CN105502308A - Waste sulfuric acid treatment method - Google Patents
Waste sulfuric acid treatment method Download PDFInfo
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- CN105502308A CN105502308A CN201510962067.8A CN201510962067A CN105502308A CN 105502308 A CN105502308 A CN 105502308A CN 201510962067 A CN201510962067 A CN 201510962067A CN 105502308 A CN105502308 A CN 105502308A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
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- C01B17/92—Recovery from acid tar or the like, e.g. alkylation acids
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Abstract
The invention discloses a waste sulfuric acid treatment method. The waste sulfuric acid treatment method includes the steps that (a), a splitting decomposition step: waste sulfuric acid is subjected to splitting decomposition in a cracking furnace, wherein the heat required by the splitting decomposition is provided by sulfur and oxygen-containing gas in the cracking furnace through combustion; (b), a purification and drying step: the cracking furnace gas obtained in the step (a) is cooled, is washed with sulfuric acid and is dried to obtain SO2-containing purified gas with the reduced water content; (c), a conversion step: the SO2 in the SO2-containing purified gas obtained in the step (b) is oxidized into SO3; (d), an absorption step: the SO3 obtained in the step (3) is absorbed by using sulfuric acid with the concentration by weight of 98.0-98.3% to obtain sulfuric acid with the concentration by weight of 98.3-98.6%, and then the sulfuric acid with the concentration by weight of 98.3-98.6% is diluted into sulfuric acid with the concentration by weight of 98.0-98.3%. The method can balance out a large amount of dilute sulfuric acid produced in the waste acid treatment process from the reaction perspective and accordingly can remarkably reduce acid-containing sewage treatment amount and discharge amount, and the waste sulfuric acid recovery rate is high.
Description
Technical field
The present invention relates to a kind for the treatment of process of industrial waste acid, particularly, relate to the treatment process that a kind of Waste Sulfuric Acid rate of recovery is high, significantly can reduce the Waste Sulfuric Acid containing sour sewage quantity.
Background technology
The vitriol oil, as a kind of industrial chemicals, industrially has and applies extremely widely.But, in the use procedure of industrial sulphuric acid, can inevitably produce a large amount of Waste Sulfuric Acids.Such as, in the manufacture of alkylate oil, at present, based on liquid acid Catalytic processes, the domestic overwhelming majority adopts sulphur acid as catalyst.
Alkylate oil has that octane value is high, steam forces down, containing advantages such as alkene and aromatic hydrocarbons, sulphur content are low, be desirable clean gasoline with high octane blend component.Produce in sulfuric acid catalysis method in the production process of alkylate oil, often can supervene a large amount of Waste Sulfuric Acids containing impurity such as oil, water, directly discharge, severe contamination will be caused to ecotope, usually it is recycled after art breading.The process of waste sulfuric acid from alkylation mainly contains following several technique:
1, production White Carbon black and oil rust remover technique
First dilute with water Waste Sulfuric Acid, volume ratio between its acid sludge and water is about 1:5-15, reach the static object isolating stand oil, the dilute sulphuric acid concentration after being separated by stand oil is divided to be 7 % by weight ~ 18 % by weight, then neutralize with sodium silicate solution, then from resultant metabisulfite solution, separate out hydrated SiO 2, obtain product through aging, washing, filtration, drying, pulverizing.
Stand oil isolated in Waste Sulfuric Acid is washed, remove most of sulfuric acid, a saponification is carried out again with alkaline solution, lightweight polymer oil reservoir and heavy polymerization oil reservoir is divided into after static, light, the reaggregation oil content that separate are not used alkaline earth metal hydroxides solution, filter at temperature 30-70 DEG C, obtain lightweight rust-preventive agent and heavy rust-preventive agent.
This technique have technical maturity, Waste Sulfuric Acid process thoroughly, utilization ratio advantages of higher, but also have that produce market demand is little, operational path is complicated, sodium silicate raw material is difficult to obtain, the dilute sulphuric acid that produces in production process and waste liquid cannot meet the deficiencies such as direct emission standard.
2, ammonium sulfate and rust-preventive agent technique is produced
Utilize ammoniacal liquor and Waste Sulfuric Acid to react and generate ammoniumsulphate soln (oil-containing is brown), ammonium sulfate concentrations is advisable with 35 % by weight ~ 38 % by weight, sedimentation oil removing, decolouring, deodorization process are carried out to ammoniumsulphate soln, obtain ammonium sulfate liquor, then obtain the ammonium sulfate product that can be used as chemical fertilizer after pervaporation, centrifugal, drying.The stand oil separated from ammoniumsulphate soln through alkali lye saponification, refiningly can obtain rust-preventive agent product.
