CN101798068B - Sulfide or thiosulfate catalytic air complete oxidation at normal temperature and pressure - Google Patents
Sulfide or thiosulfate catalytic air complete oxidation at normal temperature and pressure Download PDFInfo
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Abstract
The invention relates to a catalysis and oxidation treatment method for wastewater containing sulfide or thiosulfate, which is used for completely oxidizing sulfide and/or thiosulfate into sulfate at normal temperature and pressure by using gas as an oxidant and using a compound containing trivalent bismuth as a catalyst. The catalyst used in the invention can be recycled, which not only solves the problem that sulfide and/or thiosulfate can not be oxidized into stable sulfate by using a traditional catalytic air oxidation method, but also is beneficial to environmental protection, decreasing the investment, saving the operation cost, and realizing simple operation. Therefore, the invention can be widely applied to treatment on wastewater containing sulfide and/or thiosulfate or alkali waste liquid.
Description
Technical field
The present invention relates to a kind of method that sulfide and/or thiosulphate Catalytic Oxygen is changed into vitriol, specifically be under normal temperature, normal pressure, with air as oxygenant, with containing bismuthous compound as catalyzer, sulfide and/or thiosulphate are oxidized to the method for stable vitriol up hill and dale, belong to chemical field.
Background technology
At present, sulfur-containing waste water is mainly from production equipments such as refinery catalytic pyrolysis, coking, hydrocrackings, high sulfur-containing waste lye is mainly from the refining separation of produced device of petroleum chemicals, the pollution concentration of this class waste water is very high, wherein except that containing a large amount of sulfide or thiosulphate, also contain pollutents such as phenolic compound and oils, have fetor, equipment is had extremely strong corrodibility, and the severe contamination surrounding environment.Therefore, these waste water should not directly enter the sewage centralized processing system of full factory, generally all need to carry out pre-treatment.
Many chemical industry also can produce sulfocompound, as in the technology of preparation barium sulfate, can produce a large amount of sodium sulphite.Though sulfide has purposes very widely, as be used for the depilation of animal skin, the industrial generation of sulfide is much higher than its industrial requirement.Therefore, the processing of sulfide also becomes an extremely severe problem.The conventional treatment method of sulfide generally is to add sulfuric acid in the solution of sulfide, forms hydrogen sulfide and vitriol, then hydrogen sulfide is converted into sulfurous gas, and then is processed into sulfuric acid.But, in this process, also may produce sulphur, and elemental sulfur may be sneaked into other industrial problems of initiation in the production equipment.In addition, hydrogen sulfide has high toxicity, need take safety measures when handling, and this can cause the increase of processing cost.Therefore, many new sulfide treatment processs constantly appear in the industrial application.
Yet these treatment processs adopt the high-temperature high-voltage reaction condition to carry out catalyzed oxidation mostly:
As the US4855123 disclosed method is the catalyzed oxidation that utilizes non-impregnated C catalyst to carry out under 50-130 ℃, the condition of 0-980KPa, sodium sulphite is oxidized to sodium polysulphide and Sulfothiorine, but, Sulfothiorine also is unsettled sulfocompound, under acidic conditions, can disproportionation generate elemental sulfur, can not fundamentally sulfocompound be converted into the form of stable vitriol.US5207927, US5470486, US5338463 disclosed method all are with metal catalyst sulfide oxidation to be become vitriol for another example, wherein, the US5207927 disclosed method is the catalytic oxidation that carries out at 125-175 ℃, the condition of 7KPa-3447KPa, the US5470486 disclosed method is to carry out under 100-200 ℃, the condition of 6.9KPa-6895KPa, the US5338463 disclosed method be less than 148 ℃, carry out under less than the condition of 1378KPa.The catalytic oxidation of sulfide method of these patent disclosures is all carried out under High Temperature High Pressure, and it is recyclable not put down in writing catalyst system therefor.The CN101495404 disclosed method is as catalyzer water-soluble sulfide to be converted into water miscible vitriol with non-impregnated many carbon materials, and this method is to carry out under 115-145 ℃, the condition of 1200KPa-1800KPa, and this condition also is a high-temperature and high-pressure conditions.
Yet, adopt high temperature, high-pressure oxidation method, though can obtain oxide treatment effect preferably, the construction investment of device is big, working cost is high, system operation, complex management.
