind of production methods of large red-based g; belong to the production field of Pigment Intermediates; it is characterized in that; including at salt, nitrification, double decomposition; in such a way that o-toluidine and acetic acid are at salt; amino can be protected not oxidized and the ortho para position base of amino is changed to meta-orientating group；Nitration mixture is prepared with acetic acid, concentration of nitric acid can be effectively reduced, controls reaction speed；Analysis of material can not only be made complete using the analysis of material mode of methyl tertiary butyl ether(MTBE), and also reduce the inventory dissolved in acetic acid.It so can be realized nitrification production large red-based g under normal temperature condition, reaction condition is mild, and production risk is lower.
Description
Technical field
The present invention relates to the production fields of Pigment Intermediates, and in particular to a kind of production method of large red-based g.
Background technique
Large red-based g is organic pigment intermediate, belongs to the important composition thing of azoic dyes insoluble azo dyes, is mainly used for cotton and knits
The dyeing of object and stamp are coupled dye large red with azoic coupling component AS or AS-E (i.e. flag is red), it can also be used to silk, viscose glue and nylon fabric
Dyeing.
The production method of existing large red-based g is using o-toluidine as raw material, at room temperature with the concentrated sulfuric acid at salt, so
Afterwards under the conditions of subzero 15 DEG C of temperature, with mixed acid nitrification, then neutralizes and be made.The shortcomings that this technique is to need low-temp reaction,
It a large amount of chilled brine consumed, while producing a large amount of Waste Sulfuric Acid, cannot apply and be difficult to handle, in addition nitration reaction
Yield only has 73% or so, generates the COD of a large amount of spent acid in 100000mg/L, has seriously affected the cost price of product.
Summary of the invention
The present invention is that energy consumption present in solution prior art large red-based g production technology is high, yield is low, spent acid is difficult to locate
The technical issues of reason, provides a kind of room temperature nitrification and the production method of the large red-based g that can significantly improve product yield, has
The advantages that low energy consumption, high income, spent acid are easily handled.
The technical scheme to solve the above technical problems is that a kind of production method of large red-based g, feature exist
In including the following steps:
A) at salt: being pumped into o-toluidine, glacial acetic acid into reaction kettle, then put into monoxone, be warming up to 60-65 DEG C, and will be anti-
The hydrogen chloride gas that should be generated is extracted out by micro-vacuum；
As solvent, o-toluidine and chloroacetate reaction react glacial acetic acid at salt, and under conditions of micro-vacuum in the step
More completely, react as follows:
B) nitrify: the mixture of glacial acetic acid and nitric acid is added dropwise by head tank to 30-35 DEG C for adjustment temperature, and temperature is controlled in 30-35
Between DEG C；It reacts as follows:
C) it is added dropwise, is put into analysis of material kettle after mixing evenly, be then pumped into methyl tertiary butyl ether(MTBE) into analysis of material kettle, by filters pressing,
Solid is separated to double decomposition kettle, liquid to distillation still；
D) distillation still is warming up to 55-56 DEG C, condensing recovery methyl tertiary butyl ether(MTBE), residual acetic acid；
E) double decomposition: being added hydrochloric acid in double decomposition kettle, is warming up to 80-85 DEG C, reacts 2.0-2.5 hours, then hot pressing is filtered, filtrate
Into crystallization tank, monoxone is recycled, filter cake is washed, centrifugation is large red-based g finished product；It reacts as follows:
。
Further, the temperature of salt-forming reaction is controlled at 62 DEG C in above-mentioned steps a).
Further, the molar ratio of o-toluidine, monoxone and glacial acetic acid is 1:1.01:3 in above-mentioned steps a).
Further, the molar ratio that glacial acetic acid and nitric acid prepare nitration mixture in above-mentioned steps b) is 1:1.
Further, the molar ratio of methyl tertiary butyl ether(MTBE) and o-toluidine is 2:1 in analysis of material kettle in above-mentioned steps c).
Further, the molar ratio of hydrochloric acid and o-toluidine is 1.01:1 in double decomposition kettle in above-mentioned steps e).
Further, filters pressing temperature is 65-70 DEG C in above-mentioned steps e).
Further, metathesis reaction temperature is controlled at 80 DEG C in above-mentioned steps e).
