CN101580643B - Pollution-free production technology of direct fast black G - Google Patents

Abstract

The invention relates to a pollution-free production technology of direct fast black G, comprising the following implementation steps: firstly, primary acid coupling is carried out on nitroaniline after diazotization and H-acid; after the full reaction of the H-acid is detected, sodium carbonate is added and pH is adjusted to 8 to 8.2 to carry out secondary basic coupling; the coupling product is added into a sodium sulfide solution for reduction, and the temperature gradually raises to t of 38 DEG C to 40 DEG C in the reaction process; after the sodium carbonate is added into the reduction product after acidification to adjust the pH of a medium to 7.5 to 8, the mixture is adsorbed by activated carbon and filtered, and ternary coupling is carried out on the obtained filter liquor after diazotization and lentine; and after the reaction is detected to be end point, the materials are directly delivered to a drying tower for spray drying. In the invention, the reduced reaction solution does not need the processes of salting out, acidification and filtration, activated carbon adsorption is adopted instead. In the process, no waste liquor is generated, and environment pollution caused in the production process of dye is greatly reduced. Simultaneously, wastewater processing is not needed, and the cost is saved. The optimized technology directly transfers the reaction solution after ternary coupling into the drying tower for spray drying; and the yield and the coloring intensity of the dye are effectively increased, energy is saved, the consumption is reduced, and the effect is obvious.

Description

Direct fast black G pollution-free production technology

Technical field

The present invention relates to a kind of production technique of dyestuff, particularly a kind of direct fast black G pollution-free production technology.

Background technology

At present, the competition of substantive dyestuff industry is growing more intense, and people require also improving constantly to the textiles color, and the environmental protection dyestuff that requirement is also increasingly high, bright in luster, dye uptake is high of dyestuff, salt-free liquid dye are favourably welcome.

In the traditional processing technology of substantive dyestuff, generally through oversalting, filtration with technological process such as concentrate; Purpose is desalination, removes unreacted raw material, midbody and secondary dyestuff, sloughs moisture, to obtain the dyestuff of desired concn and purity, carries out oven drying then, and processing powder dye or directly preparing becomes liquid dye.Facts have proved that the impurity, the salinity that bring in synthetic and the salting-out process have compiled a large amount of compositions that influence dyestuffs purity, intensity and solubleness, have only the impurity that reduces in the dyestuff, tinctorial strength that salinity could improve dyestuff and dyestuffs purity etc.At present, domestic traditional DYE PRODUCTION technology mainly adopts saltouts or acid out separation dyestuff composition, and product purity is not high, and the quality product consistence of different batches is also relatively poor, and quality product is very limited.Moreover owing to used a large amount of sodium-chlor at salting-out process; Can produce a large amount of waste water again; The discharging of waste water not only makes useful matteies such as the industrial chemicals that wherein contains and midbody slattern, and also can cause great pollution to environment, is seriously restricting the Sustainable development of dyestuffs industries.

For example, existing direct fast black G is one of kind important in the substantive dyestuff, also is the wider dyestuff of a kind of range of application.Yet, having produced great amount of wastewater in this dyestuff traditional processing technology, not treated discharging can cause serious environmental to pollute.And can improve the cost of product to the processing of spent process water.

Therefore, how to simplify production technique, waste water consumption in technology, is improved the dyestuff quality, energy-saving and cost-reducing, minimizing is polluted, and is one of current urgent problem of substantive dyestuff industry.

Summary of the invention

The objective of the invention is to overcome above-mentioned weak point, a kind of direct fast black G pollution-free production technology of simplifying production technique, raising dyestuff quality, reducing production costs, purify production environment is provided.

The implementation step that is adopted for the present invention of realization above-mentioned purpose is following:

(1) p-Nitroaniline diazotization:

50～the 55mL that discharges water adds p-Nitroaniline 13g and 30% hydrochloric acid 28g, stirs after 2 hours the adding ice cube and cools to t=0～5 ℃; Add fast the 3.7g Sodium Nitrite, then with under liquid level, adding the 3.7g Sodium Nitrite in 10～30 minutes again; Reinforced back temperature t=5～10 ℃ is used congo-red test paper, starch potassium iodide paper to detect and is blueness; Continue to stir 2～2.5 hours, all be dissolved as reaction end, add in the thionamic acid again and excessive nitrite up to p-Nitroaniline;

(2) couplings:

The 150mL that discharges water adds H-acid, pulls an oar after 30～40 minutes, transfers pH=6～6.5 with soda ash, temperature t=10～12 ℃; The H-acid solution was joined in the p-Nitroaniline diazonium salt solution in 1～1.5 hour, add continued reaction 3.5～4 hours, reaction solution volume V=240～250mL;

