CN105858622A - Alkylation waste sulfuric acid resource recycling method - Google Patents
Alkylation waste sulfuric acid resource recycling method Download PDFInfo
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- CN105858622A CN105858622A CN201610335736.3A CN201610335736A CN105858622A CN 105858622 A CN105858622 A CN 105858622A CN 201610335736 A CN201610335736 A CN 201610335736A CN 105858622 A CN105858622 A CN 105858622A
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- carbide
- sulfuric acid
- acid
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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
- C01B17/90—Separation; Purification
- C01B17/92—Recovery from acid tar or the like, e.g. alkylation acids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L5/00—Solid fuels
- C10L5/40—Solid fuels essentially based on materials of non-mineral origin
- C10L5/44—Solid fuels essentially based on materials of non-mineral origin on vegetable substances
- C10L5/447—Carbonized vegetable substances, e.g. charcoal, or produced by hydrothermal carbonization of biomass
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an alkylation waste sulfuric acid resource recycling method which comprises the following steps: (1) mixed impregnation: performing mixed impregnation according to the liquid-solid weight ratio of waste sulfuric acid to a condensation carbonization agent of 1:1 to 10:1; (2) condensation carbonization reaction: performing condensation carbonization reaction on the waste sulfuric acid and the condensation carbonization agent, subjected to mixed impregnation, for 1 to 10 minutes under temperature of 95 to 145 DEG C and normal pressure of 0.05MPa to obtain carbide and waste liquid; (3) washing: backwashing the carbide for many times, and performing filtration and separation to finally obtain carbide and filtrate; (4) decolorization and deodorization: adding a decolorization and deodorization agent in an amount which is 1 to 10 percent of the weight of the filtrate for decolorization and deodorization at temperature of 50 to 100 DEG C, and performing recycling to obtain regenerated sulfuric acid; (5) carbon material recycling: employing the carbide obtained in step (3) as a fuel or further processing the carbide into activated carbon. According to the method, the alkylation waste sulfuric acid is treated under lower pressure and lower temperature, and the method is mild in device running condition, low in energy consumption, less in investment, easier to operate and lower in device maintenance cost.
Description
Technical field
The present invention relates to a kind of containing Organic substance with the resource recycle method of the high-concentration sulfuric acid of inorganic contaminants, more specifically
Ground is said, when relating to producing high-octane rating alkylate oil, and the resource recycle method of produced dead catalyst-Waste Sulfuric Acid.
Background technology
At present in petroleum refining process, produce high-octane rating alkylation oil process in lower carbon number hydrocarbons quasi-molecule alkylation
In, generally employing concentrated sulphuric acid is as catalyst, when alkylation, in purification and washing, absorption, cyclic process, in raw material
Moisture, side reaction product etc. constantly enter in concentrated sulfuric acid catalyst, and sulfuric acid concentration is gradually lowered, when concentrated sulphuric acid concentration is less than 90%
Time, it is with regard to loss of activity, then make Waste Sulfuric Acid and discharge, form waste sulfuric acid from alkylation.Produce 1 t alkymer and about produce 80-100 kg
Waste Sulfuric Acid, this acid is the colloidal liquid that a kind of viscosity is bigger, and color and luster is dark red, H2SO4Mass fraction is 82%～90%, H2O is
5%-8%, hydrocarbons (organic polymer oil) is 5%-10%.
And organic polymer oil is mainly some macromolecule alkene, alkadienes, alkyl sulfonic acid, sulfuric ester and dissolves therein
The material such as hydrogen sulfide, mercaptan, monomeric species up to more than 300 is planted.The Waste Sulfuric Acid character discharged is unstable, can give out special thorn
Swash property abnormal smells from the patient, be difficult to process, as do not dealt carefully with, it will bring serious threat and severe contamination to ecological environment.Therefore, state
Inside and outside utilize waste sulfuric acid from alkylation process and Resource recoveryization is attached great importance to.