On the other hand, a large amount of sulfur-containing waste waters that produce in field of environment engineering or waste lye also can adopt air oxidation process to handle, but under normal temperature, condition of normal pressure, the speed of oxidizing reaction is slower, have a large amount of thiosulphates in the oxidation products, oxidizing reaction is not thorough.In addition, produce bigger stink, pollutant atmosphere in the treating processes.Under normal temperature, condition of normal pressure, adopt traditional catalyzer, as iron content, contain manganese, contain zinc or contain the catalyzer of cobalt and the catalyzer of other material, though can improve the utilization ratio of air, fast reaction speed, reduce the concentration of thiosulphate by product, but still can not apace sulfide or thiosulphate be oxidized to stable vitriol up hill and dale.
Summary of the invention
In order to solve the defective that exists in the prior art, the object of the present invention is to provide a kind of under normal temperature, synthesis under normal pressure condition, can be up hill and dale sulfide and/or thiosulphate be oxidized to the method for vitriol, employed catalyzer has the advantages that to be easy to the Separation and Recovery utilization and not have secondary pollution, and does not produce hydrogen sulfide or sulfur dioxide gas in the treating processes.
In order to achieve the above object, the present invention is by the following technical solutions:
Provide a kind of sulfide and/or thiosulphate Catalytic Oxygen are changed into the method for vitriol, comprise the steps:
(1) at normal temperatures and pressures, under preferred 20 ℃-90 ℃ temperature, the pH value of reaction mixture be not less than 8.5 and contain bismuthous catalyzer in the presence of, with air as oxygenant, sulfide and/or thiosulphate and oxygen carry out oxidizing reaction, make free S in the reaction mixture
2-All be converted into SO
4 2-, S
2O
3 2-Or Bi
2S
3
(2) behind the reaction mixture pH to 1-6 with mineral acid regulating step (1), under 20 ℃-90 ℃ temperature of reaction, proceed oxidizing reaction, make trivalent bismuth and thiosulfuric acid reactant salt, generate Bi
2S
3And vitriol, and Bi
2S
3In negative sulfidion become vitriol by the air exhaustive oxidation.
Wherein, described sulfide and/or thiosulphate can be wastewater with high concentration of sulfide or the waste lyes of having removed oils and suspended contamination.
In step (1), more preferably 40-60 ℃ of temperature of reaction; Reaction times does not contain free S to satisfy in the reaction mixture
2-Be principle; It is described that to contain bismuthous catalyzer be that all can be under solutions of weak acidity generate Bi with the thiosulfuric acid reactant salt
2S
3With a kind of in the bismuth-containing compound of vitriol or their mixture, as Bismuth trinitrate, bismuth hydroxide, Bismuth Subcarbonate etc.Its amount is a principle not produce catalyst loss; The pH value of reaction mixture can be regulated by adding mineral alkali, and described mineral alkali can be sodium hydroxide or yellow soda ash, preferred sodium hydroxide.
In step (2), the preferred 40-60 of temperature of reaction ℃; Reaction times is not for to contain S to satisfy in the reaction mixture
2O
3 2-Be principle; The preferred 1.5-4.0 of pH value of reaction mixture.Described mineral acid is selected from sulfuric acid, hydrochloric acid or phosphoric acid, preferably sulfuric acid.
In quantity-produced industrial treatment device, should in the reaction mixture of described step (2), replenish and contain bismuthous catalyzer; It is described that to contain bismuthous catalyzer be that all can be under solutions of weak acidity generate Bi with the thiosulfuric acid reactant salt
2S
3With a kind of of the bismuth-containing compound of vitriol or their mixture, as Bismuth trinitrate, bismuth hydroxide, Bismuth Subcarbonate etc.Its magnitude of recruitment is a principle not occur tangible catalyst loss in the catalyst separation device of treatment system.
Step (3) be with the reaction solution of step (2) with mineral alkali adjust pH to 6～9 after, carry out solid-liquid separation, reclaim the solid bismuth-containing compound as the catalyzer of step (1) with recycle; The pH value of described step (3) is preferably 6.5-7.5; Described mineral alkali is sodium hydroxide or yellow soda ash, is preferably sodium hydroxide.
In one embodiment of the invention, the aldehydes matter that can separate out when containing acidifying in the reaction mixture of step (1) then in step (1) afterwards, can carry out the acidifying recycling of described aldehydes matter earlier, carries out step (2) again.
Wherein, the acidifying recycling of described aldehydes matter is specially: will be acidified to pH 2-6 with mineral acid from the reaction mixture of step (1), between the preferred 2.5-3.5, in medium temperature is under 40 ℃～50 ℃ conditions, carry out the recycling of aldehydes matter, and phenol recycling back gained mixed solution is carried out step (2); Described mineral acid is selected from sulfuric acid, hydrochloric acid or phosphoric acid, preferably sulfuric acid.
