CN103979502A - Regeneration method of waste sulfuric acid, and sulfuric acid produced by the method - Google Patents
Regeneration method of waste sulfuric acid, and sulfuric acid produced by the method Download PDFInfo
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- CN103979502A CN103979502A CN201410182027.7A CN201410182027A CN103979502A CN 103979502 A CN103979502 A CN 103979502A CN 201410182027 A CN201410182027 A CN 201410182027A CN 103979502 A CN103979502 A CN 103979502A
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Abstract
The invention provides a regeneration method of waste sulfuric acid and sulfuric acid produced by the method. The regeneration method includes following steps: carrying out a high-temperature cracking operation in a cracking furnace to waste sulfuric acid subjected to pressurized atomization for obtaining a product wherein the high-temperature cracking temperature is 800-1200 DEG C a high-temperature pyrolysis temperature is 800-1200 DEG C, oxygen content of gas discharged from the furnace is not less than 2mol% and reaction residence time is 1.2s-2.5s; cooling the product to 410-435 DEG C and directly carrying out a multistage catalytic oxidation reaction without a drying operation until the conversion rate of sulfur dioxide being 99%-99.8% with an interstage cooling process, wherein a reaction starting temperature T of each stage of the multistage catalytic oxidation reaction is described as T=(390+(n-m)*10) DEG C with n being an overall reaction stage number and m being a present reaction stage number; further carrying out a cooling process with a cooling temperature being 260-320 DEG C; and then carrying out the cooling process with a final cooling temperature being 60-120 DEG C. Difference between air inlet temperature and process gas outlet temperature is 50-85 DEG C. The method is simplified in process and is reasonable in equipment arrangement.
Description
Technical field
The present invention relates to the sulfuric acid of Waste Sulfuric Acid renovation process and gained.
Background technology
Petrochemical complex and organic synthesis industry are widely used the vitriol oil and make catalyzer, and this process will produce a large amount of Waste Sulfuric Acids.For example: in petroleum refining industry, use isoparaffin and alkene, under the sulphuric acid catalysis effect of 98wt%～99.5wt%, alkylated reaction occurs, produce high octane value gasoline blending component oil.Reactant continuously feeding under the excessive condition of alkene, the mixture simultaneously flowing out from reactor can obtain being respectively rich in the acid of the catalyzer vitriol oil and the oil phase that is rich in alkylate through separation.Most sour phase product can be recycled, but along with the carrying out of reaction, and water and some acid soluble hydrocarbon polymer can progress into and in the vitriol oil, cause its density loss, catalysis strength decreased.Consequent Waste Sulfuric Acid is dark red sticky glue shape liquid, distributes off-odor and is difficult to and process.In addition, some organic synthesis techniques as synthesizing methylmethacrylate (MMA) and propylene fine (AN), also produce the Waste Sulfuric Acid ammonium of about 35wt%～40wt% except producing Waste Sulfuric Acid.Once these sulfur-bearing waste entered environments will cause severe contamination, be therefore necessary industrial waste acid carry out purifying treatment and recycle.