The beneficial effects of the present invention are:
1. amino can be protected not oxidized and ortho para position by amino in such a way that o-toluidine and acetic acid are at salt
Base is changed to meta-orientating group；Nitration mixture is prepared with acetic acid, concentration of nitric acid can be effectively reduced, controls reaction speed；Using methyl- tert fourth
The analysis of material mode of base ether can not only make analysis of material complete, and also reduce the inventory dissolved in acetic acid.So it can be realized
Nitrification production large red-based g under normal temperature condition, reaction condition is mild, and production risk is lower.
2. the large red-based g that technique is produced, it is not necessary that separation is further purified, production cost is low, product yield
Up to 95% or more.
3. the recyclable hydrogen chloride gas applied, generated at salt of monoxone, glacial acetic acid and methyl tertiary butyl ether(MTBE) after reaction
It is absorbed by water, can be used for the metathesis reaction of double decomposition kettle；Wherein, glacial acetic acid is after 10 times are applied, by active carbon decoloring,
Concentration can reuse.
Specific embodiment
Embodiment 1
A kind of production method of large red-based g of the present embodiment, which comprises the steps of:
A) at salt: being pumped into o-toluidine, glacial acetic acid into reaction kettle, then put into monoxone, be warming up to 60 DEG C or so, and will be anti-
The hydrogen chloride gas that should be generated is extracted out by micro-vacuum；
B) nitrify: the mixture of glacial acetic acid and nitric acid is added dropwise by head tank at 30 DEG C for control temperature；
C) it is added dropwise, is put into analysis of material kettle after mixing evenly, be then pumped into methyl tertiary butyl ether(MTBE) into analysis of material kettle, by filters pressing,
Solid is separated to double decomposition kettle, liquid to distillation still；
D) distillation still is warming up to 55 DEG C, condensing recovery methyl tertiary butyl ether(MTBE), residual acetic acid；
E) double decomposition: being added hydrochloric acid in double decomposition kettle, controls 80 DEG C of temperature, 2.5 hours reaction time, then hot pressing at 65 DEG C
Filter, filtrate recycle monoxone into crystallization tank, and filter cake is washed, centrifugation is large red-based g finished product.
Embodiment 2
A kind of production method of large red-based g of the present embodiment, which comprises the steps of:
B) at salt: being pumped into o-toluidine, glacial acetic acid into reaction kettle, then put into monoxone, be warming up to 62 DEG C, and reaction is produced
Raw hydrogen chloride gas is extracted out by micro-vacuum；
B) nitrify: the mixture of glacial acetic acid and nitric acid is added dropwise by head tank at 32 DEG C for control temperature；
C) it is added dropwise, is put into analysis of material kettle after mixing evenly, be then pumped into methyl tertiary butyl ether(MTBE) into analysis of material kettle, by filters pressing,
Solid is separated to double decomposition kettle, liquid to distillation still；
D) distillation still is warming up to 55 DEG C, condensing recovery methyl tertiary butyl ether(MTBE), residual acetic acid；
E) double decomposition: being added hydrochloric acid in double decomposition kettle, controls 83 DEG C of temperature, 2.2 hours reaction time, then hot pressing at 67 DEG C
Filter, filtrate recycle monoxone into crystallization tank, and filter cake is washed, centrifugation is large red-based g finished product.
Embodiment 3
A kind of production method of large red-based g of the present embodiment, which comprises the steps of:
C) at salt: being pumped into o-toluidine, glacial acetic acid into reaction kettle, then put into monoxone, be warming up to 65 DEG C, and reaction is produced
Raw hydrogen chloride gas is extracted out by micro-vacuum；
B) nitrify: the mixture of glacial acetic acid and nitric acid is added dropwise by head tank at 35 DEG C for control temperature；
C) it is added dropwise, is put into analysis of material kettle after mixing evenly, be then pumped into methyl tertiary butyl ether(MTBE) into analysis of material kettle, by filters pressing,
Solid is separated to double decomposition kettle, liquid to distillation still；
D) distillation still is warming up to 56 DEG C, condensing recovery methyl tertiary butyl ether(MTBE), residual acetic acid；
E) double decomposition: being added hydrochloric acid in double decomposition kettle, controls 85 DEG C of temperature, 2.0 hours reaction time, then hot pressing at 70 DEG C
Filter, filtrate recycle monoxone into crystallization tank, and filter cake is washed, centrifugation is large red-based g finished product.