Waste sulfuric acid from alkylation is utilized to produce the production technique of ammonium sulfate and rust-preventive agent, there is technique more ripe, the advantages such as lectotype selection is easy, but nitrogenous fertilizer market domestic is at present saturated, and the market competitiveness of the ammonium sulfate fertilizer to be made up of Waste Sulfuric Acid affects larger by ammoniacal liquor, and ammonium sulphate content only has 27 % by weight, the sulfate radical SO of all the other difficult decomposition
4 2-, fertilizer efficiency is lower, and product introduction market difficulty is larger.Meanwhile, decolour, work-ing life of deodorizing composition and regeneration also needs further improvement.
3, Pintsch process industrial sulphuric acid technique
The cracking under the high temperature of 1000 ~ 1100 DEG C of sulfuric acid in waste sulfuric acid from alkylation generates SO
2splitting gas, organism wherein burns simultaneously and generates CO
2, after Pintsch process air cooling but, through acid-scrubbing cleaning, then send into conversion system, by SO under iron catalyst catalyst action
2transform and generate SO
3, then absorb with the vitriol oil of 98.3 % by weight, the vitriol oil product of production then reuses for alkyl plant, and the regeneration realizing Waste Sulfuric Acid is recycled, and the Waste Sulfuric Acid rate of recovery is about 90%.And the high-temperature tail gas that organism burns generation can also be used to produce steam; Meanwhile, burn the tail gas produced and only through simple absorption process, after discharge index can be reached, air need be entered, reach the object of protection of the environment.
This mature technology, Waste Sulfuric Acid process is more thorough, at present, be widely adopted, but most of Waste Sulfuric Acid is through Pintsch process process for preparing sulfuric acid, what mainly adopt in cleavage step is the method that gas fuel and air mixed burn to provide heat energy, the method gas fuel consumption costs is larger, simultaneously, organic compound combustion in Sweet natural gas and spent acid can produce a large amount of water, cracking process is caused to produce the dilute sulphuric acid of a large amount of sulfuric acid contents at about 2%-10%, the water balance of waste acid recovery system will be had a strong impact on, prior art is by sewage effluent pond after excessive dilute sulphuric acid neutralizing treatment, sewage disposal expense and blowdown flow rate is caused significantly to increase, cause the problem bringing again contaminated wastewater while solving spent acid pollution problem, therefore fundamentally do not solve.In addition, support the organic compound combustion in Sweet natural gas and spent acid because of introducing large quantity of air, cause SO in splitting gas
2gas concentration is diluted, and in step of converting, thermal discharge is low, in order to maintain reaction conversion ratio, electrothermal oven need be adopted to heat, cause plant energy consumption to increase.
Summary of the invention
The present invention is in order to solve in existing industrial waste sulfuric acid treating processes, especially Pintsch process process waste sulfuric acid from alkylation is adopted to prepare in the process of industrial sulphuric acid, a large amount of dilute sulphuric acid can be produced, sewage load and quantity discharged is caused significantly to increase, and the problem that the Waste Sulfuric Acid rate of recovery is low, object is the treatment process providing a kind of Waste Sulfuric Acid, particularly processes the method for the Waste Sulfuric Acid produced in alkylate oil preparation process.The method can not produce a large amount of dilute sulphuric acid, can significantly reduce containing sour sewage load and quantity discharged, and the Waste Sulfuric Acid rate of recovery is high.
To achieve these goals, the invention provides a kind for the treatment of process of Waste Sulfuric Acid, the method comprises:
A, cleavage step: make the cracking in pyrolyzer of described Waste Sulfuric Acid, wherein, the heat needed for this cracking is provided in this pyrolyzer combustion by sulphur and oxygen-containing gas;
B, purge drying step: after the pyrolyzer furnace gas cooling obtained by step a, also dry with sulfuric acid scrubbing, what be reduced water-content contains SO
2purified gas;
C, step of converting: what obtained by step b contains SO
2sO in purified gas
2be oxidized to SO
3;
D, absorption step: the SO that step c is obtained
3by the sulfuric acid absorption that concentration is 98.0 ~ 98.3 % by weight, obtain the sulfuric acid that concentration is 98.3 ~ 98.6 % by weight, then by the concentration obtained be 98.3 ~ 98.6 % by weight sulfuric acid be diluted to the sulfuric acid that concentration is 98.0 ~ 98.3 % by weight.
