CN1786079A - Preparation process of sulfur black dye and product thereof - Google Patents
Preparation process of sulfur black dye and product thereof Download PDFInfo
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- CN1786079A CN1786079A CN 200410099360 CN200410099360A CN1786079A CN 1786079 A CN1786079 A CN 1786079A CN 200410099360 CN200410099360 CN 200410099360 CN 200410099360 A CN200410099360 A CN 200410099360A CN 1786079 A CN1786079 A CN 1786079A
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- Prior art keywords
- black
- temperature
- sulfide dye
- black sulfide
- slurry
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- PGYZAKRTYUHXRA-UHFFFAOYSA-N 2,10-dinitro-12h-[1,4]benzothiazino[3,2-b]phenothiazin-3-one Chemical compound S1C2=CC(=O)C([N+]([O-])=O)=CC2=NC2=C1C=C1SC3=CC=C([N+](=O)[O-])C=C3NC1=C2 PGYZAKRTYUHXRA-UHFFFAOYSA-N 0.000 title abstract description 34
- 239000000975 dye Substances 0.000 claims abstract description 64
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 239000000463 material Substances 0.000 claims description 48
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 47
- 238000001035 drying Methods 0.000 claims description 40
- 239000002002 slurry Substances 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 22
- 238000005507 spraying Methods 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 239000007921 spray Substances 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 239000005864 Sulphur Substances 0.000 claims description 11
- 238000005987 sulfurization reaction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 8
- 125000000018 nitroso group Chemical group N(=O)* 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 claims description 5
- VYZAHLCBVHPDDF-UHFFFAOYSA-N Dinitrochlorobenzene Chemical group [O-][N+](=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 VYZAHLCBVHPDDF-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 150000003568 thioethers Chemical class 0.000 claims description 4
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 33
- 238000004043 dyeing Methods 0.000 abstract description 11
- 239000004744 fabric Substances 0.000 abstract description 3
- 238000001694 spray drying Methods 0.000 abstract description 3
- 239000000988 sulfur dye Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 32
- 239000000047 product Substances 0.000 description 21
- 235000011121 sodium hydroxide Nutrition 0.000 description 15
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 14
- 238000005406 washing Methods 0.000 description 13
- 238000009413 insulation Methods 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- 229910052708 sodium Inorganic materials 0.000 description 12
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000010792 warming Methods 0.000 description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 10
- 229920001021 polysulfide Polymers 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 235000010265 sodium sulphite Nutrition 0.000 description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 6
- 230000005587 bubbling Effects 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- FHWRLVLDNKNYGD-UHFFFAOYSA-N nitrobenzene;hydrochloride Chemical compound Cl.[O-][N+](=O)C1=CC=CC=C1 FHWRLVLDNKNYGD-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 6
- 230000001939 inductive effect Effects 0.000 description 5
- 230000004075 alteration Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007791 dehumidification Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- IQUPABOKLQSFBK-UHFFFAOYSA-M 2-nitrophenolate Chemical compound [O-]C1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-M 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000002036 drum drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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- Coloring (AREA)
- Treating Waste Gases (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates toA preparation process of sulfur dye and a product thereof, in particular to a preparation process of sulfur black dye by spray drying and a sulfur black product prepared by the preparation process; the sulfur black product prepared by the invention has 1. the diameter of sulfur black dye particles is 150-200 mu m, the particles are fine, and the specific surface area is 300-360 cm2(ii)/g, greater; the product has good wettability, fluidity and solubility, excellent application performance, difficult color spots, figured cloth and color difference after dyeing, and various fastness is higher than that of the common product. 2. The sulfur black dye has uniform particles and uniform intensity, and is not easy to cause canthus during dyeing. 3. The pollution degree to the environment is greatly reduced.
Description
Technical field
The present invention relates to preparation technology of a kind of thioxine dyes and products thereof, relate in particular to a kind of preparation technology of spraying drying black sulfide dye and made sulphur black product thereof of adopting.
Background technology
Black sulfide dye is some organic aromatic compound and sulphur or the interactional dyestuff of sodium polysulphide, because its raw material and production process are all fairly simple, with low cost, and washing and light fastness are better, therefore, being in great demand of thioxine dyes, wherein especially with black, blue two kinds of dyestuffs in consumption maximum aspect the cotton products dyeing, be the bigger kind of output in the dyestuffs industries, sulphur black is with 2,2, 4-dinitrophenol and sodium polysulphide boil in the aqueous solution and form, and its production process is:
(1) sodium sulphite and sulfur reaction generate sodium polysulphide.