Existing Waste Sulfuric Acid treatment technology mainly comprises that the high temperature of Waste Sulfuric Acid is concentrated, solvent extraction, alkali neutralization and chemical oxidation, Pintsch process etc., wherein Pintsch process technique is to process at present the most ripe, the clean method of Waste Sulfuric Acid, it comprises that cracking purification, catalyzed conversion and dry gas absorb flow process, and being specially this technology provides the high temperature of 1000 ℃～1100 ℃ that sulfuric acid is cracked into SO by combusting heavy oil or inflammable gas
2, other organism in spent acid complete oxidation is CO
2and H
2o.SO
2gas is delivered to contact process device through pickling, the operation such as dry after processing and is oxidized to sulphur trioxide, then obtains the vitriol oil of 98wt%.Some famous enterprises are as the Outokumpu of Finland (OUTO KUMPU) in the world, the Meng Moke of the U.S. (MECS) and Du Pont (DUPONT), husky cover (the SIRY CHAMON) of gondola Seeley has corresponding Pintsch process technique for the regeneration of Waste Sulfuric Acid, and what China PetroChina Company Ltd. developed can process waste sulfuric acid from alkylation and H simultaneously
2the technology of S gas manufacture level sulfuric acid, the patent document CN100537416C of its announcement is described in detail this technique: the cracking at 1000 ℃～1100 ℃ of spent acid and sour gas, H
2sO
4first dehydration generates SO
3then be reduced to SO
2, go out furnace gas and recycle for alkylated reaction through the sulfuric acid of acid-scrubbing cleaning, twice contact process conversion and twice absorption process output 98wt%.Yet there is the shortcoming that facility investment is large, production power consumption is high in existing spent acid pyrolysis recycle technique.The flow process of announcing from CN100537416C can be clear that this technical process is long, and the operating unit relating to is many, adopts contact-absorption process to prepare the vitriol oil and need carry out a series of pickling impurity removals, demist, drying treatment to cracking furnace gas, the high complicated operation of running cost.Therefore be necessary existing technique reasonably to improve.
Summary of the invention
In order to solve, in prior art, the technical process of Waste Sulfuric Acid renovation process is complicated, production energy consumption is high, high in cost of production defect in the present invention, a kind of improved Waste Sulfuric Acid renovation process is provided, produce qualified technical grade sulfuric acid, simplify operating process, realized the economic benefit of regenerating unit and the reasonable utilization of the energy.
The invention provides a kind of Waste Sulfuric Acid renovation process, comprise the steps:
(1) through the Waste Sulfuric Acid of pressurizing atomizing in pyrolyzer, under fuel and oxygen-rich air exist, carry out Pintsch process; The temperature of described Pintsch process is 800 ℃～1200 ℃; Oxygen level >=the 2mol% that goes out furnace gas of described Pintsch process; The reaction time of Pintsch process is 1.2s～2.5s;
(2) products therefrom in step (1) is cooled to 410～435 ℃, without drying treatment, directly carries out multistage catalytic oxidation to SO
2transformation efficiency 99%～99.8%; In described multistage catalyzed reaction, carry out interstage cooling; The reaction of multistage each progression of catalytic oxidation starts temperature: T=390 ℃+(n-m) * 10 ℃, wherein n is overall reaction order, and m is current reaction order;
(3) step (2) products therefrom is cooled to 260 ℃～320 ℃;
(4) in step (3), gained Process Gas and air heat-exchange realization are further cooling, and cooling outlet temperature is 60 ℃～120 ℃; Described cooling cooling rate realizes by controlling the temperature difference of air and Process Gas, and the difference of the cooling front temperature of described air and the described cooled temperature of Process Gas is 50～85 ℃.
In the present invention, described Waste Sulfuric Acid is that this area is conventional, the Waste Sulfuric Acid that the titratable acidity that is generally alkylated reaction generation in petroleum refining process is 84%～90%, also can be the Waste Sulfuric Acid ammonium of general organic synthesis industry 35wt%～40wt% that methyl methacrylate (MMA), vinyl cyanide (AN) produce as produced, or the Waste Sulfuric Acid producing in other organic chemical industry, inorganic chemical industry, iron and steel processing industry.Preferably, in order to reduce the energy consumption of device operation, the Waste Sulfuric Acid lower for concentration need be more than pre-treatment be concentrated into 60wt% simultaneously.