Preferably, described Waste Sulfuric Acid contains the H of 87 % by weight ~ 90 % by weight
2sO
4, described oxygen-containing gas is air.
Preferably, the weight ratio of described sulphur and described Waste Sulfuric Acid is (1.5-2.0): 1.
Preferably, in described cleavage step, sulphur be heated to 140 DEG C ~ 180 DEG C in advance and after oxygen-containing gas being heated to 190 DEG C ~ 210 DEG C, be passed in described pyrolyzer.
Preferably, cracking described in step a is carried out under the pressure of the temperature of 1000 DEG C ~ 1200 DEG C and-100Pa ~-500Pa.
Preferably, in described purge drying step, the described pyrolyzer furnace gas cooling obtained by step a comprises and uses waste heat boiler to move heat and/or move heat with the heat exchange of described oxygen-containing gas before entering pyrolyzer.
Preferably, obtain described in reduce water-content containing SO
2the moisture content of purified gas is for being less than 0.1g/m
3.
Preferably, in described purge drying step, described sulfuric acid scrubbing is also dry to be comprised first with the sulfuric acid scrubbing that concentration is 2-10 % by weight, then is the sulfuric acid drying of 92-95 % by weight by concentration.
Preferably, the sulfuric acid obtained after described washing in described purge drying step is made to flow into washing acid tank (14), make describedly to flow in dry acid tank (15) through described dried sulfuric acid, a part for sulfuric acid in this washing acid tank (14) and dry acid tank (15) is cycled to used in washing and the drying of pyrolyzer furnace gas, it is the dilution of the sulfuric acid of 98.3 ~ 98.6 % by weight that another part string is used for concentration described in described absorption step, and by the concentration that obtains after dilution be 98.0 ~ 98.3 % by weight sulfuric acid according to being that the equiponderant amount of sulfuric acid of the dilution of the sulfuric acid of 98.3 ~ 98.6 % by weight adds in described washing acid tank (14) and dry acid tank (15) with being used for described concentration.
Preferably, a water part required for the dilution of the sulfuric acid that concentration described in described absorption step is 98.3 ~ 98.6 % by weight comes from the sulfuric acid from described washing acid tank (14) and dry acid tank (15) string, and another part comes from make up water.
The present inventor is by repeatedly furtheing investigate, be surprised to find that, prepare in the process of industrial sulphuric acid at existing employing Pintsch process process waste sulfuric acid from alkylation, why produce a large amount of dilute sulphuric acids, when being owing to using Sweet natural gas for fuel, a large amount of water vapour can being produced after combustion of natural gas, thus in Waste Sulfuric Acid treating processes, produce a large amount of dilute sulphuric acid, and finally cause sewage load and quantity discharged significantly to increase, the Waste Sulfuric Acid rate of recovery is reduced.The present inventor is based on above-mentioned unexpected discovery, by in Waste Sulfuric Acid cleavage step, to make the sulfuric acid cracking in Waste Sulfuric Acid at the heat that pyrolyzer combustion provides with sulphur and oxygen-containing gas, thus avoid the generation of water vapour, and then avoid the generation of a large amount of dilute sulphuric acid, greatly reduce the treatment capacity containing sour sewage and quantity discharged, thus substantially increase the rate of recovery of Waste Sulfuric Acid.In addition, owing to producing sulfurous gas after sulfur burning, the content of sulfur dioxide in pyrolyzer furnace gas is raised, and then the productive rate of the vitriol oil can be improved.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the schema of the treatment process for illustration of Waste Sulfuric Acid of the present invention.
Description of reference numerals
1 pyrolyzer, 2 waste heat boilers, 3 air preheaters, 4 dynamic wave scrubbers, 5 desorption towers, 6 sizers, 7 electrostatic precipitators, 8 convertors, 9 moisture eliminators, 10 first absorption towers, 11 second absorption towers, 12 economizers, 13 tail gas absorbers, 14 washing acid tanks, 15 dry acid tanks, 16, are inhaled circulation groove, 17 2 and are inhaled circulation groove, 18 ~ 20 pumps, 21 gas blowers
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
According to the treatment process of Waste Sulfuric Acid of the present invention, the method comprises:
A, cleavage step: make the cracking in pyrolyzer of described Waste Sulfuric Acid, wherein, the heat needed for this cracking is provided in this pyrolyzer combustion by sulphur and oxygen-containing gas;
B, purge drying step: after the pyrolyzer furnace gas cooling obtained by step a, also dry with sulfuric acid scrubbing, what be reduced water-content contains SO
2purified gas;
C, step of converting: what obtained by step b contains SO
2sO in purified gas
2be oxidized to SO
3;
D, absorption step: the SO that step c is obtained
3by the sulfuric acid absorption that concentration is 98.0 ~ 98.3 % by weight, obtain the sulfuric acid that concentration is 98.3 ~ 98.6 % by weight, then by the concentration obtained be 98.3 ~ 98.6 % by weight sulfuric acid be diluted to the sulfuric acid that concentration is 98.0 ~ 98.3 % by weight.