Summary processing method to waste sulfuric acid from alkylation both at home and abroad, is roughly divided into three kinds, and one is neutralisation, i.e. dilution, in
And Waste Sulfuric Acid, production of chemicals such as ammonium sulfate, phosphate fertilizer, calcium sulfate, White Carbon black and various oil products etc.；Two is pyrolysismethod, will give up
After sulphuric acid is pyrolyzed into sulfur dioxide, prepare sulphuric acid, sulfur dioxide and sulfur；Three is oxidizing process, i.e. uses various oxidant, by sulfur waste
Organic substance in acid and oxidation of coal, after decolouring and deodorizing, obtain the sulphuric acid of low concentration, then carry out enrichment, complex acid, or directly make
With.
The chemicals that above-mentioned first method is produced, owing to sulfuric acid concentration there to be in being produced certain requirement, thus dilute
Releasing ratio can not be big, then cause organic polymer oil to separate with dilute sulfuric acid not thorough, and these chemicals commodity prices are low simultaneously, given birth to
Produce the restriction of cost, it is impossible to carry out re-refining such as washing, decolouring and deodorizing, and cause that product quality is inferior, lack the market competitiveness.
Above-mentioned second method, pyrolysismethod produces sulphuric acid etc., and investment is big, energy consumption is high, cost is high, needs large-scale production ability
Ensure that pyrolysis oven is properly functioning, if focusing on, being restricted by Waste Sulfuric Acid transport again, and economic benefit is difficult to ensure that.
The third method above-mentioned, needs to consume substantial amounts of oxidant, generates more sulfur dioxide, still needs to locate further
Reason, and cause processing cost high, and material with carbon element can not be reclaimed.
1, application number: 201210410373.7；Denomination of invention: the renovation process of a kind of waste sulfuric acid from alkylation；Summary: one
Plant the renovation process of waste sulfuric acid from alkylation, including: under Redox Condition, Waste Sulfuric Acid contacts with oxidation promoter, in Waste Sulfuric Acid
Organic substance or small carbon granule react with oxidant and obtain being converted into CO2、N2、H2O, after stripping removing, after being regenerated
Sulphuric acid.The present invention provide regeneration waste sulfuric acid from alkylation method lower pressure and at a temperature of carry out, plant running energy consumption
Low, reduce investment outlay, simple to operate, device maintenance cost is low.
2, application number: 201510387858.2；Applicant: Qingdao Aogaike Chemical Industry Co., Ltd.；Denomination of invention: one
Plant the recycle utilization of alkylate oil Waste Sulfuric Acid；Summary: the present invention relates to a kind of alkylate oil Waste Sulfuric Acid recycles skill
Art: isobutene. dimerization produces the Waste Sulfuric Acid that isobutyltrimethylmethane. produces, directly or add appropriate sulfur and be heated to 180-260 DEG C, produces
Sulfur dioxide, the sulfur dioxide that sulfur dioxide is through washing, dried generation is pure, sulphite can be produced further or pass through
The operations such as sulfur dioxide catalysis oxidation, absorption produce sulphuric acid.The Waste Sulfuric Acid that this process is reduced accounts for alkylate oil Waste Sulfuric Acid
About 40-70%.After reaction terminates, adding water in residue, scrubbed, filter pressing, concentration can produce content more than 80%
Sulphuric acid, can utilize with secondary, it is also possible to absorbs sulfur trioxide further and produces sulphuric acid.
3, application number: 201510429749.2；Applicant: science and technology Engineering Co., Ltd in sky in Shandong；Denomination of invention: process
The technique of waste sulfuric acid from alkylation；Summary: the invention belongs to Waste Sulfuric Acid process field, is specifically related to a kind of process waste sulfuric acid from alkylation
Technique, using sulfur as fuel, air is as combustion adjuvant.The present invention realizes waste sulfuric acid from alkylation at high temperature, without fuel gas
In the case of cracking process, it is thus achieved that while qualified concentrated sulphuric acid product, it is to avoid the discharge of greenhouse gases, a large amount of for alkylate oil
Production solves environmental issue, and, equipment investment is few, and technique is simple, it is possible to also obtain benefit while turning waste into wealth.