Another object of the present invention is to provide the application of described catalytic oxidation in industrial effluent is handled, be about to it and be used to purify the waste water that contains sulfide and/or thiosulphate, described waste water comprises sulfur-bearing high sulfur-bearing or high, the waste water that contains phenol or waste lye, and described waste water is to have removed oils and suspended contamination.
Another purpose of the present invention is to provide the application of described catalytic oxidation aspect preparation vitriol.
The inventive method can be under normal temperature, condition of normal pressure, as oxygenant, up hill and dale sulfide and/or thiosulphate are oxidized to stable vitriol with air, the used catalyzer of the present invention is easy to separate, and can recycle, there is not secondary pollution problem.In addition, method of the present invention can not produce hydrogen sulfide or sulfur dioxide gas, need not use special safeguard procedures in the operating process, helps saving cost, and is easy and simple to handle.The inventive method can be widely used in a plurality of fields such as chemical industry and environmental engineering.
Description of drawings
Fig. 1 adopts the inventive method to handle the technical process of wastewater with high concentration of sulfide or waste lye;
Fig. 2 adopts the inventive method to handle the technical process of high sulfur-bearing, phenol waste lye.
Embodiment
The inventive method is under normal temperature, condition of normal pressure, contain bismuthous catalyzer in the presence of, adopt air as oxygenant, thoroughly sulfide and/or thiosulphate are oxidized to the processing method of vitriol.
The nucleidic mass of bismuth is 208.98, compares with other material, and the density of bismuth-containing compound is bigger, and this provides favourable condition for the separation that guarantees catalyzer; In addition, the inventive method is under normal temperature, condition of normal pressure, carries out as oxygenant with air.Therefore, select for use under solutions of weak acidity, can generate Bi with the thiosulfuric acid reactant salt
2S
3With the bismuth-containing compound of vitriol as catalyzer of the present invention, this is the choosing that sulfide and/or thiosulphate is oxidized to the certainty of vitriol.
The inventive method mainly comprises two stages:
One, S
2-The ionic oxidation
In this stage, contain bismuthous catalyzer in the presence of, under alkaline condition, sulfide and/or thiosulphate and airborne oxygen carry out oxidizing reaction, make free S
2-All change into SO
4 2-, S
2O
3 2-Or Bi
2S
3Catalyst system therefor is that all can generate Bi with the thiosulfuric acid reactant salt under solutions of weak acidity
2S
3With a kind of in the bismuth-containing compound of vitriol or their mixture, as Bismuth trinitrate, bismuth hydroxide, Bismuth Subcarbonate etc., its amount is a principle not produce catalyst loss; This treatment stage in, the pH value of reaction mixture can descend, and the pH value of reaction mixture can be by adding the mineral alkali adjusting, the pH value is preferably and is not less than 8.5; Described mineral alkali can be sodium hydroxide or yellow soda ash, preferred sodium hydroxide.Reaction times can be according to the difference of the sulfide concentration in the waste lye, with free S
2-All change into SO
4 2-, S
2O
3 2-Or Bi
2S
3Be principle.Temperature of reaction is 20-90 ℃, preferred 40-60 ℃.
The reaction equation in this stage is:
Bi
2S
3+ air (O
2, CO
2)+OH
-→ Bi (OH)
3/ Bi (OH) CO
3+ SO
4 2-+ S
2O
3 2-
Bi (OH)
3/ Bi (OH) CO
3+ S
2-→ Bi
2S
3(black precipitate)
Two, S
2O
3 2-The ionic oxidation
In this stage, mainly be with original or newly-generated S
2O
3 2-Ion all changes into SO
4 2-Or Bi
2S
3, and the pH value of reaction mixture can rise, and therefore, at first is with mineral acid the pH value of reaction solution to be adjusted to 1～6, preferred 1.5-4.0 at 20-90 ℃, under preferred 40-60 ℃ the condition, continues under the effect of catalyzer and air carries out oxidizing reaction.Described mineral acid can be sulfuric acid, hydrochloric acid or phosphoric acid, is preferably sulfuric acid.In this stage, can according to circumstances replenish and contain bismuthous catalyzer, the catalyzer that is replenished is that all can generate Bi with the thiosulfuric acid reactant salt under solutions of weak acidity
2S
3With a kind of in the bismuth-containing compound of vitriol or their mixture, as Bismuth trinitrate, bismuth hydroxide, Bismuth Subcarbonate etc., its amount is not advisable not occur tangible catalyst loss in the catalyst separation device of treatment system.The reaction times in this stage is with free S
2O
3 2-All change into SO
4 2-Or Bi
2S
3Be principle.