By in cleavage step in the present invention, to make the sulfuric acid cracking in Waste Sulfuric Acid at the heat that pyrolyzer combustion provides with sulphur and oxygen-containing gas, with use Sweet natural gas as fuel in prior art, water can be produced after burning compare with the situation of carbonic acid gas, sulfurous gas is generated after sulfur burning, water can not be produced, thus avoid fuel combustion and introduce water vapour, and then avoid the generation of a large amount of dilute sulphuric acid, greatly reduce the treatment capacity containing sour sewage and quantity discharged, thus substantially increase the rate of recovery of Waste Sulfuric Acid.In addition, owing to producing sulfurous gas after sulfur burning, the content of sulfur dioxide in pyrolyzer furnace gas is raised, and then the productive rate of the vitriol oil can be improved.
According to the treatment process of Waste Sulfuric Acid of the present invention, wherein, described Waste Sulfuric Acid can be industrial produced various industrial waste sulfuric acids, such as, can for the Waste Sulfuric Acid produced in alkylate oil preparation process, preferred described Waste Sulfuric Acid contains the sulfuric acid of 87 ~ 90 % by weight.In this Waste Sulfuric Acid also can containing in alkylate oil production process the material that remain, usually mainly contain the material such as sulfuric ester and hydrocarbon polymer.Such as, as long as described oxygen-containing gas can meet sulfur burning just not special requirement, can be the gas such as air, oxygen.
According to the treatment process of Waste Sulfuric Acid of the present invention, wherein, in order to ensure that sulphur and oxygen-containing gas make the abundant cracking of the sulfuric acid in Waste Sulfuric Acid at the heat that pyrolyzer combustion provides, preferred used sulphur and the weight ratio of Waste Sulfuric Acid are (1.5-2.0): 1.
According to the treatment process of Waste Sulfuric Acid of the present invention, wherein, preferably in described cleavage step, sulphur be heated to 140 DEG C ~ 180 DEG C in advance and be passed in described pyrolyzer after oxygen-containing gas being heated to 190 DEG C ~ 210 DEG C.In Waste Sulfuric Acid cracking process, for the ease of sulphur being joined in pyrolyzer and being convenient to make sulfur burning, sulphur and oxygen-containing gas can be heated in advance, make sulphur be molten into liquid state, then be passed in described pyrolyzer.Sulphur is heated within the scope of said temperature, the viscosity of Molten sulphur can be ensured, guarantee the mobility of Molten sulphur.
According to the treatment process of Waste Sulfuric Acid of the present invention, wherein, cracking described in step a can be carried out usually at the temperature of 800 ~ 1500 DEG C, and cracking described in preferred steps a is carried out under the pressure of the temperature of 1000 DEG C ~ 1200 DEG C and-100Pa ~-500Pa.By making Waste Sulfuric Acid cracking under these conditions, can ensure that the sulfuric acid in Waste Sulfuric Acid is fully cracked into water vapour and SO
2.
According to the treatment process of Waste Sulfuric Acid of the present invention, in the preferred case, the described pyrolyzer furnace gas cooling obtained by step a can be lowered the temperature by the mode of heat exchange, such as, waste heat boiler can be used to move heat and/or move heat with the heat exchange of described oxygen-containing gas before entering pyrolyzer.By heat exchange, the pyrolyzer furnace gas cooling that step a can be obtained on the one hand, by heat recuperation, can utilize on the other hand again, thus, and can fully by the heat recovery and utilization of pyrolyzer furnace gas.
According to the treatment process of Waste Sulfuric Acid of the present invention, wherein, in purge drying step, after the pyrolyzer furnace gas cooling that step a is obtained, can by also dry with sulfuric acid scrubbing, reduce the water-content in cracking furnace gas, what be reduced water-content contains SO
2purified gas.Can, by the impurity removing in pyrolyzer furnace gas, the water-content in pyrolyzer furnace gas can be made to reduce on the other hand on the one hand by use sulfuric acid scrubbing is also dry.In the preferred case, obtain described in reduce water-content containing SO
2the moisture content of purified gas is for being less than 0.1g/m
3.In the preferred case, described sulfuric acid scrubbing is also dry can be comprised first with the sulfuric acid scrubbing that concentration is 2-10 % by weight, then is the sulfuric acid drying of 92-95 % by weight by concentration.
