A kind of method that bright blue waste gas reclaims and synthesizes for reactive dye
Technical field
The present invention relates to waste gas reclaims and dyestuff synthesis technical field, be specifically related to a kind of method that bright blue waste gas reclaims and synthesizes for reactive dye, the waste gas producing in copper phthalocyanine chlorosulfonation or chlorination process reclaims, and the hydrogen chloride solution of recovery and sodium hydroxymethane sulfonate solution are directly used in diazo reaction and the sulfomethylation of dyestuff in synthetic.
Background technology
In molecule, introduce sulfonic acid group or sulfonic acid chloride group can use a large amount of chlorosulfonic acids and thionyl chloride, in course of reaction, can produce the waste gas such as a large amount of hydrogen chloride, sulfur dioxide, can produce a large amount of spent acid while diluting in frozen water, spent acid is recycled.The Chinese patent application that for example publication number is CN101445219A discloses a kind of recoverying and utilizing method of spent acid, and described spent acid is to dye produce in chemical industry sulfonation or acyl sulfonation process hydrochloric, sulfuric acid and SO
2, the waste liquid that acidity is 5~40%, described method comprises: described spent acid is reacted with the salpeter solution of enough mass concentrations 60~98% and to having no irritating odor, exist and make starch potassium iodide paper to become blue, by SO
2change nitrosyl sulfuric acid into, the mixed liquor that contains nitrosyl sulfuric acid, hydrochloric acid and sulfuric acid making is back to the diazo process of dyestuff in synthetic, but in the method, does not mention that in chlorosulfonation or chlorination reaction production process, waste gas reclaims.
Publication number is the separation and recovery method that the Chinese invention patent application of CN102343197A discloses a kind of hydrogen chloride and sulfur dioxide mixture gas, it comprises the following steps: step 1, first sulfonating reaction is produced to hydrogen chloride and sulfur dioxide mixture gas, after bubbler gas washing, mist enters bubbler, remove the material that other meets water decomposition, from gas containing hydrogen chloride, sulfur dioxide and steam out wherein; Step 2, carries out one-level falling film absorption: hydrogen chloride, sulfur dioxide and steam are put into one-level film-falling absorption tower, sponge most of hydrogen chloride gas, discharge sulfur dioxide and partial oxidation hydrogen; Step 3, carries out secondary packing material absorbing: sulfur dioxide and partial oxidation hydrogen are put into secondary packed tower, and the hydrogen chloride gas of overflowing from secondary packed tower, discharges most of sulfur dioxide gas; Step 4, carry out sulfur dioxide packing material absorbing: with 15% soda ash solution, absorb the sulfur dioxide of overflowing from secondary packed tower, become sodium hydrogensulfite, control pH value between 5.5~6.0 temperature at 20~25 ℃; Step 5, vent gas treatment: this cover absorption system keeps negative pressure state by water-ring vacuum system, and circulating vacuum unit is used 15% soda ash solution.
It is at present industrial that to waste gas, recycling is confined to obtain hydrochloric acid and sodium sulfite crystal single product, the Chinese invention patent application that is CN101343038A as publication number discloses hydrogen chloride in producing of a kind of lipoic acid and the recovery method of sulfur dioxide mix waste gas, hydrogen chloride and sulfur dioxide mix waste gas are incorporated into by least a set of water absorption plant for being dissolved in the water for hydrogen chloride gas above and that be one another in series and connect by pipeline, the concentration of the hydrogen chloride solution in water absorption plant reclaims hydrogen chloride while reaching blowing concentration, in the sulfur dioxide gas vacuum of the purification obtaining after the absorbing hydrogen chloride gas in water absorption plant is drawn into reaction unit by pipeline in water absorption plant absorbing hydrogen chloride gas with sodium hydroxide solution stepwise reaction, and substep is controlled reaction temperature and adjusted stepwise pH value, obtain sodium sulfite solution, sodium sulfite solution is discharged to centrifugation centrifugal separating device from reaction unit, obtain seven water sodium sulfite crystalline solid, the mother liquor that centrifugation goes out is sent back in reaction unit.In the method, need 5 cover absorption tower devices, cost recovery is relatively high like this.
Summary of the invention
The invention provides a kind of method that bright blue waste gas reclaims and synthesizes for reactive dye, realize waste recovery comprehensive utilization, not only save exhaust-gas treatment expense, and protected environment, reduced the synthetic cost of dyestuff simultaneously.