(3) secondary coupling:

In 30～40 minutes, transfer pH=8.5～9 behind the coupling terminal point, continue reaction 3～3.5 hours with 30% soda ash solution; Reaction solution volume V=280～285mL during reaction end;

(4) reduction:

Inspection secondary coupled reaction liquid pH=8～8.2 are if adding soda ash solution on the low side is adjusted in this scope; 17.3g sodium sulphite is configured to 15% aqueous solution, joined in the reaction solution in 40～60 minutes, temperature rises to t=38～40 ℃ gradually, stir to do sulfide in 30～35 minutes and detect test, this moment reaction solution volume V=340～350mL; Test passes continued reaction 40～45 minutes;

(5) acid out, catch up with sulphur:

In 20～30 minutes, slowly add hydrochloric acid adjustment pH=1.5～2.0 in the reduzate; Keep this ambient condition effect 2～3 hours, when pH no longer rises, the basic Ex-all of the sulfurous gas in the solution, this moment, liquor capacity was V=320～330mL;

Fast black base reactant after the desulfurization is transferred pH=7～7.5 with soda ash, be stirred to and dissolve back adding 5g activated carbon fully, stir 30～40 minutes after-filtration, collect filtrating, adding 4.5g Sodium Nitrite is subsequent use;

(6) diazotization:

Add 100g ice and 5mL water in the reaction solution, add 30% hydrochloric acid 28g again, controlled temperature t=0～2 ℃ in 1～1.5 hour, add ready fast black base mixed solution, add afterreaction liquid temp t=10～12 ℃; Again the 0.8g Sodium Nitrite is mixed with 30% aqueous solution, joined in the reaction solution, use congo-red test paper, starch potassium iodide paper to detect and be blueness in 40～60 minutes; Continuation effect 3.5～4 hours, this moment reaction solution volume V=580～600mL, reaction end is with in the thionamic acid and excessive nitrite;

(7) three couplings:

35～the 40mL that discharges water adds the 7.3g mphenylenediamine, is warming up to t=40～45 ℃, and it is dissolved fully, cool the temperature to again 15～20 ℃ subsequent use;

PH=4.5～5 are transferred with soda ash in last step diazonium salt solution t=5～7 ℃ of being cooled on the rocks, detect when not developing the color with congo-red test paper, add ready mphenylenediamine solution fast, add back t=15～17 ℃; Continue to stir 30～40 minutes, add soda ash and transfer pH=6～6.5, continuation effect 3～4 hours, mphenylenediamine is little excessive during reaction end, reaction solution volume V=620～630mL;

End reaction liquid directly send the drying tower spraying drying, sets inlet temperature: 228 ℃; Temperature out: 97 ℃; Be prepared into hollow bead shape solid dye, particle diameter is 1～1.3mm.

The invention has the beneficial effects as follows:

Cleaning of non-wastewater discharge produced and save energy in the outstanding embodiment of this production technique production technique.Change direct fast black G traditional processing technology condition, the reaction solution after the reduction need not to saltout, acid out, filtration, changes activated carbon adsorption into.This process does not produce waste liquid, has significantly reduced the pollution of DYE PRODUCTION process to environment.Need not to handle waste water simultaneously, practice thrift cost.The reaction solution of this optimization technology after with three couplings directly changes the drying tower spraying drying over to; Effectively improve the yield and the tinctorial strength of dyestuff, energy-saving and cost-reducing, effect is remarkable; Simultaneously save former subsidiary material greatly, saved 10%～20% sodium-chlor that traditional method adds in proportion; It is good that spray-dried tower is handled the back consistency of product, both saved time, economizes coal, power saving, province's steam etc.For example, general substantive dyestuff is produced 300kg/h, and the inventive method is produced 500kg/h～800kg/h.Simplify production technique, reduce production costs, effectively improved quality product, increased product yield, enlarged throughput, and fundamentally solved the contaminated wastewater problem of environment.

Facts have proved that the impurity that brings in the synthetic and salting-out process of dyestuff, purity, intensity and the solubleness that salt branch greatly influences dyestuff have only the salinity that reduces in the dyestuff could improve the tinctorial strength of dyestuff.Water-insoluble can reach 0.05%, is superior to traditional technology greatly, can directly produce the consistence that keeps the different batches quality product through the spray-drying tower serialization; Eliminate the high density colorful wastewater that produces in the salting-out process, and create a stable solvent condition for adding auxiliary.Save traditional saltout, filter-pressing process has then alleviated waste water from dyestuff from the source intractability, help the smooth implementation of efforts at environmental protection.