According to the treatment process of Waste Sulfuric Acid of the present invention, wherein, in step of converting, what obtained by step b contains SO
2sO in purified gas
2be oxidized to SO
3.By SO
2be oxidized to SO
3method can be method as known in the art, such as, can in the presence of a catalyst, by the SO in splitting gas
2be oxidized to SO
3, use the vitriol oil by SO
3absorb.By SO
2be oxidized to SO
3method such as can in convertor, under the existence of catalyzer as vanadium, adopt the mode of multi-stage oxidizing, make SO
2be substantially oxidized into SO
3.
According to the treatment process of Waste Sulfuric Acid of the present invention, wherein, in absorption step, the SO that step c is obtained
3by the sulfuric acid absorption that concentration is 98.0 ~ 98.3 % by weight, obtain the sulfuric acid that concentration is 98.3 ~ 98.6 % by weight, redilution become concentration be 98.0 ~ 98.3 % by weight sulfuric acid, like this, obtain the sulfuric acid that concentration is 98.0 ~ 98.3 % by weight, achieve object Waste Sulfuric Acid process reclaimed.By the sulfuric acid that the concentration obtained is 98.3 ~ 98.6 % by weight, be diluted to the sulfuric acid of 98.0 % by weight ~ 98.3 % by weight, the sulfuric acid obtained after described washing and described drying in purge drying step can be used.By using the vitriol oil of above-mentioned concentration range to absorb, SO can be improved further
3specific absorption.
In the preferred case, in absorption step, the sulfuric acid obtained after described washing in described purge drying step is made to flow into washing acid tank 14, make describedly to flow in dry acid tank 15 through described dried sulfuric acid, a part for sulfuric acid in this washing acid tank 14 and dry acid tank 15 is cycled to used in washing and the drying of pyrolyzer furnace gas, it is the dilution of the sulfuric acid of 98.3 ~ 98.6 % by weight that another part string is used for concentration described in described absorption step, and by the concentration that obtains after dilution be 98.0 ~ 98.3 % by weight sulfuric acid according to being that the equiponderant amount of sulfuric acid of the dilution of the sulfuric acid of 98.3 ~ 98.6 % by weight adds in described washing acid tank 14 and dry acid tank 15 with being used for described concentration.By the sulfuric acid string in the washing acid tank 14 of the washing and drying that are used for pyrolyzer furnace gas in purge drying step and dry acid tank 15 is used for the dilution that concentration described in described absorption step is the sulfuric acid of 98.3 ~ 98.6 % by weight, the sulfuric acid in the washing acid tank 14 of the washing and drying that are used for pyrolyzer furnace gas and dry acid tank 15 can be realized again to utilize.Meanwhile, be that the sulfuric acid of 98.0 ~ 98.3 % by weight is according to being that the equiponderant amount of sulfuric acid of the dilution of the sulfuric acid of 98.3 ~ 98.6 % by weight adds to the concentration stabilize can guaranteeing the sulfuric acid washed in acid tank 14 and dry acid tank 15 in described washing acid tank 14 and dry acid tank 15 with being used for described concentration by the concentration that obtains after dilution.
According to the treatment process of Waste Sulfuric Acid of the present invention, wherein, a water part required for the dilution of the sulfuric acid that concentration described in described absorption step is 98.3 ~ 98.6 % by weight comes from the sulfuric acid of going here and there from described washing acid tank 14 and dry acid tank 15, and another part comes from make up water.By from stating washing acid tank 14 and dry acid tank 15 string sulfuric acid and/or make up water, effectively SO can will be absorbed
3concentration be 98.0 ~ 98.3 % by weight sulfuric acid dilution obtain the sulfuric acid that concentration is 98.3 ~ 98.6 % by weight, thus can sulfuric acid concentration stable in maintenance system.
According to the treatment process of Waste Sulfuric Acid of the present invention, in the preferred case, after absorption step, the tail gas after absorbing sulphur trioxide can be used 10 % by weight sodium hydroxide solutions carry out after absorptions processes and pass through smoke stack emission.After processing like this, eventually through SO in smoke stack emission to the tail gas in air
2concentration can be reduced to below 50ppm.
Embodiment
Below by way of enumerating embodiment and the treatment process of comparative example to Waste Sulfuric Acid of the present invention further illustrates, but the present invention is not limited to following cited embodiment.