Bright blue waste gas reclaims and for the synthetic method of reactive dye, comprises the steps:
(1) the waste gas water of the containing hydrogen chloride producing in copper phthalocyanine chlorosulfonation or chlorination process, sulfur dioxide and thionyl chloride is carried out to twice absorption successively, obtain hydrogen chloride solution;
(2) by sodium hydroxide solution spray-absorption sulfur dioxide for the waste gas after step (1) is processed; When the pH of absorption liquid value drops to 7.0-8.0, add paraformaldehyde to continue sulfur dioxide absorption, obtain sodium hydroxymethane sulfonate solution, the pH value that maintains absorption liquid in paraformaldehyde absorption process is 6-7;
(3) diazo reaction step (1) gained hydrogen chloride solution being synthesized for reactive dye; The sulfomethylation that step (2) gained sodium hydroxymethane sulfonate solution is synthesized for reactive dye.
It is as follows that the process of copper phthalocyanine chlorosulfonation and chlorination generation waste gas relates to reaction equation:
CuPc+2HOSO
2Cl→CuPcSO
2Cl+H
2SO
4+HCl↑
H
2O+HOSO
2Cl→H
2SO
4+HCl↑
H
2O+SOCl
2→SO
2↑+2HCl↑
In formula, CuPc represents copper phthalocyanine, and structural formula is as follows:
In described hydrogen chloride solution, the mass percent of hydrogen chloride is 28-32%; In described sodium hydroxymethane sulfonate solution, the mass percent of sodium hydroxymethane sulfonate is 50-55%.
Described in step (3), the step of diazo reaction is as follows:
Contain amino benzene class or the aqueous solution of naphthalene compounds, add gained hydrogen chloride solution in step (1), add enough ice cubes, with within 30~45 minutes, disperseing dropping sodium nitrite solution, 0-10 ℃ of diazo reaction 1~1.5 hour, obtain diazo component.
Preferably, contain amino benzene class or the aqueous solution of naphthalene compounds, add gained hydrogen chloride solution in step (1), add enough ice cubes, with within 30 minutes, disperseing dropping sodium nitrite solution, 0-10 ℃ of diazo reaction 1 hour, obtain diazo component.
Described in step (3), the step of sulfomethylation is as follows:
Sodium hydroxymethane sulfonate solution was disperseed to be added drop-wise to contain in amino benzene class or naphthalene class coupling component solution with 1~1.5 hour, and carry out sulfomethylation 1~1.5 hour at 40-45 ℃, obtain sulphur methyl coupling component.
Preferably, sodium hydroxymethane sulfonate solution disperseed to be added drop-wise to contain in amino benzene class or naphthalene class coupling component solution with 1 hour, and carried out sulfomethylation 1 hour at 40-45 ℃, obtained sulphur methyl coupling component.
Described in step (2), the mass concentration of sodium hydroxide solution is 10%.
Described in step (2), in sodium hydroxide solution, the mol ratio of NaOH and SO 2 in waste gas is 0.9~1:1.
Described in step (2), the mol ratio of paraformaldehyde and SO 2 in waste gas is 1~1.05:1.
Further preferably, described sulphur methyl coupling component is mixed with described diazo component, controlling temperature is 12~15 ℃, and stirring reaction regulates pH value after 3.5~4.5 hours be 6~6.5, then react 3.5~4.5 as a child must orange.
A kind of preferred technical scheme: (1) by waste gas first successively by take spray absorber I and the spray absorber II that running water is absorption liquid, when the hydrogen cloride concentration in spray absorber I reaches 28-32%, with pump, the hydrogen chloride solution of 28-32% is transferred to hydrochloric acid storage tank, spray liquid in spray absorber II is transferred to spray absorber I, and spray absorber II adds fresh running water to continue to absorb;
(2) waste gas after step (1) is processed is successively by take spray absorber III and the spray absorber IV that sodium hydroxide solution is absorption liquid, when the absorption liquid pH value in spray absorber III drops to 7.0-8.0, in spray absorber III, add graininess basic poly formaldehyde, continue to absorb, and be 6-7 by the pH value of absorption liquid in 30% sodium hydroxide solution maintenance absorption tower III, when the absorption liquid Free-formaldehyde concentration of spray absorber III is during lower than 0.1mol/L, now sodium hydroxymethane sulfonate content is at 50-55%, with pump, sodium hydroxymethane sulfonate solution is transferred to sodium hydroxymethane sulfonate storage tank, spray liquid in spray absorber IV is transferred to absorption tower III, in spray absorber IV, add 5% fresh NaOH to continue to absorb,
(3) diazo reaction step (1) gained hydrogen chloride solution being synthesized for reactive dye:
Contain amino benzene class or the aqueous solution of naphthalene compounds, add gained hydrogen chloride solution in step (1), add enough ice cubes, with within 30 minutes, disperseing dropping sodium nitrite solution, 0-10 ℃ of diazo reaction 1 hour, obtain diazo component;
The sulfomethylation that step (2) gained sodium hydroxymethane sulfonate solution is synthesized for reactive dye:
Sodium hydroxymethane sulfonate solution disperseed to be added drop-wise to 1 hour and contains in amino benzene class or naphthalene class coupling component solution, and at 30-35 ℃, made 40-45 ℃ into and carry out sulfomethylation 1 hour, obtained sulphur methyl coupling component;
(4) described sulphur methyl coupling component is mixed with described diazo component, controlling temperature is 12~15 ℃, and stirring reaction regulates pH value after 3.5~4.5 hours be 6~6.5, then reacts 3.5~4.5 and as a child must obtain reactive dye.
