CN109485021A - A kind of method of thermally conductive resolution process waste sulfuric acid from alkylation - Google Patents
A kind of method of thermally conductive resolution process waste sulfuric acid from alkylation Download PDFInfo
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- CN109485021A CN109485021A CN201910023260.3A CN201910023260A CN109485021A CN 109485021 A CN109485021 A CN 109485021A CN 201910023260 A CN201910023260 A CN 201910023260A CN 109485021 A CN109485021 A CN 109485021A
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- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
Abstract
The invention discloses a kind of methods of thermally conductive resolution process waste sulfuric acid from alkylation, include the following steps: 1) to import waste sulfuric acid from alkylation liquid in the sandwich reactor of sealing, 270-350 DEG C is heated to waste sulfuric acid from alkylation using the conduction oil in interlayer, make its decomposition, obtain the gas of multiple groups part and gradually becomes the acid pickle of solid；2) gas of the multiple groups part for obtaining upper step is passed through in the sealing container equipped with recirculated cooling water and macromolecule resin adsorbent material, is adsorbed gas into liquid phase；3) acid pickle for becoming solid that step 1) obtains is mixed with step 2) by the water of macromolecule resin adsorbent material absorption regeneration, generates sulfuric acid solution using esterlysis reaction principle；4) material that step 3) obtains is separated by solid-liquid separation with physical method, the available concentrated sulfuric acid is concentrated by heating into liquid, or ammonium hydroxide is added to become ammonium sulfate recycling in a liquid.
Description
Technical field
The invention belongs to industrial wastes processing technology fields, are related to a kind of side of thermally conductive resolution process waste sulfuric acid from alkylation
Method, and in particular to petrochemical industry alkylated reaction generates the high dangerous waste alkane of generated multiple groups part during high-knock rating gasoline component
The processing method of base sulfate liquid.
Background technique
At present both at home and abroad in low-carbon hydro carbons molecular alkyl reaction process, the sulfuric acid for generalling use high concentration is catalyzed
Agent, by purification and washing, absorption, cyclic process, moisture, side reaction product etc. in raw material constantly enter in the concentrated sulfuric acid, sulphur
Acid concentration gradually decreases, and various impurity component contents, when sulfuric acid concentration drops to 90%, are just lost and live also with increasing
Property, form the sulfuric acid mixed waste liquor of multiple groups part.It is characterized in that it is unstable, have intense irritation smell, be difficult, destroy ecological ring
Border.
Waste sulfuric acid from alkylation is a kind of multiple groups part dangerous waste mixing liquid, contains gas chromatography and inorganic matter, corrosivity is strong, is
Seriously endanger the heavily contaminated dangerous waste object of ecological environment.Processing method mainly has pyrolysis method, neutralizes conversion method, oxygen both at home and abroad at present
Change method etc., using it is more be to handle waste sulfuric acid from alkylation using thermal cracking.Currently, both at home and abroad to the place of waste sulfuric acid from alkylation
Reason, specifically there is a following several method: 1. neutralisation, i.e., by dilution, neutralize Waste Sulfuric Acid with produce ammonium sulfate, phosphate fertilizer, calcium sulfate,
The products such as White Carbon black and pitch；2. heating cracking process, Waste Sulfuric Acid Pintsch process is formed into SO2Catalysis oxidation prepares sulfuric acid again,
The method is most common processing method；3. oxidizing process removes organic matter by oxidant and obtains dilute sulfuric acid.
CN1154946A disclosed method for regenerating waste sulfuric acid for alkylation in 1997, the method be by Waste Sulfuric Acid be added deodorant,
Decolorising agent heats in a kettle obtains black sulfuric acid after deodorization, decolorization, by black sulfuric acid process and oleum
Mixing or and SO3Reactive absorption SO3The concentration of black sulfuric acid is improved, reaches industrial sulphuric acid standard, is circularly used for alkyl metaplasia
It produces.But the deodorant potassium permanganate that the method uses, which belongs to, easily makes malicious reagent, and decolorising agent is strong corrosive nitric acid, and before deodorization and discoloration
The de-oiling that must just carry out takes off slag substance and does not refer to how handling.