(2) 2,4-dinitrochlorobenzenes generate 2 through sodium hydroxide hydrolysis, the 4-sodium dinitrophenol.
(3) 2,4-sodium dinitrophenols reduce through sodium polysulphide, generate black sulfide dye through reactions such as condensation, sulfurations again.
(4) size mixing postcure black wash material drying and get finished product.
The black sulfide dye drying of prior art is to use the roller dryer drying, its principle of work is to utilize a kind of internal heating conduction type to rotate continuous drying equipment, the cylinder of rotation is by the bottom hopper, adhering to certain thickness material film, heat by pipe-line transportation to inner wall of rotary drum, be transmitted to cylinder outer wall, conduct the feed film again, make that the moisture in the material film is evaporated, dehumidification makes the material that contains moisture obtain drying, dry good material by device at the scraper shovel of cylinder surface from cylinder to the spiral conveyer that places below the scraper, by handling machinery dry material is concentrated, packing can obtain product.
Prior art adopts the roller dryer drying mainly to have following shortcoming:
A. adopt roller dryer exsiccant material dye granule bigger, general diameter is about 1mm, and the particle inequality, dye granule is thicker, and specific surface area is less, causes colorant dissolubility relatively poor, easy causing material inequality during dyeing forms color spot easily, influences dyefastness and application performance.
B. because material by sticking wall drying, certainly will cause dried dyestuff water ratio inequality, cause the dye strength inequality, cause dye aberration easily.
C. use roller drying, some material can be taken away from cylinder top along with moisture evaporated, has reduced the yield of dyestuff, and certainly will be caused pollution to environment by the material that moisture is taken away.
Summary of the invention
The present invention is directed to prior art adopts roller dryer and makes dried dyestuff water content inequality, cause dye aberration easily, and some material can be taken away from the cylinder top along with moisture evaporated, reduced the yield of dyestuff, and the shortcoming that the material of taking away pollutes the environment, provide a kind of material that can make to have good homogeneity, reduce tail gas with material environment is produced the spray-dired method of polluting.
Another object of the present invention provides a kind of have excellent every fastness and dyeing behavior, has bigger specific surface area again, and solubility property is good, and application performance is superior, the particulate black sulfide dye that cost is low.
Above-mentioned technical problem of the present invention is mainly solved by following technical proposals; A kind of preparation method of black sulfide dye, it is characterized in that, comprise the black sulfide dye intermediate and alkali reaction (2) resultant of reaction of (1) initiation (I) formula and vulcanize the black sulfide dye that reaction generates between compound or the mixture, (3) size mixing, (4) size mixing postcure black wash material through press spray dry and finished product, the dry used pressure of described press spray is 2Mpa-8Mpa; Wherein the X in (I) formula is halogens or hydroxyl, and R is a kind of in nitro, nitroso-group and the amino, R
1A kind of in nitro, nitroso-group and the amino
Drying of the present invention is the press spray drying, sulphur black slurry after sizing mixing, under the pressure of high-pressure pump, enter at a high speed from the tangential passage of spraying gun and to produce high-speed motion in the rotating room, being sprayed into droplet is dispersed in the hot gas flow, air enters the airheater heating through gas blower, enters spray-dryer then, drips contact drying with spray.Product section falls at the bottom of the tower, and part sucks primary cyclone by the one-level induced draft fan, and tail gas purifies with sack cleaner and water film dedusting and reclaims.
As preferably, described press spray exsiccant mode is to carry out from the top down, and the aperture of described nozzle is 0.8-3.0mm, and described shower nozzle number is 1-10.
As preferably, described black sulfide dye intermediate is 2, the 4-dinitrochlorobenzene, and described sulfuration compound or mixture are sulphide salt and sulphur, described alkaline solution is a sodium hydroxide solution.
As preferably, the aperture of described nozzle is 1.5-2.4mm, and described shower nozzle number is 4-8, and the dry used pressure of described press spray is 4Mpa-6Mpa.