Description of drawings

Fig. 1 is the traditional processing technology schema;

Fig. 2 is a process flow sheet of the present invention.

Embodiment

Below in conjunction with accompanying drawing and preferred embodiment, to details are as follows according to embodiment provided by the invention:

As shown in Figure 2, a kind of direct fast black G pollution-free production technology is characterized in that implementation step is following:

(1) p-Nitroaniline diazotization:

50～the 55mL that discharges water adds p-Nitroaniline 13g and 30% hydrochloric acid 28g, stirs after 2 hours the adding ice cube and cools to t=0～5 ℃; Add fast the 3.7g Sodium Nitrite, then with under liquid level, adding the 3.7g Sodium Nitrite in 10～30 minutes again; Reinforced back temperature t=5～10 ℃ is used congo-red test paper, starch potassium iodide paper to detect and is blueness; Continue to stir 2～2.5 hours, all be dissolved as reaction end, add in the thionamic acid again and excessive nitrite up to p-Nitroaniline;

(2) couplings:

The 150mL that discharges water adds H-acid, pulls an oar after 30～40 minutes, transfers pH=6～6.5 with soda ash, temperature t=10～12 ℃; The H-acid solution was joined in the p-Nitroaniline diazonium salt solution in 1～1.5 hour, add continued reaction 3.5～4 hours, reaction solution volume V=240～250mL;

(3) secondary coupling:

In 30～40 minutes, transfer pH=8.5～9 behind the coupling terminal point, continue reaction 3～3.5 hours with 30% soda ash solution; Reaction solution volume V=280～285mL during reaction end;

(4) reduction:

Inspection secondary coupled reaction liquid pH=8～8.2 are if adding soda ash solution on the low side is adjusted in this scope; 17.3g sodium sulphite is configured to 15% aqueous solution, joined in the reaction solution in 40～60 minutes, temperature rises to t=38～40 ℃ gradually, stir to do sulfide in 30～35 minutes and detect test, this moment reaction solution volume V=340～350mL; Test passes continued reaction 40～45 minutes;

(5) acid out, catch up with sulphur:

In 20～30 minutes, slowly add hydrochloric acid adjustment pH=1.5～2.0 in the reduzate; Keep this ambient condition effect 2～3 hours, when pH no longer rises, the basic Ex-all of the sulfurous gas in the solution, this moment, liquor capacity was V=320～330mL;

Fast black base reactant after the desulfurization is transferred pH=7～7.5 with soda ash, be stirred to and dissolve back adding 5g activated carbon fully, stir 30～40 minutes after-filtration, collect filtrating, adding 4.5g Sodium Nitrite is subsequent use;

(6) diazotization:

Add 100g ice and 5mL water in the reaction solution, add and add 30% hydrochloric acid 28g again, controlled temperature t=0～2 ℃ in 1～1.5 hour, add ready fast black base mixed solution, add afterreaction liquid temp t=10～12 ℃; Again the 0.8g Sodium Nitrite is mixed with 30% aqueous solution, joined in the reaction solution, use congo-red test paper, starch potassium iodide paper to detect and be blueness in 40～60 minutes; Continuation effect 3.5～4 hours, this moment reaction solution volume V=580～600mL, reaction end is with in the thionamic acid and excessive nitrite;

(7) three couplings:

35～the 40mL that discharges water adds the 7.3g mphenylenediamine, is warming up to t=40～45 ℃, and it is dissolved fully, cool the temperature to again 15～20 ℃ subsequent use;

PH=4.5～5 are transferred with soda ash in last step diazonium salt solution t=5～7 ℃ of being cooled on the rocks, detect when not developing the color with congo-red test paper, add ready mphenylenediamine solution fast, add back t=15～17 ℃; Continue to stir 30～40 minutes, add soda ash and transfer pH=6～6.5, continuation effect 3～4 hours, mphenylenediamine is little excessive during reaction end, reaction solution volume V=620～630mL;

End reaction liquid directly send the drying tower spraying drying, sets inlet temperature: 228 ℃; Temperature out: 97 ℃; Be prepared into hollow bead shape solid dye, particle diameter is 1～1.3mm.

Said direct fast black G chemical structural formula:

Technology contrast traditional processing technology (shown in Figure 1) of the present invention, technology is simple, reasonable.