CN103771353A disclosed a kind of regeneration method of waste sulfuric acid from alkylation in 2014, and the method is in redox item
Under part, Waste Sulfuric Acid is contacted with oxidation promoter, and the organic matter or small carbon particle in Waste Sulfuric Acid are converted with oxidant reaction
For CO2, N2, H20, the sulfuric acid after stripping removing, after being regenerated.The method for the regeneration waste sulfuric acid from alkylation that the invention provides
Lower pressure and at a temperature of carry out, device operation energy consumption is low, reduces investment outlay, and easy to operate, device maintenance cost is low.But the party
The service life or regeneration method of oxidation promoter is not disclosed in method.
CN105858622A disclosed a kind of waste sulfuric acid from alkylation resource recycle method in 2016, which includes following
Step: (1) it is mixed with dipping: being 1:1-10:1 hybrid infusion according to the solvent and solute weight ratio of Waste Sulfuric Acid and condensation carburization agent；(2) it is condensed
Carburizing reagent: by the Waste Sulfuric Acid after hybrid infusion be 95-145 DEG C in temperature with condensation carburization agent and pressure is normal pressure -0.05MPa
Condensation carburizing reagent 1-10 minutes is carried out, carbide and waste liquid are obtained；(3) it washs: by the multiple countercurrent washing of carbide, through filtering
After separation, carbide and filtrate are finally obtained；(4) decolouring and deodorizing: according to filtrate weight 1-10% be added decolouring and deodorizing agent in
After temperature is 50-100 DEG C of decolouring and deodorizing, recycling obtains black sulfuric acid；(5) carbon material recycles: the carbide that step (3) obtains
Active carbon is either further processed into for fuel.The method of the present invention when handling waste sulfuric acid from alkylation in lesser pressure and
It is carried out at lower temperature, device service condition is mild, and low energy consumption, with low investment, and operation is simpler, and device maintenance cost is lower.
But the method needs to consume a large amount of slurries and carbide recycles the problems such as value is indefinite.
CN106744716A disclosed a kind of method of waste sulfuric acid from alkylation Pintsch process production sulfuric acid, the method in 2017
Comprise the steps of: that (1) by Waste Sulfuric Acid pump to high-temperature cracking furnace, forms misty Waste Sulfuric Acid drop；(2) natural gas is passed through in furnace
And air, in-furnace temperature are controlled at 1000-1100 DEG C, (3) are by SO2And H2O is cooled to 330-400 DEG C；(4) it is sprayed and is increased with diluted acid
It is wet；(5) catalytic oxidation is carried out, SO is made2It is converted to SO3；(6) by SO3Gas cooling forms saturated water and steams to 260-320 DEG C
Gas；(7) by SO3Gas and air heat-exchange are realized further cooling, and cooling final temperature is 60-120 DEG C, and with the 98% of 70 DEG C
Sulfuric acid sprinkle absorbs the SO generated3, form sulfuric acid.The method process flow need to be relatively simple, but it is larger to consume energy, and Pintsch process
When, except generation SO2And H2Outside O, it is also possible to nitrogen, sulphur, the oxide of carbon and harmful substance of various complexity etc. are generated, after making
Phase SO2Purify the problems such as difficulty is big and catalysis oxidation used catalyst is poisoned.
The method that CN106744719A disclosed a kind of processing of waste sulfuric acid from alkylation and organic phase recycling in 2017, the method
The following steps are included: (1) Waste Sulfuric Acid removes suspended particulate substance by filtering pretreatment；(2) pretreated Waste Sulfuric Acid will be passed through
By filling the adsorption tower of resin, it is adsorbed on organic phase in Waste Sulfuric Acid on resin, organic phase is recycled；(3) dense with quality
Degree is that the alkaline aqueous solution of 4-16% regenerates the resin for having adsorbed organic matter as desorbing agent；(4) height being desorbed
Concentration desorption liquid is neutralized again with acid, recycles organic phase；(5) the dilute sulfuric acid waste liquid obtained after absorption in step (2) into
Row concentration, and adsorption bleaching is carried out with active carbon, the colorless and transparent concentrated sulfuric acid can be obtained.But there is also make repeatedly for the method
It is used as desorbing agent and neutralizer with alkali and acid, treatment agent consumption is big, and the salt after neutralization is difficult to the problems such as handling.