Fig. 1 is the schema of the treatment process for illustration of Waste Sulfuric Acid of the present invention.Below by way of with reference to Fig. 1, embodiment and comparative example are described in detail.
Embodiment 1
A, Waste Sulfuric Acid cleavage step
By the heating temperatures to 150 DEG C of sulphur storage tank, making the sulphur in storage tank all be fused into liquid state, be then delivered to pyrolyzer 1 in by molten sulfur fuel with 2306Kg/h by liquid sulfur pump, is the air 8740m of 205 DEG C with temperature
3/ h sprays into pyrolyzer 1 together and burns, and mainly generates SO after molten sulfur burning
2, spray in pyrolyzer 1 by Waste Sulfuric Acid (forming as shown in table 1) with 1250Kg/h, by regulating molten sulfur and air fuel amount, controlling in-furnace temperature is 1200 DEG C, makes the sulfuric acid cracking in Waste Sulfuric Acid generate SO
2and H
2o, the SO in pyrolyzer 1 in splitting gas
2content is about oxygen-containing gas content in 18.9 volume %, outlet splitting gas and is about 3 volume %, is run by step of converting main blower 21, and making in pyrolyzer 1 is negative-pressure operation, makes pyrolyzer inner air pressure maintain-200Pa.
From pyrolyzer out containing SO
2splitting gas, after moving heat by waste heat boiler 2 and air preheater 3, temperature drops to 280 DEG C, then enters purge drying step.Enter stove air after air preheater 3, temperature rises to 205 DEG C.
B, purge drying step
In purge drying step, first the splitting gas of 280 DEG C enters dynamic wave scrubber 4, and by the dilute sulphuric acid with the 2-10 % by weight sprayed, (temperature is 52 DEG C, and spray flux is 200m
3/ h) contact, moisture in dilute sulphuric acid is rapidly evaporated, splitting gas temperature also decreases simultaneously, in splitting gas, the impurity such as most dust is removed, and the splitting gas of 55 DEG C after dedusting enters packing tower 6 again to carry out sulfuric acid scrubbing (sulfuric acid concentration is 2-10 % by weight, temperature 36 DEG C, spray flux 120m
3/ h) cooling, the moisture further in removing splitting gas, splitting gas temperature is down to after below 40 DEG C, passes into electrostatic precipitator 7, to make in splitting gas sulfuric acid mist amount at 0.005g/m
3below.Return purifying step by dynamic wave scrubber 4 dilute sulphuric acid out through dilute sulphuric acid recycle pump 19 part to recycle, a part delivers to dilute acid bath 14, then delivers to absorption step by dilute sulfuric acid pump 18.(2-10 % by weight, temperature are 55 DEG C, flow 3m to part dilute sulphuric acid
3/ h) enter desorption tower 5, in desorption tower 5, pass into a large amount of air of 25 DEG C, by the most of SO dissolved in dilute sulphuric acid
2take out of, more together enter packing tower 6 with dynamic wave scrubber 4 splitting gas out.
Through purification after splitting gas (39 DEG C) in drying tower 9 with 93 % by weight sulfuric acid (49 DEG C) with 25m
3/ m
2h sprinkle, makes moisture in splitting gas be reduced to 0.1g/m
3below.
C, conversion and absorption step
At step of converting, control convertor 8 one sections of import SO
2concentration is about 9.0 % by weight, adopts V IV I-III II " 3+2 " conversion process flow process, wherein interchanger IV and interchanger V parallel operation, through purification, dried containing SO
2splitting gas, parallel connection passes into the shell side of interchanger V, IV, remerge the shell side entering interchanger I, heat exchange is carried out respectively with the reforming gas from convertor 8 the 5th section, four sections and one section outlet, interchanger I shell-side outlet splitting gas temperature is made to be 425 DEG C, then convertor 8 first paragraph is entered, by SO under vanadium catalyst effect
2be oxidized to SO
3and release a large amount of heat, the pyrolytic conversion gas of one section outlet is down to 460 DEG C through the tube side temperature of interchanger I, enter convertor 8 second segment again, the pyrolytic conversion gas of second stage exit is down to 440 DEG C through the tube side temperature of heat exchanger II, then enters convertor 8 the 3rd section continuation reaction, the tube side that three sections of outlet reforming gas enter interchanger III is cooled to about 220 DEG C, again after economizer 12 is cooled to 170 DEG C, enter the first absorption tower 10 and carry out first time absorption, absorbed SO
3after gas enter the shell side of interchanger III, II successively, heat exchanger II shell-side outlet temperature is 425 DEG C, enter convertor 8 the 4th section again and start second time conversion, reacted pyrolytic conversion gas is cooled to 425 DEG C through the tube side of interchanger IV, enter convertor 8 the 5th section again and continue reaction, reforming gas is cooled to about 170 DEG C through the tube side of interchanger V, then enters second absorption tower 11 and carries out second time absorption.Tail gas absorbs by smoke stack emission after process through 10% sodium hydroxide solution, SO in the tail gas after second time absorbs
2concentration is at below 50ppm.