In waste gas, main component is hydrogen chloride, sulfur dioxide and unreacted thionyl chloride, waste gas is first by take spray absorber I and the spray absorber II that running water is absorption liquid, thionyl chloride runs into water and resolves into immediately hydrogen chloride and sulfur dioxide, so use running water absorbing hydrogen chloride, spray absorber I is more high than the hydrogen cloride concentration of spray absorber II, when the hydrogen cloride concentration in spray absorber I reaches 30%, with pump, 30% hydrogen chloride solution is transferred to hydrochloric acid storage tank, spray liquid in spray absorber II is transferred to spray absorber I, spray absorber II adds fresh running water to continue to absorb.
Sulfur dioxide solubility in hydrogen chloride solution is very little, can enter down one spray absorber III and the spray absorber IV that to take with 10% sodium hydroxide solution be absorption liquid with air-flow, when the absorption liquid pH value in the III of absorption tower drops to 7.0-8.0, to absorption tower III, add graininess paraformaldehyde, continue to absorb, and with 30% NaOH, keep the pH=6-7 of absorption liquid in the III of absorption tower, when the free formaldehyde concentration of absorption tower III absorption liquid is during lower than 0.1mol/L, now sodium hydroxymethane sulfonate content is at 50-55%, with pump, sodium hydroxymethane sulfonate solution is transferred to sodium hydroxymethane sulfonate storage tank, spray liquid in the IV of absorption tower is transferred to absorption tower III, receiving tower IV adds 5% fresh NaOH to continue to absorb.
The waste gas problem that the present invention has produced in not only having solved and having produced; protected environment simultaneously; the hydrogen chloride solution reclaiming and solution of sodium bisulfite can directly apply in the diazo reaction and sulfomethylation of dyestuff in synthetic, and the object that not only reaches refuse cycling and reutilization has also reduced the integrated cost of dyestuff.
Accompanying drawing explanation
Fig. 1 is process chart of the present invention.
The specific embodiment
Embodiment 1
Waste gas recycling
To dry 1# reaction pot, add 2500 kilograms of chlorosulfonic acids, open and stir, add at leisure 400 kilograms of copper phthalocyanines, in reinforced process, temperature is controlled at below 90 ℃, stir 60 minutes, after material all dissolves, material is all transferred to 2# reaction pot, 2# reaction pot is opened and is stirred, with steam, slowly heat, in 2 hours, be warming up to 138 ℃, and be incubated 5 hours at 138-140 ℃, in temperature-rise period, produce large quantity of exhaust gas and take hydrogen chloride as main, insulation reaction finishes rear with cooling water temperature to 85 ℃, in 2 hours, drip 520 kilograms of thionyl chlorides, and temperature is controlled 86-87 ℃ when dripping thionyl chloride, thionyl chloride drips and finishes rear stirring 2 hours, with being steam heated to 105 ℃, and be incubated 3 hours at 104-106 ℃, with compressed air, from 2# reaction pot bottom valve, blow, bubbling 5 hours, blow, bubbling finishes rear with cooling water temperature to 50 ℃, dripping thionyl chloride and later stage air blowing, bubbling all produces a large amount of waste gas, comprise hydrogen chloride, sulfur dioxide and unreacted thionyl chloride
In waste gas, main component is hydrogen chloride, sulfur dioxide and unreacted thionyl chloride, waste gas is first by take running water as absorption liquid spray absorber I and spray absorber II, thionyl chloride runs into water and resolves into immediately hydrogen chloride and sulfur dioxide, so use running water absorbing hydrogen chloride, spray absorber I is more high than spray absorber II hydrogen cloride concentration, when spray absorber I hydrogen cloride concentration can reach 30%, with pump, 30% hydrogen chloride solution is transferred to hydrochloric acid storage tank, spray liquid in spray absorber II is transferred to spray absorber I, spray absorber II adds fresh running water to continue to absorb.
Sulfur dioxide solubility in hydrogen chloride solution is very little, can enter down one with by 10% sodium hydroxide solution absorption liquid spray absorber III and spray absorber IV with air-flow, when spray absorber III absorption liquid pH value drops to 7.0-8.0, to spray absorber III, add 200 kilograms of graininess paraformaldehydes, continue to absorb, and with 30% NaOH, keep the pH=6-7 of spray absorber (III) absorption liquid, when the free formaldehyde concentration of spray absorber III absorption liquid is during lower than 0.1mol/L, now sodium hydroxymethane sulfonate content is at 50-55%, with pump, sodium hydroxymethane sulfonate solution is transferred to sodium hydroxymethane sulfonate storage tank, spray liquid in spray absorber IV is transferred to spray absorber III, spray absorber IV adds 5% fresh NaOH to continue to absorb.Technological process as shown in Figure 1.