CN106744723A disclosed a kind of regeneration method of waste sulfuric acid from alkylation in 2017, and the method is in redox item
Under part, Waste Sulfuric Acid is contacted with hydrogen peroxide, and the organic matter or small carbon particle in Waste Sulfuric Acid are converted into hydroperoxidation
Carbon dioxide, nitrogen and water, the sulfuric acid after stripping removing, after being regenerated.But the method do not account for yet other impurities removal and
Recycling problem, it is difficult to really realize to purpose environment-friendly after Waste Sulfuric Acid processing.
Therefore, it is necessary to reasonably be improved prior art.
Summary of the invention
The present invention is directed to waste sulfuric acid from alkylation, and the present invention provides a kind of sides of thermally conductive resolution process waste sulfuric acid from alkylation
Method, it is main so that the high-risk waste sulfuric acid from alkylation liquid of multiple groups part is decomposed into two part of gas-solid and is recycled benefit using sealing is thermally conductive
With making Waste Sulfuric Acid become the resource that can re-use, and treatment process itself does not generate secondary pollution.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of method of thermally conductive resolution process waste sulfuric acid from alkylation, includes the following steps:
1) waste sulfuric acid from alkylation liquid is imported in the sandwich reactor of sealing, using the conduction oil in interlayer to alkylation
Waste Sulfuric Acid is heated to 270-350 DEG C, makes its decomposition, obtains the gas of multiple groups part and gradually becomes the acid pickle of solid；
2) gas of the multiple groups part for obtaining upper step is passed through equipped with recirculated cooling water and macromolecule resin adsorbent material
In sealing container, it is adsorbed gas into liquid phase；
3) acid pickle for becoming solid for obtaining step 1) and step 2) are adsorbed again by macromolecule resin adsorbent material
Raw water mixing, generates sulfuric acid solution using esterlysis reaction principle；
4) material that step 3) obtains is separated by solid-liquid separation with physical method, available dense sulphur is concentrated by heating into liquid
Acid, or ammonium hydroxide is added to become ammonium sulfate recycling in a liquid；
Macromolecule resin adsorbent material described in step 2) be it is a kind of had by sulfonic acid group with amide group two it is opposite
The high molecular polymer of functional group's synthesis of charge, is by polystyrene storng-acid cation exchange resin, N, N- dimethyl propylene
Acrylamide (DMAM) and the mixing of initiator potassium persulfate, in thermostatic container, under nitrogen protection, reaction, cooling, washing,
It dries in the shade to obtain, the polystyrene storng-acid cation exchange resin, is storng-acid cation exchange resin, model 001*7
(732), (734) 001*4, the polystyrene storng-acid cation exchange resin, N,N-DMAA and excessively two
Potassium sulfate, according to the mass ratio of 80:20:1,70-80 DEG C of reaction temperature, reaction time 10-12 hour.
Waste sulfuric acid from alkylation is heated using the conduction oil in interlayer described in step 1) of the present invention, is useless to heat
Acid solution 1kg meter, heating power 1000-1500w, heat-conducting oil heating time 0.5-1h are heated to 320-350 DEG C.
The gas that multiple groups part is obtained described in step 2) is passed through equipped with recirculated cooling water and macromolecule resin adsorbent material
It in sealing container, is adsorbed gas into liquid phase, is to obtain H2O、CO2、SO3、SO2、H2The gases such as S, gas by examining online
It surveys instrument to be respectively delivered in different sealing absorption tower, and is water-cooled, be then converted to it with the absorption of macromolecule resin adsorbent material
Its substance generates hydrosulphuric acid as hydrogen sulfide is reacted with water.
Step 2) is to carry out cooling to gas using water and enter macromolecule resin adsorbent material contactor, utilizes high score
Simultaneous with two kinds of opposite charges in subtree rouge adsorbent material molecule, hydrosulphuric acid etc. is absorbed, to make water and wherein be dissolved
Substance separation, recycle water.
Thermostatic container described in step 2) is the three-necked bottle of constant temperature.
The mass ratio of recirculated cooling water described in step 2) and macromolecule resin adsorbent material is 2-4:1.