In the various embodiments described above, the molar ratio of o-toluidine, monoxone and glacial acetic acid is 1:1.01:3, step in step a)
It is rapid b) in glacial acetic acid and nitric acid to prepare the molar ratio of nitration mixture be 1:1, methyl tertiary butyl ether(MTBE) and adjacent methyl in analysis of material kettle in step c)
The molar ratio of aniline is 2:1, and the molar ratio of hydrochloric acid and o-toluidine is 1.01:1 in double decomposition kettle in step e).
In addition, for the process for accelerating metathesis reaction, can also add into double decomposition kettle in the various embodiments described above step e)
Enter catalyst, catalyst type can be selected from interphase catalyst such as NaZn13、KCd13、CaZn13、CaBe13、LaBe13、
ThBe13、Cu5Zn8、Fe5Zn21、Cu31Sn8At least one of, wherein the molar ratio of ortho-aminotoluene and catalyst is
10000000:1.For catalyst in metathesis reaction due to measuring very little, the amount remained in large red-based g is smaller, does not influence to produce
Product quality；Most of catalyst stays in mother liquor after washing centrifugation, and sewage treatment is transferred to carry out biochemical treatment.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (10)
1. a kind of production method of large red-based g, which comprises the steps of:
A) at salt: being pumped into o-toluidine, glacial acetic acid into reaction kettle, then put into monoxone, be warming up to 60-65 DEG C, and will be anti-
The hydrogen chloride gas that should be generated is extracted out by micro-vacuum；
B) nitrify: the mixture of glacial acetic acid and nitric acid is added dropwise by head tank to 30-35 DEG C for adjustment temperature, and temperature is controlled in 30-35
Between DEG C；
C) it is added dropwise, is put into analysis of material kettle after mixing evenly, be then pumped into methyl tertiary butyl ether(MTBE) into analysis of material kettle, by filters pressing,
Solid is separated to double decomposition kettle, liquid to distillation still；
D) distillation still is warming up to 55-56 DEG C, condensing recovery methyl tertiary butyl ether(MTBE), residual acetic acid；
E) double decomposition: being added hydrochloric acid in double decomposition kettle, is warming up to 80-85 DEG C, reacts 2.0-2.5 hours, then hot pressing is filtered, filtrate
Into crystallization tank, monoxone is recycled, filter cake is washed, centrifugation is large red-based g finished product.
2. the production method of large red-based g according to claim 1, which is characterized in that salt-forming reaction in above-mentioned steps a)
Temperature control at 62 DEG C.
3. the production method of large red-based g according to claim 1 or 2, which is characterized in that adjacent methyl in above-mentioned steps a)
The molar ratio of aniline, monoxone and glacial acetic acid is 1:1.01:3.
4. the production method of large red-based g according to claim 1, which is characterized in that in above-mentioned steps b) glacial acetic acid with
The molar ratio that nitric acid prepares nitration mixture is 1:1.
5. the production method of large red-based g according to claim 1, which is characterized in that in above-mentioned steps c) in analysis of material kettle
The molar ratio of methyl tertiary butyl ether(MTBE) and o-toluidine is 2:1.
6. the production method of large red-based g according to claim 1, which is characterized in that double decomposition kettle in above-mentioned steps e)
The molar ratio of middle hydrochloric acid and o-toluidine is 1.01:1.
7. the production method of large red-based g according to claim 1 or 6, which is characterized in that filters pressing temperature in above-mentioned steps e)
Degree is 65-70 DEG C.
8. the production method of large red-based g according to claim 1 or 6, which is characterized in that double decomposition in above-mentioned steps e)
Reaction temperature is controlled at 80 DEG C.
9. the production method of large red-based g according to claim 1, which is characterized in that double decomposition is anti-in above-mentioned steps e)
Should during be additionally added interphase catalyst, the molar ratio of ortho-aminotoluene and catalyst is 10000000:1.
10. the production method of large red-based g according to claim 9, which is characterized in that the catalyst selects NaZn13、
KCd13、CaZn13、CaBe13、LaBe13、ThBe13、Cu5Zn8、Fe5Zn21、Cu31Sn8At least one of.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111825565A (en) * | 2020-08-10 | 2020-10-27 | 山东安迪新型材料有限公司 | Preparation method of naphthol AS-PH |
| CN114127047A (en) * | 2019-08-08 | 2022-03-01 | 弗门尼舍有限公司 | 2-acetylpyrroline precursors |
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