In step of the present invention (1), first there is dehydration reaction and generate SO in Waste Sulfuric Acid in pyrolyzer
3, SO then
3reductive cleavage is SO
2, according to pyrolyzer fire box temperature and the residence time, will produce a small amount of SO
3, the equation that reaction relates to is as follows:
H
2sO
4(liquid) → SO
3(gas)+H
2o (gas)-175.9kJ/mol (1)
SO
3(gas) → SO
2(gas)+1/2O
2(gas)-99kJ/mol (2)
While containing ammonium salt in spent acid, also having nitrogen discharges:
(NH
4)
2SO
4+O
2→N
2+SO
2+4H
2O (3)
NH
4HSO
4+1/4O
2→1/2N
2+SO
2+5/2H
2O (4)
In addition, for the waste sulfuric acid from alkylation producing in petroleum refining process, generally also contain the hydrocarbon polymer of 8wt%～14wt%, oxygenolysis in the lump in pyrolyzer:
Organic polymer+O
2→ CO
2+ H
2o (5)
In the present invention, preferably, the Waste Sulfuric Acid eddy flow through pressurizing atomizing in step (1) sprays in pyrolyzer.
In the present invention, preferably, the oxygen content of described oxygen-rich air is generally 29mol%～60mol%.
In the present invention, the fuel described in step (1) is that this area is conventional, and preferably, described fuel is fuel gas and/or fuel heavy oil.Better, the combustible exhaust gas of all right using appts of fuel.Described fuel value is>=5500Kcal/Nm
3.
In the present invention, preferably, the temperature of described Pintsch process is 950 ℃～1050 ℃.
In the present invention, preferably, the described oxygen level that goes out furnace gas is 6～14mol%.
In the present invention, preferably, the reaction time of described Pintsch process is 1.5s～1.8s.
In the present invention, preferably, cooling described in step (2) carries out in water cooler.
In the present invention, preferably, the transformation efficiency described in step (2) is 99.2%.
In the present invention, preferably, also carry out dust removal process after cooling in step (2), then carry out catalytic oxidation; Better, described dust removal process is carried out dedusting through high temperature resistant precision ceramic filter.
In the present invention, preferably, cooling in step (2) after, the heat of recovery is for the production of mesohigh saturation steam, supplements oxygen-rich air and regulates SO
2concentration is 3.3～4mol%.When Waste Sulfuric Acid of the present invention is the Waste Sulfuric Acid of titanium dioxide industry by-product, wherein contain the FeSO of 5wt%～8wt%
4and the vitriol of the metal such as a small amount of Ti, Al, Mn, Ca, Mg, in Pintsch process process, can produce metallic dust, preferably at Process Gas cooler outlet, high temperature resistant precision ceramic filter is installed for this reason and is removed, this is high temperature resistant, and precision ceramic filter can realization of industrialization.
In the present invention, described multistage catalytic oxidation is this area popular response, and in multistage catalytic oxidation, the reaction formula of main reaction is
In the present invention, preferably, described multistage catalytic oxidation is 2～5 grades of catalytic oxidations; Better, described multistage catalyzed reaction is 2～3 grades of catalytic oxidations.
In the present invention, preferably, described interstage cooling is used interchanger carry out cooling or directly spray into air cooling-down; Preferably, the cooling mesolow saturation steam of using of described interchanger is as heat-eliminating medium.Better, when using interchanger cooling, with mesolow saturation steam, as heat-eliminating medium, carrying out heat recuperation, the superheated vapour of by-product can be used for promoting compressor turbine acting energy efficient.
In the present invention, preferably, described multistage catalytic oxidation carries out in horizontal type fixed bed reactor.
In the present invention, in described multistage catalyzed reaction, catalyzer is that this area is conventional, on the catalyzer screen of general filling and reactor bottom; Preferably, the catalyzer in described multistage catalytic oxidation is V
2o
5catalyst based.
In the present invention, preferably, the cooling temperature described in step (3) is 260 ℃～290 ℃; What cooling temperature was better is 260～285 ℃.
Wherein, preferably, cooling described in step (3) carries out in interchanger.Better, described also use in cooling mesolow saturation steam as heat-eliminating medium to produce high-pressure saturated steam or superheated vapour, described mesolow saturation steam refers to that pressure is the saturation steam of 0.5MPag～7.8MPag.