Wherein, contain bismuthous catalyzer and thiosulfuric acid reactant salt, generate bismuth trisulfide and vitriol, and the negative divalent sulfur in the bismuth trisulfide can be completely oxidized to vitriol by air, reaction equation is:
Bi
3+(make-up catalyst)+S
2O
3 2-→ Bi
2S
3+ SO
4 2-
Bi(OH)
3/Bi(OH)CO
3+S
2O
3 2-→Bi
2S
3+SO
4 2-
Bi
2S
3+O
2+H
+→Bi(OH)
3+SO
4 2-
In the method for the invention, used catalyzer can recycle and reuse, and this mainly is by post reaction mixture being regulated pH to 6-9 with mineral alkali, between the preferred 6.5-7.5, carry out solid-liquid separation then, reclaiming the solid bismuth-containing compound as S
2-The catalyzer of ionic oxide formation is realized the purpose of recycle.Described mineral alkali is sodium hydroxide or yellow soda ash, is preferably sodium hydroxide.This link helps saving cost and environment protection.In industrial application, described recovery is by with pump the mode that the bismuth-containing compound of separation unit bottoms is promoted in the once desulfurization reactor being realized.Its technical process as shown in Figure 1.Wherein, when the amount of air was guaranteed, the internal circulating load of catalyzer was big more, and the speed of desulphurization reaction is also fast more, and treatment effect is just good more.The normal reliability that will guarantee separating effect in service.
In one embodiment of the invention, the aldehydes matter that can separate out when initial mixed solution contains acidifying as refinery catalytic gasoline waste lye of refining, so, is carrying out S
2-After the ionic oxidation, should carry out the acidifying and the recycling of aldehydes matter earlier, and then carry out S
2O
3 2-The ionic oxidation.Described acidifying and recycling are the pH to 2-6 that regulates mixed solution with mineral acid, and preferred 2.5-3.5 has aldehydes matter this moment and floats and discharged automatically to the top of phenol retrieving arrangement, reclaim aldehydes matter after isolated liquid carry out S again
2O
3 2-The ionic oxidation; Described mineral acid is sulfuric acid, hydrochloric acid or phosphoric acid, preferably sulfuric acid.Its technical process as shown in Figure 2.
The invention will be further described below in conjunction with preferred embodiment, it should be understood that these embodiment only are used for the purpose of illustration, never limit protection scope of the present invention.
Embodiment 1
Preparation of catalysts:
Take by weighing 7.5 gram Bi (NO
3)
35H
2O adds 200ml water in beaker, add NaOH and stirring then, and the pH that regulates the gained mixed solution is 7.0, thereby obtains catalyst B i (OH)
3
1, S
2-The ionic oxidation:
Take by weighing 50 gram Na
2S9H
2O and gained catalyst mix also add in the 2000ml beaker, add about 1600ml water again, carry out the aeration oxidizing reaction under 50 ℃ temperature, make free S
2-All be converted into SO
4 2-, S
2O
3 2-Or Bi
2S
3In the reaction process,, make it more than 8.5 by adding the pH of sodium hydroxide solution conditioned reaction mixed solution.
Reaction equation is:
Bi
2S
3+ air (O
2, CO
2)+OH
-→ Bi (OH)
3/ Bi (OH) CO
3+ SO
4 2-+ S
2O
3 2-
Bi (OH)
3/ Bi (OH) CO
3+ S
2-→ Bi
2S
3(black precipitate)
S
2-Detection:
React after 24 hours, get about 50ml reaction mixture and filter.Get about 15ml filtrate in 50 milliliters beaker, add a little CoSO
47H
2O finds not have the CoS precipitation of black to produce, and has generated blue Co (OH)
2There is not free S in precipitation in this explanation reaction mixture substantially
2-Ion.
S
2O
3 2-Detection:
Other gets about 15ml filtrate in 50 milliliters beaker, and to wherein dripping several dilute sulphuric acids, adjust pH is about 1.0～2.0, finds that after a while liquid becomes muddy, and produces white deposits gradually, in this explanation reaction mixture S is arranged
2O
3 2-Exist.
2, S
2O
3 2-The ionic oxidation:
In the reaction mixture of step 1, add Bi (NO
3)
3Catalyzer as a supplement, with dilute sulphuric acid with its pH regulator to 1.5-4.0, carry out the aeration oxidizing reaction under 50 ℃ the water-bath, make trivalent bismuth ion and thiosulfuric acid reactant salt, generate Bi
2S
3And vitriol, and Bi
2S
3In negative divalent sulfur become vitriol by the air exhaustive oxidation.