As preferably, described size mixing postcure black wash material drying and the finished product whole process be in full temperature control state, the temperature of wherein controlling inlet air is 120 ℃-200 ℃, the temperature of outlet air is 30 ℃-100 ℃, the temperature of slurry is 50 ℃-110 ℃, the solid solid content 25-50% of slurry before the control spraying.
Those of ordinary skill is thought because the viscosity ratio of dyestuff is bigger; adopt press spray exsiccant mode can make slurry stop up shower nozzle, not only influence the drying effect of slurry, and usually can cause the damage of shower nozzle; this is a technology barrier, so they can not walk this mistaken ideas all the time.
The inventor once also entered into such mistaken ideas, but by the discovery that studies for a long period of time: because traditional technology has adopted the method for drum drying, this method will certainly cause the particle of material bigger, the particle inequality, Color is poor, the inventor adopts rational mixing method, full temperature control state carries out spraying drying, greatly reduce the viscosity of slurry, and the chance that adopts suitable pressure and nozzle bore to make the slurry of technology of the present invention stop up shower nozzle has significantly reduced, the black sulfide dye particle that spraying drying produces is less, be evenly distributed, Color improves greatly.
As preferably, described size mixing postcure black wash material drying and the process of finished product adopts full temperature control state, the temperature of wherein controlling inlet air is 150 ℃-180 ℃, the temperature of outlet air is 60 ℃-90 ℃, the temperature of slurry is 75 ℃-100 ℃, and the solid solid content of slurry is 35%-45% before the control spraying.
A kind of black sulfide dye, warp (1) causes the black sulfide dye intermediate and alkali reaction (2) resultant of reaction of (I) formula and vulcanizes between compound or the mixture and react, (2) size mixing, (3) size mixing and make after press spray is dry, it is characterized in that, described black sulfide dye particulate diameter is 150-200 μ m, and specific surface area is 300-360cm
2/ g; Wherein the X in (I) formula is halogens or hydroxyl, and R is a kind of in nitro, nitroso-group and the amino, and R1 is a kind of in nitro, nitroso-group and the amino;
R1
The sulphur black slurry is after the press spray drying, and general diameter is 150-200um, and the specific surface area of product is 300-360cm
2/ g.Product has good flowability, wettability, performances such as solubleness height.By after the spraying drying, dyestuff has good homogeneity simultaneously.Thereby make black sulfide dye reach the top standard of like product at dyeing and printing and dyeing application performance.
As preferably, described black sulfide dye intermediate is 2,4-dinitrochlorobenzene or 2, and 2, 4-dinitrophenol or 2,4-dinitrobenzene phenates, described sulfuration compound or mixture are sulphide salt and sulphur, described alkaline solution is a sodium hydroxide solution.
As preferably, described black sulfide dye particulate diameter is 160-180 μ m, and specific surface area is 320-340cm
2/ g.
Therefore, the present invention produces black sulfide dye that black sulfide dye and prior art produce and compares and have the following advantages:
1. the black sulfide dye particle diameter is 150-200um, and be to compare about 1mm with the sulphur black particle diameter of prior art, particle is thinner, specific surface area is big, product has preferably wettability, flowability and solvability preferably, application performance is superior, is difficult for causing color spot, figured cloth and aberration after the dyeing, and every fastness is than general height.
2. black sulfide dye uniform particles, uniform intensity is difficult for causing the look corner of the eyes when dyeing.
3. the degree of environmental pollution reduces greatly.
Description of drawings
Fig. 1 is a kind of process flow sheet of prior art
Embodiment
Further set forth the beneficial effect of black sulfide dye of the present invention by the following examples with reference examples.
Embodiment 1
A. the preparation of sodium polysulphide: in the 500ml there-necked flask, add 150 parts in water, be warmed up to 80 ℃, add 150 parts in 60% Sodium Sulphide, stir, add 105 parts in sulphur until whole dissolvings, after adding, standby 98 ℃ of insulation reaction 2 hours.
B. hydrolysis: in the 500ml there-necked flask, add 100 parts in water, 2,150 parts of 4-nitro Benzene Chloride drip 210 parts of 30% caustic soda solns at 70 ℃, and are 100 ℃ of insulation reaction 1 hour, standby.