The acid pickle for becoming solid and step 2) for obtaining step 1) described in step 3) are adsorbed by macromolecule resin
The water of material absorption regeneration mixes, and is mixed according to 6 ﹕, 2 volume ratio, is the compound configuration according to energy esterlysis sulfuric acid in solids
Depending on the amount of water, recycling sulfuric acid solution is reacted using esterlysis, obtains sulfuric acid solution and reuse.
Step 4) is to separate the solids insoluble in liquid with the mixture liquid for being dissolved in water, recycling
It utilizes, does not generate the sulfuric acid solution recycled to ecological environmental pollution and selected by utility value and cost, be converted into ammonium sulfate
Or concentration reuse is heated to ammonium sulfate.
Macromolecule resin adsorbent material used in the present invention is entwined on a kind of crosslinked with charge base
There is the polymer of the nemutogen of oppositely charged function base, there are two different groups, separation principles to be for tool: being to pass through the opposite sex
The effect of attracting (electrostatic) attracts each other the electrolyte that electrostatic is had in waste liquid, in synthesis macromolecule surface, without electrostatic
Discharge, thus reach metal ion, acid radical anion is separated from water effect, utilize synthesis macromolecule and waste liquid in electrolyte inhale
The power of attached power is rinsed with pure water, so that deliquescent metal solion and acid solution separation.
Compared to the prior art, the present invention has the advantages that
1, the present invention using conduction oil heat in interlayer reaction kettle make acid pickle realization gas solid separation, heating temperature compared with
It is low, it is also not required to that various reaction reagents are added.It is different using the temperature of various compound heat resolves, to the high dangerous waste alkyl of multiple groups part
Various gases can be separately recovered in heating temperature difference by changing sulfate liquid；It decomposes and waves according to each component in waste sulfuric acid from alkylation
Temperature difference is sent out, realizes that each component volatilization is separated with heating power by controlling different heating times.
2, for the present invention using heat-conducting oil heating to 320-350 DEG C, heat transfer endangers multiple groups part height in hermetically sealed reactor
Waste Sulfuric Acid mixed liquor heating, so that multiple groups part height is endangered organic matter, inorganic matter in Waste Sulfuric Acid and resolve at different temperature
Different gases are separated with solid.
3, the present invention only heats acid pickle with conduction oil, and heating temperature is lower (less than 350 DEG C), heating process
In, task substance is added not into acid pickle, no secondary " three wastes " generate, because with special macromolecule resin adsorption material is contained
The water of material adsorbs the sour gas that heat-conducting oil heating spent acid generates, and sour gas is no longer diffused into atmosphere, absorption
The water of sour gas is blocked by high molecular material again, becomes clean water regeneration.
Specific embodiment
Below with examples illustrate the present invention, but the invention is not limited to these embodiments.
Embodiment 1
Alkylation spent acid (being 1kg, heating power 1000w meter with treating capacity) processing method that sulfuric acid concentration is 86%, packet
Include following steps:
1) waste sulfuric acid from alkylation liquid is imported from storage tank with the extracting of acid corrosion-resistant centrifugal pump to the sandwich reactor of sealing
In, the waste sulfuric acid from alkylation in sandwich reactor is heated using the conduction oil (Oil-temperature control is 300-330 DEG C) in interlayer,
Acid pickle temperature is promoted to 90-150 DEG C in 5min, moisture etc. in acid pickle is made gradually to volatilize；Again in 15min will again by
Acid pickle temperature is promoted to 150-200 DEG C, is made organic matter and sulfuric acid etc. in acid pickle that redox reaction occur, is obtained CO2Deng
Gas；Acid liquor temperature is finally promoted sulfuric acid etc. in the organic matter and acid solution for make remaining to 200-300 DEG C in 20min to occur
Redox reaction, esterlysis reaction are decomposed, and CO is obtained2、SO3、SO2、H2The gas of the multiple groups part such as S；Liquid in sandwich reactor
Solid is gradually become, after solid content reaches 97%, solid is taken out, that is, completes moisture contained by alkylation acid pickle and steams
Hair, oxidation operation decomposition etc.；
2) 1) it will evaporate or decompose under 90-150 DEG C of step, 150-200 DEG C, 200-300 DEG C of this 3 different temperatures ranges
The gas of the multiple groups part arrived each leads into the sealing different from 3 of macromolecule resin adsorbent material equipped with recirculated cooling water and holds
In device, it is adsorbed gas into liquid phase；
3) step 2) water that wherein gaseous matter is discharged, pH value have been adsorbed by the high molecular material in different sealing container
Obtain pure water in 5.5-6.5, then through membrane separation (pH value 6-7, conductivity are 200 μ s)；
4) solid containing residual acid for obtaining step 1) mixes (solid: the body of water with the regeneration pure water that step 3) obtains
Product ratio=6:2), concentration 50%-60% sulfuric acid solution is generated using esterlysis reaction principle etc.；
5) material that the sulfuric acid concentration for obtaining step 4) is 50%-55% carries out solid-liquid point with physical method (centrifuge separation)
From, the available concentrated sulfuric acid for being 68%-73% at concentration to liquid pressure-reducing distillation and concentration, or directly isolated
In 68%-73% sulfuric acid solution plus ammonium hydroxide becomes ammonium sulfate recycling；
The macromolecule resin adsorbent material be by 001*7 (732) resin, N, N- dimethylacrylamide (DMAM) and
Initiator potassium persulfate is mixed according to the mass ratio of 80:20:1, in constant temperature three-necked bottle, under nitrogen protection, 70 DEG C of reactions
It 12 hours, cools down, wash, drying in the shade to obtain.