Reaction equation is:
Bi
3+(make-up catalyst)+S
2O
3 2-→ Bi
2S
3+ SO
4 2-
Bi(OH)
3/Bi(OH)CO
3+S
2O
3 2-→Bi
2S
3+SO
4 2-
Bi
2S
3+O
2+H
+→Bi(OH)
3+SO
4 2-
S
2O
3 2-Ionic detects:
Should be noted that: generally, the solution of thiosulphate (as pH between 1～4) when acidifying, sulphur is separated out because of the disproportionation reaction that thiosulphate takes place in the capital, but having when containing bismuthous catalyzer and existing, there is no sulphur in the acidification reaction process and separate out, the disproportionation reaction of this explanation thiosulphate is thoroughly suppressed.
In the reaction process, can detect S by the following method
2O
3 2-Whether react completely to follow the tracks of reaction:
The reaction mixture that takes a morsel with about 7.0 after-filtration of sodium hydroxide adjust pH, is got filtrate, drips dilute sulphuric acid and transfers pH to 1～2, and solution begins to become muddy after a while, and separates out sulphur at leisure.Meanwhile, the COD value that records this filtrate is 935.4mg/L.Illustrate and also have S in the reaction solution
2O
3 2-Exist.
React after 56 hours, the reaction mixture that takes a morsel is adjusted to its pH value with sodium hydroxide approximately 7.0, filters then, and the COD that records filtrate is 21.9mg/L.With dilute sulphuric acid filtrate being acidified to the pH value is 1～2, and long-time the placement, and the disproportionation reaction phenomenon of no thiosulphate produces.This illustrates S
2O
3 2-By exhaustive oxidation.
3, after reaction is finished, with sodium hydroxide with the pH regulator of reaction mixture to 6-9, have the good solid of settling property to separate out this moment, and this solid is a bismuth-containing compound, is mainly a kind of in bismuth trisulfide, bismuth hydroxide, the Bismuth Subcarbonate or their mixture; Adopt the solid-liquid separation settling vessel with the catalyst recycling of solid recovery as step 1.
Embodiment 2
Select 0.8g Bi (NO for use
3)
35H
2O adds Na as catalyzer
2CO
3And stir, the pH that regulates the gained mixed solution is 7.0, thereby obtains catalyst B i (OH) CO
3
Take by weighing 15 gram Na
2S9H
2O be dissolved in 700 ml waters and and catalyst mix, the sulfide content of gained mixed solution is about 2800mg/L.
The temperature of reaction of step 1 is 20 ℃, and the reaction times is 65 hours.
The temperature of reaction of step 2 is 20 ℃, and the catalyzer that replenishes is a bismuth hydroxide, with dilute phosphoric acid with the pH regulator of reaction mixture to 1.5-4.0, aerated reaction 20 hours.
After finishing, reaction, carries out solid-liquid separation with behind the yellow soda ash adjusting pH to 6.5-7.5.
Get the liquid after a part is separated, the COD value that records parting liquid is 27.5mg/L.
Embodiment 3
Take by weighing 15 gram Bi (NO
3)
35H
2O in 2000 milliliters beaker, adds water and stirs, and add sodium hydroxide, and the pH value of mixture is adjusted to about 7.0.
Take by weighing 8.4 gram Na
2S9H
2O adds it to above-mentioned mixture, adds water to 1400 milliliters scale marks, and stirring reaction makes S
2-Complete reaction generates Bi
2S
3Precipitation (because Bismuth trinitrate is excessive, S
2-All precipitated, finish so can be considered the once desulfurization reaction).
Place 50 ℃ water-bath to carry out aeration in above-mentioned beaker, with dilute hydrochloric acid the pH value of reaction mixture is adjusted in 1～4 the scope.
Behind the aerated reaction 6 hours, get a part of mixed solution, hydro-oxidation sodium is adjusted to its pH value about 7.0, filters then, gets a part of filtrate, after wherein adding dilute hydrochloric acid, again to wherein adding BaCl
22H
2O, in the pH value was 1～2 scope, the muddiness of white appearred in stirring reaction in the mixed solution, after placement after a while, the BaSO of white occurs
4Deposit seeds.Get another part filtrate, adding hcl acidifying to pH value is 1～2, and after long-time the placement, the disproportionation reaction that there is no thiosulphate produces.There is not S substantially in these reacting phenomenon explanations in the reaction mixture
2O
3 2-, and Bi
2S
3Can under acidic conditions, be completely oxidized to vitriol by air.