C, sulfuration: in the 1000ml autoclave, add hydrolyzation material and the sodium polysulfide solution of having got ready, 100 ℃ of reactions 1 hour, sealed pot cover then, be warming up to 140 ℃, 120 ℃ of reactions 7 hours, reaction pressure was controlled at 0.1Mpa, after reaction is finished, exhaust, the caustic soda of the stink damp body and function 30% of discharging is recycled into sodium sulphite.
D, oxidation, filtration: the material that will vulcanizate is put into the 2000ml beaker, adds the water of 500ml, is warmed up to 50 ℃ and with gas blower air is fed under the liquid level, and bubbling air two hours filters well-oxygenated material with vacuum pump, washing.
E. size mixing: the filter cake after will washing is put into the 1000ml beaker, adds the water of 300ml, is warming up to 60 ℃, adds 30 parts in 60% Sodium Sulphide, stirs 45 minutes.
F, drying: the sulphur black slurry that will mix up, under the pressure of 2Mpa high-pressure pump, enter the rotating room at a high speed from the tangential passage of spraying gun, make slurry in the rotating room, produce high-speed motion, be sprayed into droplet and be dispersed in the hot gas flow, air enters the airheater heating through gas blower, the control inlet air temperature is 120 ℃, and the temperature of slurry is 50 ℃, and the solid content of slurry is controlled at 45%, enter spray-dryer then, with the droplet contact drying.Product section falls at the bottom of the tower.Air themperature is 30 ℃ during outlet, and part sucks primary cyclone by one-level air inducing, and tail gas purifies with sack cleaner and water film dedusting and reclaims.The black sulfide dye particle diameter majority of gained is 200um, and specific surface area is 300cm
2/ g, wettability can, solvability 180g/l, flowability can, particle is (wherein particle diameter is that 200um accounts for 90%) relatively evenly, the sulphur black that tail gas is taken away ten thousand/following (promptly dry sulphur black that 1 ton of sulphur black tail gas takes away below 0.01kg).
Embodiment 2
A. the preparation of sodium polysulphide: in the 500ml there-necked flask, add 150 parts in water, be warmed up to 85 ℃, add 150 parts in 60% Sodium Sulphide, stir, add 105 parts in sulphur until whole dissolvings, after adding, standby 99 ℃ of insulation reaction 2 hours.
B. hydrolysis: in the 500ml there-necked flask, add 100 parts in water, 2,150 parts of 4-nitro Benzene Chloride drip 210 parts of 30% caustic soda solns at 80 ℃, and are 102 ℃ of insulation reaction 1 hour, standby.
C, sulfuration: in the 1000ml autoclave, add hydrolyzation material and the sodium polysulfide solution of having got ready, 100 ℃ of reactions 1 hour, sealed pot cover then, be warming up to 140 ℃, 130 ℃ of reactions 7 hours, reaction pressure was controlled at 0.12Mp, after reaction is finished, exhaust, the caustic soda of the stink damp body and function 30% of discharging is recycled into sodium sulphite.
D, oxidation, filtration: the material that will vulcanizate is put into the 2000ml beaker, adds the water of 500ml, is warmed up to 60 ℃ and with gas blower air is fed under the liquid level, and bubbling air two hours filters well-oxygenated material with vacuum pump, washing.
E. size mixing: the filter cake after will washing is put into the 1000ml beaker, adds the water of 300ml, is warming up to 70 ℃, adds 30 parts in 60% Sodium Sulphide, stirs 35 minutes.
F, drying: the sulphur black slurry that will mix up, under the pressure of 6Mpa high-pressure pump, enter the rotating room at a high speed from the tangential passage of spraying gun, make slurry in the rotating room, produce high-speed motion, be sprayed into droplet and be dispersed in the hot gas flow, air enters the airheater heating through gas blower, the control inlet air temperature is 150 ℃, and the temperature of slurry is 75 ℃, and the solid content of slurry is controlled at 43%, enter spray-dryer then, with the droplet contact drying.Product section falls at the bottom of the tower.Air themperature is 60 ℃ during outlet, and part sucks primary cyclone by one-level air inducing, and tail gas purifies with sack cleaner and water film dedusting and reclaims.The black sulfide dye particle diameter majority of gained is 180um, and specific surface area is 320cm
2/ g, wettability is better, and solvability 190g/l is better mobile, particle very even (wherein particle diameter is that 180um accounts for more than 95%), the sulphur black that tail gas is taken away ten thousand/following (promptly dry sulphur black that 1 ton of sulphur black tail gas takes away below 0.01kg).