Embodiment 2
Alkylation spent acid (being 5kg, heating power 1000w meter with treating capacity) processing method that sulfuric acid concentration is 88%, packet
Include following steps:
1) waste sulfuric acid from alkylation liquid is imported from storage tank with the extracting of acid corrosion-resistant centrifugal pump to the sandwich reactor of sealing
In, the waste sulfuric acid from alkylation in sandwich reactor is heated using the conduction oil (Oil-temperature control is 300-330 DEG C) in interlayer,
Acid pickle temperature is promoted to 90-150 DEG C in 20min, moisture etc. in acid pickle is made gradually to volatilize；It again will again in 45min
Acid pickle temperature is promoted to 150-200 DEG C, makes organic matter and sulfuric acid etc. in acid pickle that redox reaction occur, obtains CO2
Equal gases；Acid liquor temperature is finally promoted into the hair such as sulfuric acid in the organic matter and acid solution for make remaining to 200-300 DEG C in 60min
Raw redox reaction, esterlysis reaction are decomposed, and CO is obtained2、SO3、SO2、H2The gas of the multiple groups part such as S；Liquid in sandwich reactor
Body gradually becomes solid, and after solid content reaches 97%, solid is taken out, that is, completes moisture contained by alkylation acid pickle
Evaporation, oxidation operation decomposition etc.；
2) 1) it will evaporate or decompose under 90-150 DEG C of step, 150-200 DEG C, 200-300 DEG C of this 3 different temperatures ranges
The gas of the multiple groups part arrived each leads into the sealing different from 3 of macromolecule resin adsorbent material equipped with recirculated cooling water and holds
In device, it is adsorbed gas into liquid phase；
3) step 2) water that wherein gaseous matter is discharged, pH value have been adsorbed by the high molecular material in different sealing container
Obtain pure water in 5.5-6.5, then through membrane separation (pH value 6-7, conductivity are 200 μ s)；
4) solid containing residual acid for obtaining step 1) mixes (solid: the body of water with the regeneration pure water that step 3) obtains
Product ratio=6:2), concentration 50%-60% sulfuric acid solution is generated using esterlysis reaction principle etc.；
5) material that the sulfuric acid concentration for obtaining step 4) is 53%-58% carries out solid-liquid point with physical method (centrifuge separation)
From, the available concentrated sulfuric acid for being 70%-75% at concentration to liquid pressure-reducing distillation and concentration, or directly isolated
In 53%-58% sulfuric acid solution plus ammonium hydroxide becomes ammonium sulfate recycling；
The macromolecule resin adsorbent material be by 001*7 (732) resin, N, N- dimethylacrylamide (DMAM) and
Initiator potassium persulfate is mixed according to the mass ratio of 80:20:1, in constant temperature three-necked bottle, under nitrogen protection, 70 DEG C of reactions
It 12 hours, cools down, wash, drying in the shade to obtain.
