CN104628670A

CN104628670A - 6-nitro-1,2-diazoxynaphthalene-4-sulfonic acid and preparation method thereof

Info

Publication number: CN104628670A
Application number: CN201410616340.7A
Authority: CN
Inventors: 吴秀荣; 叶友余; 聂锋
Original assignee: Jiujiang Shanshui Technology Co Ltd
Current assignee: Jiujiang Shanshui Technology Co Ltd
Priority date: 2014-11-05
Filing date: 2014-11-05
Publication date: 2015-05-20

Abstract

The invention relates to chemical products and preparation methods thereof, and particularly relates to 6-nitro-1,2-diazoxynaphthalene-4-sulfonic acid and a preparation method thereof. The product is prepared by the following method: adding sulfuric acid into a reaction container, stirring and freezing to reduce the temperature to 0-20 DEG C; then, gradually adding a dried oxysome product under a heat-preservation condition, and stirring; dropwise adding mixed acid which is quantitatively prepared, carrying out heat preservation and stirring for 4 hours to a terminal, transferring the material into a diluting kettle, adding water and auxiliaries into the diluting kettle in advance, controlling the temperature being 25-35 DEG C, pressing and filtering after the material is separated, and drying to obtain 6-nitro-1,2-diazoxynaphthalene-4-sulfonic acid. By adopting the method, the caking problem of 6-nitro-1,2-diazoxynaphthalene-4-sulfonic acid in production, transportation and storage processes can be solved.

Description

A kind of 6-nitre body and preparation method thereof

Technical field

The present invention relates to Chemicals and preparation method, particularly 6-nitre body and preparation method thereof.

Background technology

6-nitre body, also referred to as 6-nitre, i.e. 6-nitro-1,2-diazoxy naphthalene-4-sulfonic acid, English name: 6-nitro-1-daizo-2-naphthol-4-sulfonic acid, No. CAS: 5366-84-7, molecular formula: C ₁₀h ₅n ₃o ₆s, molecular weight: 295.Molecular structure:

Very easily water-soluble, its saturated aqueous solution can recrystallization in the hot water, adds hydrochloric acid or sulfuric acid also can separate out yellow crystal, starts to decompose, have sharply decomposing phenomenon, can not decompose under normal conditions during burning when being heated to 203 DEG C.Be important naphthalene series dye intermediate, be widely used in and manufacture acid mordant black dyestuff and metallized dye, as Mordant Black T, black A etc.6-nitre is yellow or brown color crystallization, and namely the 6-nitre without anti-caking process lump in two weeks, is unfavorable for standing storage, and the use properties of the 6-nitre after caking is also had a strong impact on.Therefore, 6-nitro anti-caking agent is developed for storage, the transport of 6-nitre and as Intermediate Preparation naphthalene series dye, there is important effect.Anti-caking agent is often used to improve its performance in prior art.

Existing anti-caking agent, mostly is inorganics and easily lumps the anti-caking agent of product.As " powdering and caking resisting agent for urea " patent that application number is 200410061339.Component and the weight percentage thereof of disclosed anti-hard caking agent are: high molecular polymer 1 ~ 20%, tensio-active agent 2% ~ 25%, viscosity modifier 2% ~ 25%, defoamer 0.05% ~ 25%, sanitas 0.05% ~ 1%, water 50% ~ 90%.The main drawback of this anti-hard caking agent is: the anti-caking process being only applicable to urea fertilizer, is not suitable for the anti-caking process of organism 6-nitre; Its component reaches six kinds, and production cost is high.

And for example application number is " crystal controls emulsion form ammonium nitrate crystals anti-hard caking agent " patent of 02128014, component and the weight percentage thereof of disclosed anti-hard caking agent are: crystal control agent 10 ~ 30%, non-blushing thinner 30 ~ 60%, emulsifying agent 2 ~ 5%, stablizer 0.5 ~ 3%, solvent 20 ~ 50%.The main drawback of this anti-hard caking agent is: be only applicable to the caking preventing ammonium nitrate crystals inorganic salt, is not suitable for the anti-caking process of organism 6-nitre; Its component reaches five kinds, and production cost is high.

The object of the application is exactly the preparation method by improving 6-nitre body, to reach the object finally improving product caking performance.

Summary of the invention

Technical problem to be solved by this invention solves 6-nitre body in the problem of producing, transport and lump in storage process.

The invention provides one and there is superperformance, be i.e. non-caking 6-nitre body.

Present invention also offers the preparation method of above-mentioned 6-nitre body.

Technical scheme provided by the invention is:

Nitrated: in dry enamel reaction still, to add sulfuric acid, oxysome solid is added equably under agitation condition, carry out jacket refrigerating after making beating evenly and cool to 10-20 °, start the mixed solution dripping nitric acid and sulfuric acid, after dripping, within insulation reaction 4-6 hour, arrive terminal at 15-20 °.

Dilution press filtration: add a certain amount of water in dilution still, then proceeded in 1-2 hour by nitrification liquid, control temperature in the kettle is 25-35 °, crystallize out particle, after having diluted, stirring 1-2 as a child carried out press filtration and dried up, and obtained orange crystals.

Product quality indicator

Sequence number	Index name	Index
			1	Outward appearance	Orange crystals
2	Content % >=	72
			3	6-nitre body purity % (HPLC) >=	90
4	8-nitre body purity (HPLC)≤	7
			5	Acidity, %≤	6

Product of the present invention and preparation method thereof has following advantage:

On market, content is 70-75% substantially, and present invention process synthesis is 79-85% substantially, and crystal material content is high, non-caking benefit:

1. do not lump, dispersing property is good.