Embodiment 3
A. the preparation of sodium polysulphide: in the 500ml there-necked flask, add 150 parts in water, be warmed up to 90 ℃, add 150 parts in 60% Sodium Sulphide, stir, add 105 parts in sulphur until whole dissolvings, after adding, standby 100 ℃ of insulation reaction 2 hours.
B. hydrolysis: in the 500ml there-necked flask, add 100 parts in water, 2,150 parts of 4-nitro Benzene Chloride drip 210 parts of 30% caustic soda solns at 90 ℃, and are 105 ℃ of insulation reaction 1 hour, standby.
C, sulfuration: in the 1000ml autoclave, add hydrolyzation material and the sodium polysulfide solution of having got ready, 100 ℃ of reactions 1 hour, sealed pot cover then, be warming up to 140 ℃, 140 ℃ of reactions 7 hours, reaction pressure was controlled at 0.13Mp, after reaction is finished, exhaust, the caustic soda of the stink damp body and function 30% of discharging is recycled into sodium sulphite.
D, oxidation, filtration: the material that will vulcanizate is put into the 2000ml beaker, adds the water of 500ml, is warmed up to 80 ℃ and with gas blower air is fed under the liquid level, and bubbling air two hours filters well-oxygenated material with vacuum pump, washing.
E. size mixing: the filter cake after will washing is put into the 1000ml beaker, adds the water of 300ml, is warming up to 80 ℃, adds 30 parts in 60% Sodium Sulphide, stirs 45 minutes.
F, drying: the sulphur black slurry that will mix up, under the pressure of 5Mpa high-pressure pump, enter the rotating room at a high speed from the tangential passage of spraying gun, make slurry in the rotating room, produce high-speed motion, be sprayed into droplet and be dispersed in the hot gas flow, air enters the airheater heating through gas blower, the control inlet air temperature is 180 ℃, and the temperature of slurry is 90 ℃, and the solid content of slurry is controlled at 40%, enter spray-dryer then, with the droplet contact drying.Product section falls at the bottom of the tower.Air themperature is 90 ℃ during outlet, and part sucks primary cyclone by one-level air inducing, and tail gas purifies with sack cleaner and water film dedusting and reclaims.The black sulfide dye particle diameter majority of gained is 160um, and specific surface area is 340cm
2/ g, wettability is better, solvability 220g/l, mobile better, uniform particles (wherein particle diameter is that 160um accounts for more than 95%), the sulphur black that tail gas is taken away ten thousand/following (promptly dry sulphur black that 1 ton of sulphur black tail gas takes away below 0.01kg).
Embodiment 4
A. the preparation of sodium polysulphide: in the 500ml there-necked flask, add 150 parts in water, be warmed up to 90 ℃, add 150 parts in 60% Sodium Sulphide, stir, add 105 parts in sulphur until whole dissolvings, after adding, standby 100 ℃ of insulation reaction 2 hours.
B. hydrolysis: in the 500ml there-necked flask, add 100 parts in water, 2,150 parts of 4-nitro Benzene Chloride drip 210 parts of 30% caustic soda solns at 100 ℃, and are 103 ℃ of insulation reaction 1 hour, standby.
C, sulfuration: in the 1000ml autoclave, add hydrolyzation material and the sodium polysulfide solution of having got ready, 100 ℃ of reactions 1 hour, sealed pot cover then, be warming up to 140 ℃, 130 ℃ of reactions 7 hours, reaction pressure was controlled at 0.14Mp, after reaction is finished, exhaust, the caustic soda of the stink damp body and function 30% of discharging is recycled into sodium sulphite.
D, oxidation, filtration: the material that will vulcanizate is put into the 2000ml beaker, adds the water of 600ml, is warmed up to 70 ℃ and with gas blower air is fed under the liquid level, and bubbling air two hours filters well-oxygenated material with vacuum pump, washing.
E. size mixing: the filter cake after will washing is put into the 1000ml beaker, adds the water of 400ml, is warming up to 90 ℃, adds 30 parts in 60% Sodium Sulphide, stirs 45 minutes.