Embodiment 4
Take by weighing 4 gram Na
2S
2O
35H
2O in 1000 milliliters beaker, adds an amount of water and stirs, subsequently to wherein adding 1.0 gram Bi (NO
3)
35H
2O adds water to 700 milliliters scale marks, in 50 ℃ water-bath, heats, and aerated reaction, and in mixed solution, drip dilute sulphuric acid (owing to do not have S in the mixed solution
2-, have only S
2O
3 2-Exist, finish so can be considered the once desulfurization reaction process), the pH value of mixed solution is controlled between 1.5～3.0.In this process, find mixed solution yellowing, brown successively, become black at last.The generation of this phenomenon is Bi
3+With S
2O
3 2-Reaction generates Bi
2S
3And SO
4 2-Process.
After reaction is carried out 2 hours, get the partial reaction mixed solution, hydro-oxidation sodium is adjusted to about 7.0 after-filtration with its pH value, drips dilute sulphuric acid in filtrate, and its pH value is adjusted between 1～2, finds to have the disproportionation reaction phenomenon of thiosulphate to take place, i.e. S
2O
3 2-Do not transformed fully.
After reaction is carried out 12 hours, get the partial reaction mixed solution, hydro-oxidation sodium is adjusted to about 7.0 after-filtration with its pH value, drips dilute sulphuric acid in filtrate, and its pH value is adjusted between 1～2, after leaving standstill for a long time, does not have the disproportionation reaction phenomenon of thiosulphate to produce.This explanation thiosulphate has been reformed completely into vitriol and Bi
2S
3Precipitation.
According to the conclusion of embodiment 3 as can be known, be converted to Bi in the Sulfothiorine
2S
3Sedimentary that part of sulphur is 1～4 in the pH value, and temperature of reaction is under 50 ℃ the condition, can be oxidised with air to vitriol fully.
Embodiment 5
Take by weighing 1.2g Bi (NO
3)
35H
2O adds a spot of water and stirs, and transfers the pH value of mixed solution to be about 7.0 with NaOH.
Take by weighing 5 gram Na
2S9H
2O and 3.5 gram Na
2S
2O
35H
2O is dissolved in 700 ml waters after the mixing, mix with above-mentioned mixed solution then.
The temperature of reaction of step 1 is 90 ℃, and the reaction times is 15 hours.
The temperature of reaction of step 2 is 90 ℃, and the reaction times is 8 hours, and the catalyzer that replenishes is a bismuth hydroxide, with phosphoric acid with the pH regulator of reactant to 1.5-4.0.
After finishing, reaction, carries out solid-liquid separation with behind the sodium hydroxide adjusting pH to 6.5-7.0.
Record that the COD of liquid is 31.5mg/L after the solid-liquid separation.
Embodiment 6
Take from the wastewater with high concentration of sulfide of certain chemical enterprise, remove oils and impurity such as suspended substance wherein after, recording its sulfide concentration is 1937mg/L.Getting 1000ml drops in the once desulfurization reactor, the mixture that adds 1.0g bismuth hydroxide and 1.5g Bismuth Subcarbonate, add sodium hydroxide and regulate its pH greater than 8.5, the temperature of regulating the once desulfurization reactor is 50 ℃, and feeding pressurized air carries out the aeration oxidizing reaction.
In the reaction process, by S among the embodiment 1
2-Detection method follow the tracks of reaction process.
React after 20 hours S
2-Ionic reaction is complete, and reaction mixture is introduced in the secondary desulphurization reactor, according to response situation make-up catalyst Bismuth trinitrate, and regulates the pH to 1.5-4.0 of mixed solution with dilute sulphuric acid, feeds pressurized air, aerated reaction under 50 ℃ temperature.
In the reaction process, by S among the embodiment 1
2O
3 2-The ionic detection method is followed the tracks of reaction process.
React after 10 hours S
2O
3 2-Ionic reaction is complete, with mixed solution introduce carry out in the equipment for separating liquid from solid settlement separate.In industrialized unit, can adopt mono-pump that the solid matter of separation unit bottoms is promoted in the once desulfurization reactor as catalyst recycling.Technical process as shown in Figure 1.
Embodiment 7
Take from the catalytic gasoline caustic prescrub waste lye of certain petroleum chemical enterprise, record its S
2-Concentration is 21439mg/L, and COD is 276574mg/L, and the concentration of volatile phenol is 109530mg/L, and the pH value is 13.7.