Embodiment 3
Alkylation spent acid (being 10kg, heating power 1000w meter with treating capacity) processing method that sulfuric acid concentration is 90%, packet
Include following steps:
1) waste sulfuric acid from alkylation liquid is imported from storage tank with the extracting of acid corrosion-resistant centrifugal pump to the sandwich reactor of sealing
In, the waste sulfuric acid from alkylation in sandwich reactor is heated using the conduction oil (Oil-temperature control is 330-350 DEG C) in interlayer,
Acid pickle temperature is promoted to 90-150 DEG C in 40min, moisture etc. in acid pickle is made gradually to volatilize；It again will again in 60min
Acid pickle temperature is promoted to 150-200 DEG C, makes organic matter and sulfuric acid etc. in acid pickle that redox reaction occur, obtains CO2
Equal gases；Acid liquor temperature is finally promoted into the hair such as sulfuric acid in the organic matter and acid solution for make remaining to 200-300 DEG C in 75min
Raw redox reaction, esterlysis reaction are decomposed, and CO is obtained2、SO3、SO2、H2The gas of the multiple groups part such as S；Liquid in sandwich reactor
Body gradually becomes solid, and after solid content reaches 97%, solid is taken out, that is, completes moisture contained by alkylation acid pickle
Evaporation, oxidation operation decomposition etc.；
2) it will evaporate or decompose under 90-150 DEG C of step 1), 150-200 DEG C, 200-300 DEG C of this 3 different temperatures ranges
The gas of the multiple groups part arrived each leads into the sealing different from 3 of macromolecule resin adsorbent material equipped with recirculated cooling water and holds
In device, it is adsorbed gas into liquid phase；
3) step 2) water that wherein gaseous matter is discharged, pH value have been adsorbed by the high molecular material in different sealing container
Obtain pure water in 5.5-6.5, then through membrane separation (pH value 6-7, conductivity are 200 μ s)；
4) solid containing residual acid for obtaining step 1) mixes (solid: the body of water with the regeneration pure water that step 3) obtains
Product ratio=6:2), concentration 55%-60% sulfuric acid solution is generated using esterlysis reaction principle etc.；
5) material that the sulfuric acid concentration for obtaining step 4) is 55%-60% carries out solid-liquid point with physical method (centrifuge separation)
From, the available concentrated sulfuric acid for being 73%-80% at concentration to liquid pressure-reducing distillation and concentration, or directly isolated
In 55%-60% sulfuric acid solution plus ammonium hydroxide becomes ammonium sulfate recycling；
The macromolecule resin adsorbent material be by 001*7 (732) resin, N, N- dimethylacrylamide (DMAM) and
Initiator potassium persulfate is mixed according to the mass ratio of 80:20:1, in constant temperature three-necked bottle, under nitrogen protection, 70 DEG C of reactions
It 12 hours, cools down, wash, drying in the shade to obtain.
Comparative example
Alkylation spent acid (being 1kg, heating power 1000w meter with treating capacity) processing method that sulfuric acid concentration is 86%, packet
Include following steps:
1) waste sulfuric acid from alkylation liquid is imported from storage tank with the extracting of acid corrosion-resistant centrifugal pump to the sandwich reactor of sealing
In, the waste sulfuric acid from alkylation in sandwich reactor is heated using the conduction oil (Oil-temperature control is 300-330 DEG C) in interlayer,
Acid pickle temperature is promoted to 90-150 DEG C in 5min, moisture etc. in acid pickle is made gradually to volatilize；Again in 15min will again by
Acid pickle temperature is promoted to 150-200 DEG C, is made organic matter and sulfuric acid etc. in acid pickle that redox reaction occur, is obtained CO2Deng
Gas；Acid liquor temperature is finally promoted sulfuric acid etc. in the organic matter and acid solution for make remaining to 200-300 DEG C in 20min to occur
Redox reaction, esterlysis reaction are decomposed, and CO is obtained2、SO3、SO2、H2The gas of the multiple groups part such as S；Liquid in sandwich reactor
Solid is gradually become, after solid content reaches 97%, solid is taken out, that is, completes moisture contained by alkylation acid pickle and steams
Hair, oxidation operation decomposition etc.；
2) 1) it will evaporate or decompose under 90-150 DEG C of step, 150-200 DEG C, 200-300 DEG C of this 3 different temperatures ranges
The gas of the multiple groups part arrived each leads into 3 different sealing containers equipped with recirculated cooling water, gas is made to be adsorbed entrance
Liquid phase；