F, drying: the sulphur black slurry that will mix up, under the pressure of 7Mpa high-pressure pump, enter the rotating room at a high speed from the tangential passage of spraying gun, make slurry in the rotating room, produce high-speed motion, be sprayed into droplet and be dispersed in the hot gas flow, air enters the airheater heating through gas blower, the control inlet air temperature is 180 ℃, and the temperature of slurry is 100 ℃, and the solid content of slurry is controlled at 35%, enter spray-dryer then, with the droplet contact drying.Product section falls at the bottom of the tower.Air themperature is 100 ℃ during outlet, and part sucks primary cyclone by one-level air inducing, and tail gas purifies with sack cleaner and water film dedusting and reclaims.The black sulfide dye particle diameter majority of gained is 150um, and specific surface area is 360cm
2/ g, wettability can, solvability 240g/l, flowability can, particle is (wherein particle diameter is that 150um accounts for more than 90%) evenly, the sulphur black that tail gas is taken away ten thousand/following (promptly dry sulphur black that 1 ton of sulphur black tail gas takes away below 0.1kg).
Embodiment 5
A. the preparation of sodium polysulphide: in the 500ml there-necked flask, add 150 parts in water, be warmed up to 90 ℃, add 150 parts in 60% Sodium Sulphide, stir, add 105 parts in sulphur until whole dissolvings, after adding, standby 100 ℃ of insulation reaction 2 hours.
B. hydrolysis: in the 500ml there-necked flask, add 100 parts in water, 2,150 parts of 4-nitro Benzene Chloride drip 210 parts of 30% caustic soda solns at 100 ℃, and are 105 ℃ of insulation reaction 1 hour, standby.
C, sulfuration: in the 1000ml autoclave, add hydrolyzation material and the sodium polysulfide solution of having got ready, 100 ℃ of reactions 1 hour, sealed pot cover then, be warming up to 140 ℃, 140 ℃ of reactions 7 hours, reaction pressure was controlled at 0.14Mp, after reaction is finished, exhaust, the caustic soda of the stink damp body and function 30% of discharging is recycled into sodium sulphite.
D, oxidation, filtration: the material that will vulcanizate is put into the 2000ml beaker, adds the water of 600ml, is warmed up to 60 ℃ and with gas blower air is fed under the liquid level, and bubbling air two hours filters well-oxygenated material with vacuum pump, washing.
E. size mixing: the filter cake after will washing is put into the 1000ml beaker, adds the suitably water of (how many ml), is warming up to 80 ℃, adds 30 parts in 60% Sodium Sulphide, stirs 45 minutes.
F, drying: the sulphur black slurry that will mix up, under the pressure of 6Mpa high-pressure pump, enter the rotating room at a high speed from the tangential passage of spraying gun, make slurry in the rotating room, produce high-speed motion, be sprayed into droplet and be dispersed in the hot gas flow, air enters the airheater heating through gas blower, the control inlet air temperature is 150 ℃, and the temperature of slurry is 85 ℃, and the solid content of slurry is controlled at 40%, enter spray-dryer then, with the droplet contact drying.Product section falls at the bottom of the tower.Air themperature is 75 ℃ during outlet, and part sucks primary cyclone by one-level air inducing, and tail gas purifies with sack cleaner and water film dedusting and reclaims.The black sulfide dye particle diameter majority of gained is 170um, and specific surface area is 330cm
2/ g, wettability can, solvability 205g/l, flowability can, particle very even (wherein particle diameter is that 170um accounts for more than 95%), the sulphur black that tail gas is taken away ten thousand/following (promptly dry sulphur black that 1 ton of sulphur black tail gas takes away below 0.1kg).
The comparative example 1
A. the preparation of sodium polysulphide: in the 500ml there-necked flask, add 150 parts in water, be warmed up to 90 ℃, add 150 parts in 60% Sodium Sulphide, stir, add 105 parts in sulphur until whole dissolvings, after adding, standby 100 ℃ of insulation reaction 2 hours.
B. hydrolysis: in the 500ml there-necked flask, add 100 parts in water, 2,150 parts of 4-nitro Benzene Chloride drip 210 parts of 30% caustic soda solns at 100 ℃, and are 105 ℃ of insulation reaction 1 hour, standby.