Long pot life still can not lump (particularly in exit procedure, the time is long).

2. easy to operate, reduce labor force.

Simple at subsequent production dosing operation, without the need to breaking into pieces.

3. yield is improved.

Owing to not luming, after feeding intake, dispersed with stirring is effective, is convenient to react completely.

4. improve and be directly sprayed into product power part.

Content is high, and acidity is low, then the inorganic salt amount produced reduces, and improves product capability part of subsequent product Direct spraying drying.

5. reduce costs.

Free acidity is low, reduces the alkali consumption for neutralizing, and reduces raw materials cost.

6. intermediary's transportation cost is reduced.

Be all a cabinet, folding hundred amount raisings more than 10%, then unit price freight charges reduce.

Embodiment

The present invention is further described according to following embodiment, and those skilled in the art can understand, following embodiment only plays the effect of explanation to the present invention.Without departing from the premise in the spirit of the present invention, any improvement the present invention done and substituting all within the scope of protection of the invention.The medicine used in embodiment and reagent are commercially available prod.

Embodiment 1:

Sulfuric acid 1000kg is added in 1500L reactor, stir frozen cooling to 0 ~ 20 DEG C, then add oxysome dry product 300kg under heat-retaining condition gradually, stir 4 hours, drip the nitration mixture quantitatively prepared, 10 ~ 20 DEG C of insulated and stirred after 4 hours to terminal, proceeded to by material in dilution still and (add water in advance, auxiliary agent in dilution still), control temperature is 25 ~ 35 DEG C, material carries out press filtration after separating out, and dries up to obtain orange crystals (yield is 89.65%).

Route:

Result and discussion:

Sulfuric acid and oxysome weight ratio: sulfuric acid provides certain acidity mainly as solvent with for nitrated, and sulfuric acid acid is on the low side, dissolve difficulty, acidity is on the low side, and yield is on the low side

Weight ratio	Transformation efficiency %	Content %	Nitre body HPLC
				3/1	86.51	73.56	90.51
3.1/1	87.35	75.68	91.35
				3.2/1	88.64	79.25	91.69
3.3/1	89.65	81.67	91.75
				3.5/1	89.54	81.58	91.68

The increase of sulfuric acid amount, transformation efficiency improves, and content is also higher, but too much sulfuric acid can increase the process of Material Cost and sewage

Be best close to 3.3:1

The impact of nitrated temperature: along with the raising of temperature, yield is on the low side gradually, considers the difficulty of the too low operation of temperature, best in the reaction of 15-20 degree

Temperature	Transformation efficiency %	Content %	Nitre body HPLC
				0-5	87.95	81.26	91.32
5-15	88.16	80.31	91.58
				15-20	89.65	79.25	92.13
25-30	85.67	79.39	92.06
				30-35	82.38	79.64	91.68

Additive dosage is on the impact of material crystal: it is very large namely to add the impact that auxiliary agent lumps on material, and adding assistant material content is not low, and crystal is bad, places and namely lumps for several days, and significantly improve the crystal formation of material after adding auxiliary agent, and storage period increases.

Additive dosage	Content %	Caking performance
			0.0	73.56	Within several days, namely lump
0.001	76.49	Within 45 days, start caking
			0.003	78.64	Within 90 days, start caking
0.007	81.34	Within 365 days, start caking
			0.010	81.06	Within 365 days, start caking

Claims

1. a 6-nitre body, is characterized in that described product is prepared by following method:

(1) in reaction vessel, add sulfuric acid, stir frozen cooling to 0 ~ 20 DEG C;

(2) then add oxysome dry product gradually under heat-retaining condition, stir;

(3) drip the nitration mixture that quantitatively prepares, insulated and stirred is after 4 hours to terminal, and proceeded to by material in dilution still, add water in advance, auxiliary agent in dilution still, control temperature is, material carries out press filtration after separating out, dry product.

2. obtain product according to claim 1, it is characterized in that described product is prepared by following method: in 1500L reactor, add sulfuric acid 1000kg, stir frozen cooling to 0 ~ 20 DEG C, then oxysome dry product 300kg is added under heat-retaining condition gradually, stir 4 hours, drip the nitration mixture quantitatively prepared, 10 ~ 20 DEG C of insulated and stirred after 4 hours to terminal, material is proceeded in dilution still, add water in advance, auxiliary agent in dilution still, control temperature is 25 ~ 35 DEG C, material carries out press filtration after separating out, dry product.

3. the preparation method of 6-nitre body described in claim 1, is characterized in that described method comprises the steps: that (1) adds sulfuric acid in reaction vessel, stirs frozen cooling to 0 ~ 20 DEG C;

4. preparation method according to claim 3, it is characterized in that described method comprises the steps: to add sulfuric acid 1000kg in 1500L reactor, stir frozen cooling to 0 ~ 20 DEG C, then oxysome dry product 300kg is added under heat-retaining condition gradually, stir 4 hours, drip the nitration mixture quantitatively prepared, 10 ~ 20 DEG C of insulated and stirred after 4 hours to terminal, material is proceeded in dilution still, add water in advance, auxiliary agent in dilution still, control temperature is 25 ~ 35 DEG C, material carries out press filtration after separating out, dry product.