In the present invention, preferably, the cooling outlet temperature described in step (4) is T=20 ℃+Tdp, and wherein Tdp is sulphuric acid dew point temperature, 1000/Tdp=2.276-0.0294ln (P
h2O)-0.0858ln (P
sO3), P wherein
h2Oand P
sO3be partial component pressure, the unit of described partial component pressure is mmHg.
In the present invention, preferably, the cooling outlet temperature described in step (4) is 105～120 ℃.
In the present invention, preferably, cooling described in step (4) carries out in sulfuric acid vapor condenser.
In the process of cooling described in step (3) and (4), SO in Process Gas
3heshui is formed to H
2sO
4, and there is H
2sO
4the above concentration H of vapor condensation simmer down to 93%
2sO
4, collect sulfuric acid product.
In the present invention, preferably, in step (4), the cooling outlet temperature of Process Gas is 60 ℃-110 ℃.
Wherein, preferably, the difference of the cooling front temperature of the air described in step (4) and the described cooled temperature of Process Gas is 55～70 ℃.
Wherein, preferably, the noncondensable gas process coarse separation obtaining after described step (4) is cooling is emptying process directly, and the Coalescence Separation of described noncondensable gas can be used the coarse separation equipment of this area routine.
The present invention also provides a kind of sulfuric acid being made by above-mentioned Waste Sulfuric Acid renovation process.
Meeting on the basis of this area general knowledge, above-mentioned each optimum condition, can arbitrary combination, obtains the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material be commercially available obtaining all.
Positive progressive effect of the present invention is: the invention provides the method for brand-new Waste Sulfuric Acid regeneration, technical process is greatly simplified, device layout is reasonable, easy and simple to handle, remarkable in economical benefits, and complex energy utilization ratio is high.The H obtaining through regeneration of sulfuric acid method of the present invention
2sO
4product concentration can reach 93wt%～98wt%, can be adjusted into according to specific needs the technical grade vitriol oil of constant density for use.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the embodiment of the present invention.
Embodiment
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, according to ordinary method and condition, or selects according to catalogue.
Embodiment 1:
Waste Sulfuric Acid composition sees the following form, and uses the oxygenized air combustion supporting of 29%mol in pyrolyzer.
Table 1
The technical process of this programme can be referring to Fig. 1.Charging spent acid is that scission reaction occurs in S1 at pyrolyzer, specifically referring to equation (1), (2), (5), pyrolyzer temperature of reaction is 1020 ℃, by combusting heavy oil or fuel gas, realized, wherein combustion air is preferably above-mentioned 29%mol oxygen-rich air, going out oxygen residual volume in furnace gas is 3mol%, and Waste Sulfuric Acid 99.5% is reduced to SO
2, remain as SO
3, produce a large amount of H simultaneously
2o, Pintsch process reaction time is 1.5s.
Go out furnace gas and be cooled to 420～425 ℃ through interchanger S2, the heat of recovery, for the production of mesohigh saturation steam, supplements oxygen-rich air and regulates SO
2concentration is 4mol%, after hot precipitator S3 trapping removes metal dirt, enters multistage catalyticreactor S4, oxidation SO
2generate SO
3, adopt the mode of interstage cooling to remove heat production mesohigh saturation steam, reaction order is 3 grades, SO
2conversion rate at tube exit is 99.35%.The temperature in of multistage each progression of catalytic oxidation is: T=390 ℃+(3-m) * 10 ℃, wherein m is current reaction order.
Catalyzer in described multistage catalytic oxidation is V
2o
5catalyst based.