3) step 2) wherein gaseous matter has been adsorbed by the alkaline aqueous solution dissolution in different sealing container, for adsorbing
The aqueous slkali mass percentage concentration of 90-150 DEG C of emergent gas is 1%；For adsorbing the aqueous slkali matter of 150-200 DEG C of emergent gas
Measuring percentage concentration is 1.5%；Aqueous slkali mass percentage concentration for adsorbing 200-300 DEG C of emergent gas is 2.5%；3 connect
The pH value of water solution for having received emergent gas is controlled in 4.5-6.5, into industrial park centralization sewage treatment plant；
4) solid containing residual acid for obtaining step 1) mixes (solid: volume ratio=6:2 of water) with pure water, utilizes ester
It solves reaction principle etc. and generates concentration 45%-48% sulfuric acid solution；
5) material that the sulfuric acid concentration for obtaining step 4) is 45%-48% carries out solid-liquid point with physical method (centrifuge separation)
From, the available sulfuric acid for being 60%-70% at concentration to liquid pressure-reducing distillation and concentration, or directly in isolated 45%-
In 48% sulfuric acid solution plus ammonium hydroxide becomes ammonium sulfate recycling；
6) alkaline aqueous solution described in is sodium carbonate liquor, and aqueous slkali dosage is determined with acidometer on-line testing, with final
PH value of water solution control after absorption is 4.5-6.5；
7) escape various gases with the waste sulfuric acid from alkylation that alkaline aqueous solution adsorbs thermally conductive resolution process (is with sour gas
It is main), finally obtained salting liquid enters sewage treatment plant and is further processed.
Claims (6)
1. a kind of method of thermally conductive resolution process waste sulfuric acid from alkylation, which comprises the steps of:
1) waste sulfuric acid from alkylation liquid is imported in the sandwich reactor of sealing, using the conduction oil in interlayer to alkylation sulfur waste
Acid is heated to 270-350 DEG C, makes its decomposition, obtains the gas of multiple groups part and gradually becomes the acid pickle of solid；
2) gas of the multiple groups part for obtaining upper step is passed through the sealing equipped with recirculated cooling water Yu macromolecule resin adsorbent material
In container, it is adsorbed gas into liquid phase；
3) acid pickle for becoming solid for obtaining step 1) and step 2) pass through macromolecule resin adsorbent material absorption regeneration
Water mixing generates sulfuric acid solution using esterlysis reaction principle；
4) material that step 3) obtains is separated by solid-liquid separation with physical method, the available concentrated sulfuric acid is concentrated by heating into liquid,
Or ammonium hydroxide is added to become ammonium sulfate recycling in a liquid；
Macromolecule resin adsorbent material described in step 2) be it is a kind of by sulfonic acid group with amide group two with opposite charges
Functional group synthesis high molecular polymer, be by polystyrene storng-acid cation exchange resin, N, N- dimethyl allene acyl
Amine and the mixing of initiator potassium persulfate, in thermostatic container, under nitrogen protection, react, cool down, wash, drying in the shade to obtain, institute
The polystyrene storng-acid cation exchange resin stated, is storng-acid cation exchange resin, and model 001*7,001*4 is described
Polystyrene storng-acid cation exchange resin, N,N-DMAA and potassium persulfate, according to the matter of 80:20:1
Amount ratio, 70-80 DEG C of reaction temperature, reaction time 10-12 hour.
2. a kind of method of thermally conductive resolution process waste sulfuric acid from alkylation according to claim 1, it is characterised in that: step 1)
Described heats waste sulfuric acid from alkylation using the conduction oil in interlayer, is the heating power to heat in terms of acid pickle 1kg
1000-1500w, heat-conducting oil heating time 0.5-1h, is heated to 320-350 DEG C.
3. a kind of method of thermally conductive resolution process waste sulfuric acid from alkylation according to claim 1, it is characterised in that: step 2)
Described obtains the gas of multiple groups part, is passed through in the sealing container equipped with recirculated cooling water and macromolecule resin adsorbent material, makes
Gas is adsorbed into liquid phase, is to obtain H2O、CO2、SO3、SO2、H2S, gas, gas are respectively delivered to by on-line detector
It in different sealing absorption tower, and is water-cooled, is then converted to other materials with the absorption of macromolecule resin adsorbent material.