Through transforming the SO generated
3gas (temperature is 168 DEG C) in absorption tower with concentration be 98.0 ~ 98.3 % by weight sulfuric acid (temperature is 53 DEG C, spray flux is 24m
3/ m
2h) absorb, obtain the sulfuric acid that concentration is 98.3 ~ 98.6 % by weight, SO
3specific absorption can reach more than 99.95%, by the sulfuric acid in use washing acid tank 14 and dry acid tank 15 and make up water, is diluted at the sulfuric acid by concentration being 98.3 ~ 98.6 % by weight sulfuric acid that concentration is 98.0 ~ 98.3 % by weight.Residual exhaust (63 DEG C) enters tail gas absorber 13, and tail gas absorbs by smoke stack emission after process through 10% sodium hydroxide solution, SO in tail gas
2concentration is at below 50ppm.SO
2transformation efficiency, SO
3specific absorption and product purity as shown in table 3.
Embodiment 2 and 3
Except use table 1 Suo Shi become be grouped into waste sulfuric acid from alkylation, change except cracking condition according to table 2, operate similarly to Example 1.SO
2transformation efficiency and SO
3specific absorption as shown in table 3.
Comparative example 1
Except in Waste Sulfuric Acid cleavage step, use substitute gas sulphur as beyond fuel, operate similarly to Example 1.SO
2transformation efficiency and SO
3specific absorption as shown in table 3.In addition, owing to producing a large amount of water vapour after combustion of natural gas, in purge drying step, a large amount of dilute sulphuric acid is created.
Table 1
Table 2
Table 3
| SO 2Transformation efficiency (%) | SO 3Specific absorption (%) | |
| Embodiment 1 | 99.93 | 99.97％ |
| Embodiment 2 | 99.93 | 99.95 |
| Embodiment 3 | 99.92 | 99.97 |
| Comparative example 1 | 98 | 99.91 |
Acid-bearing wastewater quantity discharged measures
By adopting the treatment process of the Waste Sulfuric Acid of embodiment 1 and comparative example 1, respectively 10500 tons of Waste Sulfuric Acids are processed, the amount of the acid-bearing wastewater produced in embodiment 1 545 tons, in comparative example 1 produce the amount 4009 tons of acid-bearing wastewater.
By using sulphur to burn as fuel in the present invention, make the sulfuric acid cracking in Waste Sulfuric Acid, with use Sweet natural gas as fuel in prior art, water can be produced after burning compare with the situation of carbonic acid gas, generate sulfurous gas after sulfur burning, can not water be produced, thus avoid fuel combustion and introduce water vapour, and then avoid the generation of a large amount of dilute sulphuric acid, greatly reduce the treatment capacity containing sour sewage and quantity discharged, thus substantially increase the rate of recovery of Waste Sulfuric Acid.In addition, owing to producing sulfurous gas after sulfur burning, the content of sulfur dioxide in splitting gas is raised, and then the productive rate of the vitriol oil can be improved.
In addition, by the recycling to energy in system, the consumption of fuel gas can be reduced, reduce the running cost of device.
Below the preferred embodiment of the present invention is described in detail by reference to the accompanying drawings; but; the present invention is not limited to the detail in above-mentioned embodiment; within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. a treatment process for Waste Sulfuric Acid, the method comprises:
A, cleavage step: make the cracking in pyrolyzer of described Waste Sulfuric Acid, wherein, the heat needed for this cracking is provided in this pyrolyzer combustion by sulphur and oxygen-containing gas;
B, purge drying step: after the pyrolyzer furnace gas cooling obtained by step a, also dry with sulfuric acid scrubbing, what be reduced water-content contains SO
2purified gas;
C, step of converting: what obtained by step b contains SO
2sO in purified gas
2be oxidized to SO
3;
D, absorption step: the SO that step c is obtained
3by the sulfuric acid absorption that concentration is 98.0 ~ 98.3 % by weight, obtain the sulfuric acid that concentration is 98.3 ~ 98.6 % by weight, then by the concentration obtained be 98.3 ~ 98.6 % by weight sulfuric acid be diluted to the sulfuric acid that concentration is 98.0 ~ 98.3 % by weight.