S
2-Ionic oxidation: with 5 gram Bi (OH) CO
3Mix adding once desulfurization reactor with the above-mentioned catalytic gasoline caustic prescrub of 2000ml waste lye, under 40 ℃ temperature, carry out the aeration oxidizing reaction.
S
2-Ionic detects: react after 60 hours, detect with Lead acetate paper, find the black that test paper has shown when initial reaction stage detects, become light color, do not have S substantially in this explanation reaction mixture
2-Exist.
The acidifying of phenol and recovery: will introduce the phenol retrieving arrangement from the mixed solution of once desulfurization reactor, with sulfuric acid the pH value of mixed solution is adjusted to 2-6, there are this moment a large amount of aldehydes matter come-ups to separate out, subsequently mixture is transferred in the tubualted bottle, under 40 ℃ temperature, after treating that aldehydes matter come-up is separated, emit liquid from the bottom of tubualted bottle.
S
2O
3 2-The ionic oxidation: the mixed solution that will reclaim behind the phenol is introduced the secondary desulphurization reactor, regulates pH value to 1.5～4.0 with dilute sulphuric acid, under 40 ℃ temperature, carries out the aeration oxidizing reaction.
S
2O
3 2-Ionic detects:
React after 24 hours, get about 150ml mixed solution, with sodium hydroxide its pH value is adjusted to about 7.0 after-filtration, with dilute sulphuric acid the 30ml pH value of filtrate is transferred to 1～2 then, filtrate after the acidifying (is remained on water temperature under the higher temperature, to prevent to produce the xln of sodium sulfate, if because of volatilization filtrate volume is reduced at 40 ℃, answer moisturizing to original volume) water-bath in leave standstill 2 hours after, precipitation produces.Almost there has not been thiosulphate in this explanation mixed solution.Meanwhile, the volatile phenol concentration that records filtrate is 4179mg/L, and sulfide concentration is 2.1mg/L, and COD is 12763mg/L.In industrial installation, produce topsoil for avoiding volatile organic matter, the head space gas in regulating tank, phenol retrieving arrangement and the phenol basin should be caused and carry out water seal and gas washing processing in the water seal scrubber tower.In addition, also the tail gas in once desulfurization reactor and the secondary desulphurization reactor should be caused and carry out gas washing in the water seal scrubber tower and handle.Technical process as shown in Figure 2.
The above only is preferred embodiment of the present invention, only is illustrative for the purpose of the present invention, and nonrestrictive.Those skilled in the art is understood, and can carry out many changes to it in the spirit and scope that claim of the present invention limited, revise, even equivalence, but all will fall within the scope of protection of the present invention.
Claims (17)
1. one kind changes into the method for vitriol with sulfide and/or thiosulphate Catalytic Oxygen, it is characterized in that, comprises the steps:
(1) under 20 ℃-90 ℃ temperature of reaction, containing in the presence of the bismuthous catalyzer, the pH value of reaction mixture is not less than under 8.5 the condition, with air as oxygenant, sulfide and/or thiosulphate and oxygen carry out oxidizing reaction, make free S in the reaction mixture
2-All be converted into SO
4 2-, S
2O
3 2-Or Bi
2S
3
(2) with behind the reaction mixture adjusting pH to 1-6 of mineral acid with step (1), under 20 ℃-90 ℃ temperature of reaction, proceed oxidizing reaction, make thiosulphate in the presence of bismuthous, generate Bi
2S
3And vitriol, and Bi
2S
3In negative divalent sulfur become vitriol by the air exhaustive oxidation.
2. method according to claim 1 is characterized in that, described sulfide and/or thiosulphate are wastewater with high concentration of sulfide or the waste lyes of having removed oils and suspended contamination.
3. method according to claim 1 is characterized in that, in the described step (1), temperature of reaction is 40 ℃-60 ℃; Reaction times does not contain free S to satisfy in the reaction mixture
2-Be principle; It is described that to contain bismuthous catalyzer be that all can be under solutions of weak acidity generate Bi with the thiosulfuric acid reactant salt
2S
3With a kind of in the bismuth-containing compound of vitriol or their mixture, its amount is a principle not produce catalyst loss; The pH value of reaction mixture is regulated by adding mineral alkali, and described mineral alkali is sodium hydroxide or yellow soda ash.
4. method according to claim 3 is characterized in that, described to contain bismuthous catalyzer be Bismuth trinitrate, bismuth hydroxide or Bismuth Subcarbonate.
5. method according to claim 3 is characterized in that described mineral alkali is a sodium hydroxide.