C, sulfuration: in the 1000ml autoclave, add hydrolyzation material and the sodium polysulfide solution of having got ready, 100 ℃ of reactions 1 hour, sealed pot cover then, be warming up to 140 ℃, 140 ℃ of reactions 7 hours, reaction pressure was controlled at 0.13Mpa, after reaction is finished, exhaust, the caustic soda of the stink damp body and function 30% of discharging is recycled into sodium sulphite.
D, oxidation, filtration: the material that will vulcanizate is put into the 2000ml beaker, adds the water of 500ml, is warmed up to 60 ℃ and with gas blower air is fed under the liquid level, and bubbling air two hours filters well-oxygenated material with vacuum pump, washing.
E. size mixing: the filter cake after will washing is put into the 1000ml beaker, adds the water of 450ml, is warming up to 80 ℃, adds 30 parts in 60% Sodium Sulphide, stirs 45 minutes.
F. dry: that the black sulfide dye that mixes up is added the roller dryer drying, the cylinder of rotation is by the bottom hopper, adhering to certain thickness material film, heat by pipe-line transportation to inner wall of rotary drum, be transmitted to cylinder outer wall, conduct the feed film again, make that the moisture in the material film is evaporated, dehumidification, make the material that contains moisture obtain drying, dry good material by device at the scraper shovel of cylinder surface from cylinder to the spiral conveyer that places below the scraper, by handling machinery that dry material is concentrated, packing can obtain product.
Table 1: the contrast of the material performance of two kinds of dry gained of drying installation
| Group | Particle diameter (um) | Specific surface area (cm 2/g) | Solvability (g/l) | The ratio of the sulphur black that tail gas is taken away and the sulphur black of oven dry |
| The roller drying group | 1000±400 | 50±25 | 75±15 | Less than 0.1% |
| The spraying drying group | 175±25 | 330±30 | 210±30 | Less than 0.01% |
Annotate: spraying drying group and roller drying group compare, P＜0.01
Table 2: other property comparison of material of two kinds of dry gained of drying installation
| Group | Wettability | Mobile | The uniform particles degree |
| The roller drying group | Generally | Generally | The particle diameter distribution inequality, wherein the 900um-1100um diameter accounts for 30%～40% |
| The spraying drying group | Fine | Fine | Particle diameter distribution is even, and wherein the 150um-200um diameter accounts for more than 90% |
From top embodiment and comparative example as can be seen:
1. the dry gained black sulfide dye of press spray particle diameter is 150-200um, and is to compare about 1mm with the sulphur black particle diameter of prior art, and particle is thinner, specific surface area 300-360cm
2/ g is bigger; Product has preferably wettability, flowability and solvability preferably, and application performance is superior, is difficult for causing color spot, figured cloth and aberration after the dyeing, and every fastness is than general height.
2. black sulfide dye uniform particles, uniform intensity is difficult for causing the look corner of the eyes when dyeing.
3. the degree of environmental pollution reduces greatly.
Claims (10)
1. the preparation method of a black sulfide dye, it is characterized in that, comprise the black sulfide dye intermediate and alkali reaction (2) resultant of reaction of (1) initiation (I) formula and vulcanize the black sulfide dye that reaction generates between compound or the mixture, (3) size mixing, (4) size mixing postcure black wash material through press spray dry and finished product, the dry used pressure of described press spray is 2Mpa-8Mpa; Wherein the X in (I) formula is halogens or hydroxyl, and R is a kind of in nitro, nitroso-group and the amino, R
1A kind of in nitro, nitroso-group and the amino
2. the preparation method of black sulfide dye according to claim 1 is characterized in that, described press spray exsiccant mode is to carry out from the top down, and the aperture of described nozzle is 0.8-3.0mm, and described shower nozzle number is 1-10.
3. the preparation method of black sulfide dye according to claim 1, it is characterized in that, described black sulfide dye intermediate is 2,4-dinitrochlorobenzene or 2,2, 4-dinitrophenol or 2,4-dinitrobenzene phenates, described sulfuration compound or mixture are sulphide salt and sulphur, described alkaline solution is a sodium hydroxide solution.
4. according to the preparation method of right 1 or 2 or 3 described black sulfide dyes, it is characterized in that the aperture of described nozzle is 1.5-2.4mm, described shower nozzle number is 4-8, and the dry used pressure of described press spray is 4Mpa-6Mpa.