Multistage catalytic reaction products is cooled to 260 ℃ through interchanger S6, and mesolow saturation steam is as heat-eliminating medium heat exchange, and the heat of recovery, in order to produce mesohigh saturation steam, then makes liquid H by air cooling to 60 ℃ in sulfuric acid vapor condenser S5
2sO
4from gas phase, separate out and obtain pure sulfuric acid product, air, as heat-eliminating medium, enters interchanger S5 and carries out heat exchange.Cooling outlet temperature is T=20 ℃+Tdp, and wherein Tdp is sulphuric acid dew point temperature, 1000/Tdp=2.276-0.0294ln (P
h2O)-0.0858ln (P
sO3), P wherein
h2Oand P
sO3be partial component pressure, the unit of described partial component pressure is mmHg.
Cooling rate realizes by controlling the temperature difference of air and Process Gas, and inlet air temp and the process gas outlet temperature difference are 65 ℃.
Sulfuric acid product flows out and after cooling, sends battery limit (BL) from bottom, and the non-condensable gas of top exit is through coalescing separator S7 trapping H
2sO
4clean emptying after aerosol.
After the sequence of operations such as Pintsch process, catalysis relieving haperacidity, vapor condensation, can obtain pure 96wt% sulfuric acid, the rate of recovery is 95% (mass ratio).
Embodiment 2:
Waste Sulfuric Acid composition sees the following form, and uses the oxygenized air combustion supporting of 45mol% in pyrolyzer.
Table 2
The technical process of this programme can be referring to Fig. 1.Charging spent acid is that scission reaction occurs in S1 at pyrolyzer, specifically referring to equation (1), (2), (5), pyrolyzer temperature of reaction is 1150 ℃, by combusting heavy oil or fuel gas, realized, wherein combustion air is preferably above-mentioned 45%mol oxygen-rich air, going out oxygen residual volume in furnace gas is 5mol%, and Waste Sulfuric Acid 99.73% is reduced to SO
2, remain as SO
3, produce a large amount of H simultaneously
2o.Pintsch process reaction time is 1.3s.
Go out furnace gas and be cooled to 430～435 ℃ through interchanger S2, the heat of recovery, for the production of mesohigh saturation steam, supplements oxygen-rich air and regulates SO
2concentration is 4mol%, after hot precipitator S3 trapping removes metal dirt, enters multistage catalyticreactor S4, oxidation SO
2generate SO
3, adopt the mode of interstage cooling to remove heat production mesohigh saturation steam, reaction order is 4 grades, SO
2conversion rate at tube exit is 99.7%.The temperature in of multistage each progression of catalytic oxidation is: T=390 ℃+(4-m) * 10 ℃, m is current reaction order.
Catalyzer in described multistage catalytic oxidation is V
2o
5catalyst based.
Multistage catalytic reaction products is cooled to 290 ℃ through interchanger S6, and mesolow saturation steam is as heat-eliminating medium heat exchange, and the heat of recovery, in order to produce mesohigh saturation steam, then makes liquid H by air cooling to 60 ℃ in sulfuric acid vapor condenser S5
2sO
4from gas phase, separate out and obtain pure sulfuric acid product.
Cooling rate realizes by controlling the temperature difference of air and Process Gas, and inlet air temp and the process gas outlet temperature difference are 60 ℃.
Sulfuric acid product flows out and after cooling, sends battery limit (BL) from bottom, and the non-condensable gas of top exit is through coalescing separator S7 trapping H
2sO
4clean emptying after aerosol.
After the sequence of operations such as Pintsch process, catalysis relieving haperacidity, vapor condensation, can obtain pure 97.5wt% sulfuric acid, the rate of recovery is 97% (mass ratio).
Embodiment 3:
Waste Sulfuric Acid composition sees the following form, and uses air (oxygen level is 20.7%mol) combustion-supporting in pyrolyzer.
Table 3
The technical process of this programme can be referring to Fig. 1.Charging spent acid is that scission reaction occurs in S1 at pyrolyzer, specifically referring to equation (1), (2), (5), pyrolyzer temperature of reaction is 950 ℃, by combusting heavy oil or fuel gas, realized, wherein combustion air is preferably above-mentioned air, going out oxygen residual volume in furnace gas is 4.3mol%, and Waste Sulfuric Acid 99.35% is reduced to SO
2, remain as SO
3, produce a large amount of H simultaneously
2o.Pintsch process reaction time is 1.7s.