Table 1: the technical indicator of the inventive method and produced in conventional processes product contrasts as follows:

The key technical indexes	The inventive method	Traditional method
			Water-insoluble	0.05％	0.2％
Solubleness (100 ℃)	100g/L	70g/L
			The pH value	8.5～9	8.5～9
Light fastness	3～4 grades	3～4 grades

The index that dye solution solid content that the inventive method is produced and intensity significantly are superior to adopting prior art; Effectively improve the yield and the tinctorial strength of dyestuff, have very strong competitive power with its stable quality, preferential price, make product improve a class, market outlook are boundless.Simultaneously, the present invention reduces the generation of pollutent in the production process to greatest extent, carries out cleaner production.Can reduce waste discharge significantly, the pollution problem that fundamentally solves dye industry.DYE PRODUCTION economic benefit of the present invention is very remarkable, and its development prospect is very optimistic, has enormous potentialities.

Above-mentioned with reference to embodiment to the detailed description that this direct fast black G pollution-free production technology carries out, be

Illustrative rather than determinate, therefore in the variation and the modification that do not break away under the general plotting of the present invention, should belong within protection scope of the present invention.

Claims (1)

1. direct fast black G pollution-free production technology is characterized in that implementation step is following:

(1) p-Nitroaniline diazotization:

50～the 55mL that discharges water adds p-Nitroaniline 13g and 30% hydrochloric acid 28g, stirs after 2 hours the adding ice cube and cools to t=0～5 ℃; Add fast the 3.7g Sodium Nitrite, then with under liquid level, adding the 3.7g Sodium Nitrite in 10～30 minutes again; Reinforced back temperature t=5～10 ℃ is used congo-red test paper, starch potassium iodide paper to detect and is blueness; Continue to stir 2～2.5 hours, all be dissolved as reaction end, add in the thionamic acid again and excessive nitrite up to p-Nitroaniline;

(2) couplings:

The 150mL that discharges water adds H-acid, pulls an oar after 30～40 minutes, transfers pH=6～6.5 with soda ash, temperature t=10～12 ℃; The H-acid solution was joined in the p-Nitroaniline diazonium salt solution in 1～1.5 hour, add continued reaction 3.5～4 hours, reaction solution volume V=240～250mL;

(3) secondary coupling:

In 30～40 minutes, transfer pH=8.5～9 behind the coupling terminal point, continue reaction 3～3.5 hours with 30% soda ash solution; Reaction solution volume V=280～285 mL during reaction end;

(4) reduction:

Inspection secondary coupled reaction liquid pH=8～8.2 are if adding soda ash solution on the low side is adjusted in this scope; 17.3g sodium sulphite is configured to 15% aqueous solution, joined in the reaction solution in 40～60 minutes, temperature rises to t=38～40 ℃ gradually, stir to do sulfide in 30～35 minutes and detect test, this moment reaction solution volume V=340～350mL; Test passes continued reaction 40～45 minutes;

(5) acid out, catch up with sulphur:

In 20～30 minutes, slowly add hydrochloric acid adjustment pH=1.5～2.0 in the reduzate; Keep this ambient condition effect 2～3 hours, when pH no longer rises, the basic Ex-all of the sulfurous gas in the solution, this moment, liquor capacity was V=320～330mL;

Fast black base reactant after the desulfurization is transferred pH=7～7.5 with soda ash, be stirred to and dissolve back adding 5g activated carbon fully, stir 30～40 minutes after-filtration, collect filtrating, adding 4.5g Sodium Nitrite is subsequent use;

(6) diazotization:

Add 100g ice and 5mL water in the reaction solution, add 30% hydrochloric acid 28g again, controlled temperature t=0～2 ℃ in 1～1.5 hour, add ready fast black base mixed solution, add afterreaction liquid temp t=10～12 ℃; Again the 0.8g Sodium Nitrite is mixed with 30% aqueous solution, joined in the reaction solution, use congo-red test paper, starch potassium iodide paper to detect and be blueness in 40～60 minutes; Continuation effect 3.5～4 hours, this moment reaction solution volume V=580～600mL, reaction end is with in the thionamic acid and excessive nitrite;

(7) three couplings:

35～the 40mL that discharges water adds the 7.3g mphenylenediamine, is warming up to t=40～45 ℃, and it is dissolved fully, cool the temperature to again 15～20 ℃ subsequent use;

PH=4.5～5 are transferred with soda ash in last step diazonium salt solution t=5～7 ℃ of being cooled on the rocks, detect when not developing the color with congo-red test paper, add ready mphenylenediamine solution fast, add back t=15～17 ℃; Continue to stir 30～40 minutes, add soda ash and transfer pH=6～6.5, continuation effect 3～4 hours, mphenylenediamine is little excessive during reaction end, reaction solution volume V=620～630mL;

End reaction liquid directly send the drying tower spraying drying, sets inlet temperature: 228 ℃; Temperature out: 97 ℃; Be prepared into hollow bead shape solid dye, particle diameter is 1～1.3mm.

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