4. a kind of method of thermally conductive resolution process waste sulfuric acid from alkylation according to claim 1, it is characterised in that: step 2)
The thermostatic container is the three-necked bottle of constant temperature.
5. a kind of method of thermally conductive resolution process waste sulfuric acid from alkylation according to claim 1, it is characterised in that: step 2)
The mass ratio of the recirculated cooling water and macromolecule resin adsorbent material is 2-4:1.
6. a kind of method of thermally conductive resolution process waste sulfuric acid from alkylation according to claim 1, it is characterised in that: step 3)
The acid pickle for becoming solid that step 1) is obtained and step 2) passes through macromolecule resin adsorbent material absorption regeneration
Water mixing is mixed according to 6 ﹕, 2 volume ratio, depending on the amount of the compound configuration water of energy esterlysis sulfuric acid in solids, is utilized
Esterlysis reaction recycling sulfuric acid solution, obtains sulfuric acid solution and reuse.
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| CN201910023260.3A CN109485021A (en) | 2019-01-10 | 2019-01-10 | A kind of method of thermally conductive resolution process waste sulfuric acid from alkylation |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86101738A (en) * | 1986-03-15 | 1987-03-25 | 刘清林 | The waste acid recycling method of sulfuric acid alkylation |
| US4985118A (en) * | 1987-03-24 | 1991-01-15 | Konica Corporation | Method for treating photographic process waste liquor through concentration by evaporation |
| US5989391A (en) * | 1995-04-27 | 1999-11-23 | Nissan Chemical Industries, Ltd. | Reaction product of sulfonated amino resin and amino group-containing substance and papermaking process |
| CN105000536A (en) * | 2015-07-03 | 2015-10-28 | 青岛奥盖克化工股份有限公司 | Recycling technology of alkylate oil waste sulfuric acid |
| CN105600997A (en) * | 2016-03-17 | 2016-05-25 | 广西钦州环科水处理有限公司 | Method for treating waste liquid generated by metal pickling |
| CN105858622A (en) * | 2016-05-19 | 2016-08-17 | 广西南宁东和新赢环保技术有限公司 | Alkylation waste sulfuric acid resource recycling method |
| CN106966370A (en) * | 2017-03-17 | 2017-07-21 | 常州大学 | A kind of high-efficient treatment method of alkylate oil Waste Sulfuric Acid |
| CN107792836A (en) * | 2016-08-31 | 2018-03-13 | 中国石油化工股份有限公司 | The renovation process and device of a kind of waste sulfuric acid from alkylation |
-
2019
- 2019-01-10 CN CN201910023260.3A patent/CN109485021A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86101738A (en) * | 1986-03-15 | 1987-03-25 | 刘清林 | The waste acid recycling method of sulfuric acid alkylation |
| US4985118A (en) * | 1987-03-24 | 1991-01-15 | Konica Corporation | Method for treating photographic process waste liquor through concentration by evaporation |
| US5989391A (en) * | 1995-04-27 | 1999-11-23 | Nissan Chemical Industries, Ltd. | Reaction product of sulfonated amino resin and amino group-containing substance and papermaking process |
| CN105000536A (en) * | 2015-07-03 | 2015-10-28 | 青岛奥盖克化工股份有限公司 | Recycling technology of alkylate oil waste sulfuric acid |
| CN105600997A (en) * | 2016-03-17 | 2016-05-25 | 广西钦州环科水处理有限公司 | Method for treating waste liquid generated by metal pickling |
| CN105858622A (en) * | 2016-05-19 | 2016-08-17 | 广西南宁东和新赢环保技术有限公司 | Alkylation waste sulfuric acid resource recycling method |
| CN107792836A (en) * | 2016-08-31 | 2018-03-13 | 中国石油化工股份有限公司 | The renovation process and device of a kind of waste sulfuric acid from alkylation |
| CN106966370A (en) * | 2017-03-17 | 2017-07-21 | 常州大学 | A kind of high-efficient treatment method of alkylate oil Waste Sulfuric Acid |
Non-Patent Citations (1)
| Title |
|---|
| 张振儒: "烷基化废硫酸回收技术探讨", 《石油化工环境保护》 * |
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