Go out furnace gas and be cooled to 430～435 ℃ through interchanger S2, the heat of recovery, for the production of mesohigh saturation steam, supplements oxygen-rich air and regulates SO
2concentration is 3.3mol%, after hot precipitator S3 trapping removes metal dirt, enters multistage catalyticreactor S4, oxidation SO
2generate SO
3, adopt the mode of interstage cooling to remove heat production mesohigh saturation steam, reaction order is 4 grades, SO
2conversion rate at tube exit is 99.35%.The temperature in of multistage each progression of catalytic oxidation is: T=390 ℃+(4-m) * 10 ℃, m is current reaction order.Catalyzer in described multistage catalytic oxidation is V
2o
5catalyst based.
Multistage catalytic reaction products is cooled to 310 ℃ through interchanger S6, and mesolow saturation steam is as heat-eliminating medium heat exchange, and the heat of recovery, in order to produce mesohigh saturation steam, then makes liquid H by air cooling to 60 ℃ in sulfuric acid vapor condenser S5
2sO
4from gas phase, separate out and obtain pure sulfuric acid product.Sulfuric acid product flows out and after cooling, sends battery limit (BL) from bottom, and the non-condensable gas of top exit is through coalescing separator S7 trapping H
2sO
4clean emptying after aerosol.
Cooling rate realizes by controlling the temperature difference of air and Process Gas, and inlet air temp and the process gas outlet temperature difference are 68 ℃.
After the sequence of operations such as Pintsch process, catalysis relieving haperacidity, vapor condensation, can obtain pure 97.3wt% sulfuric acid, the rate of recovery is 95.5% (mass ratio).
Embodiment 4
Waste Sulfuric Acid composition sees the following form, and uses air (oxygen level is 60%mol) combustion-supporting in pyrolyzer.
Table 4
The technical process of this programme can be referring to Fig. 1.Charging spent acid is that scission reaction occurs in S1 at pyrolyzer, specifically referring to equation (1), (2), (5), pyrolyzer temperature of reaction is 950 ℃, by combusting heavy oil or fuel gas, realized, wherein combustion air is preferably above-mentioned air, going out oxygen residual volume in furnace gas is 16mol%, and Waste Sulfuric Acid 99.2% is reduced to SO
2, remain as SO
3, produce a large amount of H simultaneously
2o.The reaction time of Pintsch process is 1.8s.
Go out furnace gas and be cooled to 410～415 ℃ through interchanger S2, mesolow saturation steam is as heat-eliminating medium heat exchange, and the heat of recovery, for the production of mesohigh saturation steam, supplements oxygen-rich air and regulates SO
2concentration is 3.3mol%, after hot precipitator S3 trapping removes metal dirt, enters multistage catalyticreactor S4, oxidation SO
2generate SO
3, adopt the mode of interstage cooling to remove heat production mesohigh saturation steam, reaction order is 2 grades, SO
2conversion rate at tube exit is 99.35%.The temperature in of multistage each progression of catalytic oxidation is: T=390 ℃+(2-m) * 10 ℃, m is current reaction order.Catalyzer in described multistage catalytic oxidation is V
2o
5catalyst based.
Multistage catalytic reaction products is cooled to 320 ℃ through interchanger S6, and the heat of recovery, in order to produce mesohigh saturation steam, then makes liquid H by air cooling to 120 ℃ in sulfuric acid vapor condenser S5
2sO
4from gas phase, separate out and obtain pure sulfuric acid product.Sulfuric acid product flows out and after cooling, sends battery limit (BL) from bottom, and the non-condensable gas of top exit is through coalescing separator S7 trapping H
2sO
4clean emptying after aerosol.Cooling rate realizes by controlling the temperature difference of air and Process Gas, and inlet air temp and the process gas outlet temperature difference are 85 ℃.