2. method according to claim 1, wherein, described Waste Sulfuric Acid contains the H of 87 % by weight ~ 90 % by weight
2sO
4, described oxygen-containing gas is air.
3. method according to claim 1, wherein, the weight ratio of described sulphur and described Waste Sulfuric Acid is (1.5-2.0): 1.
4. method according to claim 1, wherein, in described cleavage step, is heated to 140 DEG C ~ 180 DEG C in advance and after oxygen-containing gas being heated to 190 DEG C ~ 210 DEG C, is passed in described pyrolyzer by sulphur.
5. method according to claim 1, wherein, cracking described in step a is carried out under the pressure of the temperature of 1000 DEG C ~ 1200 DEG C and-100Pa ~-500Pa.
6. method according to claim 1, wherein, in described purge drying step, the described pyrolyzer furnace gas cooling obtained by step a comprises and uses waste heat boiler to move heat and/or move heat with the heat exchange of described oxygen-containing gas before entering pyrolyzer.
7. method according to claim 1, wherein, what reduce water-content described in obtaining contains SO
2the moisture content of purified gas is for being less than 0.1g/m
3.
8. method according to claim 1, wherein, in described purge drying step, described sulfuric acid scrubbing is also dry to be comprised first with the sulfuric acid scrubbing that concentration is 2-10 % by weight, then is the sulfuric acid drying of 92-95 % by weight by concentration.
9. method according to claim 8, wherein, the sulfuric acid obtained after described washing in described purge drying step is made to flow into washing acid tank (14), make describedly to flow in dry acid tank (15) through described dried sulfuric acid, a part for sulfuric acid in this washing acid tank (14) and dry acid tank (15) is cycled to used in washing and the drying of pyrolyzer furnace gas, it is the dilution of the sulfuric acid of 98.3 ~ 98.6 % by weight that another part string is used for concentration described in described absorption step, and by the concentration that obtains after dilution be 98.0 ~ 98.3 % by weight sulfuric acid according to being that the equiponderant amount of sulfuric acid of the dilution of the sulfuric acid of 98.3 ~ 98.6 % by weight adds in described washing acid tank (14) and dry acid tank (15) with being used for described concentration.
10. method according to claim 9, wherein, a water part required for the dilution of the sulfuric acid that concentration described in described absorption step is 98.3 ~ 98.6 % by weight comes from the sulfuric acid from described washing acid tank (14) and dry acid tank (15) string, and another part comes from make up water.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106976896A (en) * | 2017-05-17 | 2017-07-25 | 北京华元昊峰科技有限公司 | A kind of utilization waste sulfuric acid from alkylation produces the method and system of epsom salt |
| CN112694066A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Waste sulfuric acid liquid oxygen cracking system and cracking method |
| CN113620456A (en) * | 2021-06-30 | 2021-11-09 | 南通醋酸化工股份有限公司 | Solvent recovery and waste acid treatment system and method suitable for producing acesulfame potassium |
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| CN1751984A (en) * | 2004-09-20 | 2006-03-29 | 中国石油天然气股份有限公司 | Treatment technology of producing sulfuric acid from alkylated spent sulfuric acid through high temperature decomposition |
| CN105152140A (en) * | 2015-07-21 | 2015-12-16 | 山东中天科技工程有限公司 | Process for treating alkylated waste sulfuric acid |
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| CN1751984A (en) * | 2004-09-20 | 2006-03-29 | 中国石油天然气股份有限公司 | Treatment technology of producing sulfuric acid from alkylated spent sulfuric acid through high temperature decomposition |
| CN105152140A (en) * | 2015-07-21 | 2015-12-16 | 山东中天科技工程有限公司 | Process for treating alkylated waste sulfuric acid |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106976896A (en) * | 2017-05-17 | 2017-07-25 | 北京华元昊峰科技有限公司 | A kind of utilization waste sulfuric acid from alkylation produces the method and system of epsom salt |
| CN106976896B (en) * | 2017-05-17 | 2019-10-15 | 北京华元昊峰科技有限公司 | A kind of method and system using waste sulfuric acid from alkylation production epsom salt |
| CN112694066A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Waste sulfuric acid liquid oxygen cracking system and cracking method |
| CN112694066B (en) * | 2019-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Waste sulfuric acid liquid oxygen cracking system and cracking method |
| CN113620456A (en) * | 2021-06-30 | 2021-11-09 | 南通醋酸化工股份有限公司 | Solvent recovery and waste acid treatment system and method suitable for producing acesulfame potassium |
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