6. method according to claim 1 is characterized in that, in the described step (2), temperature of reaction is 40 ℃-60 ℃; Reaction times does not contain free S to satisfy in the reaction mixture
2O
3 2-Be principle; The pH value of reaction mixture is 1.5-4.0; Described mineral acid is selected from sulfuric acid, hydrochloric acid or phosphoric acid.
7. method according to claim 6 is characterized in that described mineral acid is a sulfuric acid.
8. method according to claim 1 is characterized in that, according to circumstances, replenishes in the reaction mixture of described step (2) and contains bismuthous catalyzer; It is described that to contain bismuthous catalyzer be that all can be under solutions of weak acidity generate Bi with the thiosulfuric acid reactant salt
2S
3With a kind of in the bismuth-containing compound of vitriol or their mixture, its magnitude of recruitment is a principle tangible catalyst loss not occur.
9. method according to claim 8 is characterized in that, described to contain bismuthous catalyzer be Bismuth trinitrate, bismuth hydroxide or Bismuth Subcarbonate.
10. method according to claim 1, it is characterized in that, further carry out step (3), be with the reaction solution of step (2) with mineral alkali adjust pH to 6～9 after, carry out solid-liquid separation, reclaim the solid bismuth-containing compound as the catalyzer of step (1) with recycle; Described mineral alkali is sodium hydroxide or yellow soda ash.
11. method according to claim 10 is characterized in that, the pH value of described step (3) reaction solution is 6.5-7.5; Described mineral alkali is a sodium hydroxide.
12. method according to claim 1 is characterized in that, during the aldehydes matter that can separate out when containing acidifying in the reaction mixture of step (1), in step (1) afterwards, carries out the acidifying recycling of described aldehydes matter earlier, carries out step (2) again.
13. method according to claim 12, it is characterized in that, the acidifying recycling of described aldehydes matter is specially: will be acidified to pH 2-6 with mineral acid from the reaction mixture of step (1), be under 40 ℃～50 ℃ the condition in temperature, the aldehydes matter that phenol retrieving arrangement top is separated out reclaims, and will reclaim back gained liquid through phenol and carry out step (2); Described mineral acid is selected from sulfuric acid, hydrochloric acid or phosphoric acid.
14. method according to claim 13 is characterized in that, described pH is between the 2.5-3.5.
15. method according to claim 13 is characterized in that, described mineral acid is a sulfuric acid.
16. the application of each described method of claim 1-15 in industrial effluent is handled, promptly be used to purify the application of the waste water that contains sulfide and/or thiosulphate, described waste water comprises sulfur-bearing high sulfur-bearing or high, the waste water that contains phenol or waste lye, and described waste water has been removed oils and suspended contamination.
17. the application of each described method of claim 1-15 in preparation vitriol.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5207927A (en) * | 1992-03-18 | 1993-05-04 | Uop | Treatment of an aqueous stream containing water-soluble inorganic sulfide compounds |
| US5597546A (en) * | 1995-08-29 | 1997-01-28 | National Science Council | Selective oxidation of hydrogen sulfide in the presence of bismuth-based catalysts |
| CN1579956A (en) * | 2003-08-08 | 2005-02-16 | 罗德春 | Method for treating high-sulphur-phenol waste alkali liquor under normal temperature and pressure conditions |
| CN101495404A (en) * | 2006-05-24 | 2009-07-29 | 萨克特本化学有限责任公司 | Method for the catalytic oxidation of sulfide to sulfate |
-
2010
- 2010-03-29 CN CN2010101403497A patent/CN101798068B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5207927A (en) * | 1992-03-18 | 1993-05-04 | Uop | Treatment of an aqueous stream containing water-soluble inorganic sulfide compounds |
| US5597546A (en) * | 1995-08-29 | 1997-01-28 | National Science Council | Selective oxidation of hydrogen sulfide in the presence of bismuth-based catalysts |
| CN1579956A (en) * | 2003-08-08 | 2005-02-16 | 罗德春 | Method for treating high-sulphur-phenol waste alkali liquor under normal temperature and pressure conditions |
| CN101495404A (en) * | 2006-05-24 | 2009-07-29 | 萨克特本化学有限责任公司 | Method for the catalytic oxidation of sulfide to sulfate |
Non-Patent Citations (2)
| Title |
|---|
| 姜峰等.含硫废水的处理与研究进展.《兰州理工大学学报》.2004,第30卷(第5期),第68-70页，1.1氧化法，1.2化学药品反应除硫. * |
| 王鹤洲等.炼油厂酸性废水及碱渣综合处理技术的改进.《化工技术经济》.2005,第23卷(第2期),第45页,1,酸性水及碱渣综合处理技术. * |
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