Claims (10)
1. a Waste Sulfuric Acid renovation process, is characterized in that, it comprises the steps:
(1) through the Waste Sulfuric Acid of pressurizing atomizing in pyrolyzer, under fuel and oxygen-rich air exist, carry out Pintsch process; The temperature of described Pintsch process is 800 ℃～1200 ℃; Oxygen level >=the 2mol% that goes out furnace gas of described Pintsch process; The reaction time of Pintsch process is 1.2s～2.5s;
(2) products therefrom in step (1) is cooled to 410～435 ℃, without drying treatment, directly carries out multistage catalytic oxidation to SO
2transformation efficiency 99%～99.8%; In described multistage catalyzed reaction, carry out interstage cooling; The reaction of multistage each progression of catalytic oxidation starts temperature: T=390 ℃+(n-m) * 10 ℃, wherein n is overall reaction order, and m is current reaction order;
(3) step (2) products therefrom is cooled to 260 ℃～320 ℃;
(4) in step (3), gained Process Gas and air heat-exchange realization are further cooling, and cooling outlet temperature is 60 ℃～120 ℃; Described cooling cooling rate realizes by controlling the temperature difference of air and Process Gas, and the difference of the cooling front temperature of described air and the described cooled temperature of Process Gas is 50～85 ℃.
2. Waste Sulfuric Acid renovation process as claimed in claim 1, is characterized in that, the Waste Sulfuric Acid eddy flow through pressurizing atomizing in step (1) sprays in pyrolyzer; The oxygen content of described oxygen-rich air is 29mol%～60mol%; Described fuel is fuel gas and/or fuel heavy oil, and described fuel value is>=5500Kcal/Nm
3.
3. Waste Sulfuric Acid renovation process as claimed in claim 1, is characterized in that, the temperature of described Pintsch process is 950 ℃～1050 ℃;
And/or the described oxygen level that goes out furnace gas is 6～14mol%;
And/or the reaction time of described Pintsch process is 1.5s～1.8s;
And/or the transformation efficiency described in step (2) is 99.2%;
And/or cooling described in step (2) carries out in water cooler;
And/or, also carry out dust removal process after cooling in step (2), then carry out catalytic oxidation, wherein, described dust removal process is preferably carried out dedusting through high temperature resistant precision ceramic filter.
4. Waste Sulfuric Acid renovation process as claimed in claim 1, is characterized in that, described multistage catalytic oxidation is 2～5 grades of catalytic oxidations; Preferably, described multistage catalyzed reaction is 2～3 grades of catalytic oxidations.
5. Waste Sulfuric Acid renovation process as claimed in claim 1, is characterized in that, described interstage cooling is used interchanger carry out cooling or directly spray into air cooling-down; Preferably, the cooling mesolow saturation steam of using of described interchanger is as heat-eliminating medium.
6. Waste Sulfuric Acid renovation process as claimed in claim 1, is characterized in that, described multistage catalytic oxidation carries out in horizontal type fixed bed reactor, and/or the catalyzer in described multistage catalytic oxidation is V
2o
5catalyst based.
7. Waste Sulfuric Acid renovation process as claimed in claim 1, is characterized in that, the cooling temperature described in step (3) is 260 ℃～290 ℃, is preferably 260～285 ℃.
8. Waste Sulfuric Acid renovation process as claimed in claim 7, is characterized in that, cooling described in step (3) carries out in interchanger; Preferably, described cooling middle mesolow saturation steam is as heat-eliminating medium, and described mesolow saturation steam refers to that pressure is the saturation steam of 0.5MPag～7.8MPag.