5. according to the preparation method of claim 1 or 2 or 3 described black sulfide dyes, it is characterized in that, described size mixing postcure black wash material drying and the finished product whole process be in full temperature control state, the temperature of wherein controlling inlet air is 120 ℃-200 ℃, the temperature of outlet air is 30 ℃-100 ℃, the temperature of slurry is 50 ℃-110 ℃, the solid solid content 25-50% of slurry before the control spraying.
6. the preparation method of black sulfide dye according to claim 4, it is characterized in that, described size mixing postcure black wash material drying and the process of finished product adopts full temperature control state, the temperature of wherein controlling inlet air is 120 ℃-200 ℃, the temperature of outlet air is 30 ℃-100 ℃, the temperature of slurry is 50 ℃-110 ℃, the solid content 25-50% of slurry before the control spraying.
7. the preparation method of black sulfide dye according to claim 6, it is characterized in that, described size mixing postcure black wash material drying and the process of finished product adopts full temperature control state, the temperature of wherein controlling inlet air is 150 ℃-180 ℃, the temperature of outlet air is 60 ℃-90 ℃, the temperature of slurry is 75 ℃-100 ℃, and the solid solid content of slurry is 35%-45% before the control spraying.
8. black sulfide dye, warp (1) causes the black sulfide dye intermediate and alkali reaction (2) resultant of reaction of (I) formula and vulcanizes between compound or the mixture and react, (2) size mixing, (3) size mixing and make after press spray is dry, it is characterized in that, described black sulfide dye particulate diameter is 150-200 μ m, and specific surface area is 300-360cm
2/ g; Wherein the X in (I) formula is halogens or hydroxyl, and R is a kind of in nitro, nitroso-group and the amino, and R1 is a kind of in nitro, nitroso-group and the amino;
9. the preparation method of black sulfide dye according to claim 8, it is characterized in that, described black sulfide dye intermediate is 2,4-dinitrochlorobenzene or 2,2, 4-dinitrophenol or 2,4-dinitrobenzene phenates, described sulfuration compound or mixture are sulphide salt and sulphur, described alkaline solution is a sodium hydroxide solution.
10. according to Claim 8 or 9 described black sulfide dyes, it is characterized in that described black sulfide dye particulate diameter is 160-180 μ m, specific surface area is 320-340cm
2/ g.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174272A (en) * | 2011-03-17 | 2011-09-07 | 浙江长征化工有限公司 | Preparation method and product of sulphur black dye |
| CN113582849A (en) * | 2020-04-30 | 2021-11-02 | 浙江省常山长盛化工有限公司 | Method for producing sulfur black based on mixed low oil of physically purified 2, 4-dinitrochlorobenzene |
| CN111100475B (en) * | 2020-01-08 | 2022-02-18 | 山西临汾染化(集团)有限责任公司 | Preparation method of sulfur dye |
| CN115011140A (en) * | 2022-06-28 | 2022-09-06 | 石家庄腾辉化工有限公司 | High-yield vulcanized black processing technology |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9224368D0 (en) * | 1992-11-20 | 1993-01-13 | Sandoz Ltd | Improvements in or relating to organic compounds |
| TR199600348A2 (en) * | 1995-05-03 | 1996-11-21 | Clariant Int Ltd | Sulfur dyes, their manufacture and use. |
| CN1180705C (en) * | 2002-01-11 | 2004-12-22 | 北京山宝新技术开发中心 | Technological process of producing banana powder |
-
2004
- 2004-12-27 CN CNB2004100993608A patent/CN100494288C/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174272A (en) * | 2011-03-17 | 2011-09-07 | 浙江长征化工有限公司 | Preparation method and product of sulphur black dye |
| CN111100475B (en) * | 2020-01-08 | 2022-02-18 | 山西临汾染化(集团)有限责任公司 | Preparation method of sulfur dye |
| CN113582849A (en) * | 2020-04-30 | 2021-11-02 | 浙江省常山长盛化工有限公司 | Method for producing sulfur black based on mixed low oil of physically purified 2, 4-dinitrochlorobenzene |
| CN115011140A (en) * | 2022-06-28 | 2022-09-06 | 石家庄腾辉化工有限公司 | High-yield vulcanized black processing technology |
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| CN100494288C (en) | 2009-06-03 |
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