The application in dyestuff is synthetic of 30% hydrogen chloride solution and 50-55% sodium hydroxymethane sulfonate solution
In reaction pot A, add water 2000L, 239 kilograms of J acid, are warming up to 30 ℃, stir 30 minutes, with 30% liquid caustic soda, dissolve, control pH=6.5-7, get 800 kilograms of the sodium hydroxymethane sulfonate solution (content 50%) of above-mentioned recovery, with 60 minutes, be uniformly dispersed and drop in J acid solution, temperature is controlled at 40-42 ℃, reacts 4 hours, and paper using chromatograph detects to J acid fluorescence spot and disappears for reaction end, obtain sulphur methyl J acid, stand-by.
In reaction pot B, add water 1000L, 562 kilograms of para-esters, 280 kilograms of 30% hydrogen chloride solutions that add 1500 kilograms, ice and above-mentioned recovery, disperse to stir 1 hour, with dispersion in 30 minutes, drip 460 kilograms of 30% sodium nitrite solutions, temperature is controlled at below 5 ℃, diazo reaction 1 hour, natrium nitrosum with sulfamic acid decomposing excessive, obtain para-ester diazo liquid, sulphur methyl J acid solution synthetic in reaction pot A is joined rapidly in para-ester diazo liquid, temperature is controlled at 12-15 ℃, stirring reaction 4 hours, add lentamente again sodium bicarbonate powder, control pH=6-6.5, and maintain reaction 4 hours, obtain orange, structural formula is as follows:
Embodiment 2
Waste gas recovery and treatment method is with embodiment 1
The application in dyestuff is synthetic of 30% hydrogen chloride solution reclaiming and 50-55% sodium hydroxymethane sulfonate solution
In reaction pot A, add water 2000L, 2,188 kilograms of 4-diamino benzene sulfonic acids, be warming up to 30 ℃, stir 30 minutes, with 30% liquid caustic soda, dissolve, control pH=6.5-7, get 800 kilograms of the sodium hydroxymethane sulfonate solution (content 50%) of above-mentioned recovery, evenly drop in 2,4-diamino benzene sulfonic acid sodium solution with 60 minutes, temperature is controlled at 40-42 ℃, react 4 hours, paper using chromatograph detection to 2,4-diamino benzene sulfonic acid fluorescence spot disappears for reaction end, obtains 2,4(N-sulphur methyl)-diamino benzene sulfonic acid sodium, stand-by
In reaction pot B, add water 500L, 281 kilograms of para-esters, 140 kilograms of 30% hydrogen chloride solutions that add 800 kilograms, ice and above-mentioned recovery, disperse to stir 1 hour, with dispersion in 30 minutes, drip 230 kilograms of 30% sodium nitrite solutions, temperature is controlled at below 5 ℃, diazo reaction 1 hour, natrium nitrosum with sulfamic acid decomposing excessive, obtain para-ester diazo liquid, by in reaction pot A synthetic 2, 4(N-sulphur methyl)-diamino benzene sulfonic acid sodium solution joins in para-ester diazo liquid lentamente, temperature is controlled at 12-15 ℃, with sodium bicarbonate powder, control pH=6-6.5 simultaneously, and maintain reaction 4 hours, obtain weld, structural formula is as follows:
The dyestuff that the dye well preparing is directly used pure raw material to prepare contrasts, and data are as following table 1 and table 2
Table 1
Table 2
Table 1 adopts following standard with the test of table 2 performance index:
The general condition regulation of GB/T2374-2007 dyeing colour examining
The coloured light of GB/T2387-2003 reactive dye and strength detection method
The mensuration of the degree of fixation of GB/T2391-2006 reactive dye
The mensuration of GB/T3671.1-1996 water-soluble dye solubility and steady dissolution
GB/T4841.1-2006 dyeing standard depth colour atla
GB/T6678-2003 chemical products sampling general provisions
GB/T3920-1997 textile color stability test colour fastness to rubbing
GB/T3921-2008 textile color stability test fastness to soaping
GB/T3922-1995 textile colour fastness to perspiration test method
Bright blue waste gas absorbs into hydrochloric acid and sodium hydroxymethane sulfonate solution through substep, and be directly used in reactive dye synthetic, from table 1 and table 2, detecting data can find out, almost identical with dyestuff quality, performance that on market, hydrochloric acid, the pure raw material synthesized of sodium hydroxymethane sulfonate obtain, the hydrochloric acid of recovery and sodium hydroxymethane sulfonate solution can be used for the production of dyestuff completely.