9. Waste Sulfuric Acid renovation process as claimed in claim 1, is characterized in that, the cooling outlet temperature described in step (4) is 105～120 ℃; Preferably, the cooling outlet temperature of described Process Gas is 60 ℃～110 ℃;
And/or the cooling outlet temperature described in step (4) is T=20 ℃+Tdp, wherein Tdp is sulphuric acid dew point temperature, 1000/Tdp=2.276-0.0294ln (P
h2O)-0.0858ln (P
sO3), P wherein
h2Oand P
sO3be partial component pressure, the unit of described partial component pressure is mmHg;
And/or cooling described in step (4) carries out in sulfuric acid vapor condenser;
And/or the difference of the cooling front temperature of the air described in step (4) and the described cooled temperature of Process Gas is 55～70 ℃;
And/or the noncondensable gas process coarse separation obtaining after described step (4) is cooling is emptying process directly, the Coalescence Separation of described noncondensable gas is used the coarse separation equipment of this area routine.
10. the sulfuric acid that prepared by the Waste Sulfuric Acid renovation process as described in claim 1～9 any one.
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| CN105567359A (en) * | 2015-12-23 | 2016-05-11 | 裴舜尧 | Pollution-free isooctane regeneration production line |
| CN108033433A (en) * | 2017-10-26 | 2018-05-15 | 青岛海湾集团有限公司 | A kind of industrial waste acid processing system |
| CN108069406A (en) * | 2016-11-15 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of renovation process of waste sulfuric acid from alkylation |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002284509A (en) * | 2001-03-28 | 2002-10-03 | Osaka Gas Co Ltd | Treatment method of spent sulfuric acid and the treatment equipment |
| 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 |
| KR100691165B1 (en) * | 2005-08-19 | 2007-03-09 | 권영식 | Method for recovering of h2so4 produced in pickling process |
| CN103395750A (en) * | 2013-07-22 | 2013-11-20 | 江苏永纪化工设备有限公司 | Technology for making acid by combined incineration of waste sulfuric acid and hydrogen sulfide and used incinerator |
-
2014
- 2014-04-30 CN CN201410182027.7A patent/CN103979502B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002284509A (en) * | 2001-03-28 | 2002-10-03 | Osaka Gas Co Ltd | Treatment method of spent sulfuric acid and the treatment equipment |
| 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 |
| KR100691165B1 (en) * | 2005-08-19 | 2007-03-09 | 권영식 | Method for recovering of h2so4 produced in pickling process |
| CN103395750A (en) * | 2013-07-22 | 2013-11-20 | 江苏永纪化工设备有限公司 | Technology for making acid by combined incineration of waste sulfuric acid and hydrogen sulfide and used incinerator |
Non-Patent Citations (2)
| Title |
|---|
| 孙正东: "炼厂酸性气制硫酸原理及工艺综述", 《硫磷涉及与粉体工程》, no. 6, 30 November 2010 (2010-11-30), pages 5 - 18 * |
| 纪罗军等: "我国废硫酸的资源化利用与循环经济", 《硫酸工业》, no. 5, 31 December 2008 (2008-12-31), pages 11 - 17 * |
Cited By (8)
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| CN105567359A (en) * | 2015-12-23 | 2016-05-11 | 裴舜尧 | Pollution-free isooctane regeneration production line |
| CN105567359B (en) * | 2015-12-23 | 2017-12-08 | 廖光青 | A kind of pollution-free isooctane regeneration process units |
| CN108069406A (en) * | 2016-11-15 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of renovation process of waste sulfuric acid from alkylation |
| CN108069406B (en) * | 2016-11-15 | 2019-12-13 | 中国石油化工股份有限公司 | Regeneration method of alkylation waste sulfuric acid |
| CN108033433A (en) * | 2017-10-26 | 2018-05-15 | 青岛海湾集团有限公司 | A kind of industrial waste acid processing system |
| CN108033433B (en) * | 2017-10-26 | 2020-04-24 | 青岛海湾集团有限公司 | Industrial waste acid treatment system |
| 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 |
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