4, application number: 201410200204.X；Applicant: Shandong gold really heavy oil Chemical Engineering Technology academy；Denomination of invention: one
Plant sulfuric acid process alkylation acid-restoring plant dilute acid pretreatment system；Summary: a kind of sulfuric acid process alkylation acid-restoring plant diluted acid
Processing system, belongs to petroleum refining technology field, including packed tower, it is characterized in that, at packed tower thin acid pump inlet suction tube line
On, switchable two groups of gauze filters in parallel are set；On packed tower outlet line Shang Fen bis-tunnel, a road is through diluted acid plate heat exchange
Return to packed tower top after device cooling, to draw respectively under the control of dilute acid streams gauge and regulation valve as washing diluted acid, another road
Enter drying tower circulating slot, a suction tower circulating slot, two suction tower circulating slots.The present invention had both saved softening water consumption, reduced again at diluted acid
Science and engineering sequence, alleviates the pressure of sewage disposal, the abnormal flavour produced when eliminating diluted acid discharge, saves quick lime consumption simultaneously, and minimizing sets
Standby power consumption, reduces the amount of labour.
5, application number: 201410200204.X；Applicant: Shandong gold really heavy oil Chemical Engineering Technology academy；Denomination of invention: one
Plant sulfuric acid process alkylation acid-restoring plant dilute acid pretreatment system；Summary: a kind of sulfuric acid process alkylation acid-restoring plant diluted acid
Processing system, belongs to petroleum refining technology field, including packed tower, it is characterized in that, at packed tower thin acid pump inlet suction tube line
On, switchable two groups of gauze filters in parallel are set；On packed tower outlet line Shang Fen bis-tunnel, a road is through diluted acid sheet heat exchanger
Return to packed tower top after cooling, to introduce respectively under the control of dilute acid streams gauge and regulation valve as washing diluted acid, another road
Drying tower circulating slot, a suction tower circulating slot, two suction tower circulating slots.The present invention had both saved softening water consumption, reduced again dilute acid pretreatment
Operation, alleviates the pressure of sewage disposal, the abnormal flavour produced when eliminating diluted acid discharge, saves quick lime consumption simultaneously, reduces equipment
Power consumption, reduces the amount of labour.
6, applicant: straight bravely；Application number: 201310625176.1；Denomination of invention: during a kind of sulfuric acid process alkylation produces
The method and apparatus of Waste Sulfuric Acid concentration；Summary: the present invention relates to sulfuric acid process alkylation production field, in particular to one
The method and apparatus of Waste Sulfuric Acid concentration in sulfuric acid process alkylation production.The side of Waste Sulfuric Acid concentration in this sulfuric acid process alkylation production
Method, including: the Waste Sulfuric Acid after in-depth being processed mixes with oleum, is configured to the sulfur that mass percent concentration is 100%
Acid；The equipment of Waste Sulfuric Acid concentration in this sulfuric acid process alkylation production, including: blender, first flow actuator, second flow are adjusted
Save device, for carrying the first input duct of Waste Sulfuric Acid after in-depth processes, the second input duct and drain pipe road；First feed liquor
Pipeline and the second input duct are connected with the entrance of blender, and drain pipe road is connected with the outlet of blender, and first flow regulates
Device is arranged in the first input duct, and second flow actuator is arranged in the second input duct.This method and apparatus can be very
Well Waste Sulfuric Acid is recycled, solve Waste Sulfuric Acid and directly arrange outward the problem polluted the environment.
Wherein, the technical scheme of document 1 and the technology of the present invention are pressed close to most, mainly under Redox Condition, and Waste Sulfuric Acid
Contacting with oxidation promoter, Organic substance or small carbon granule in Waste Sulfuric Acid react with oxidant and obtain being converted into CO2、N2、H2O,
After stripping removing, the sulphuric acid after being regenerated, this method is in processing procedure, simply simply by Organic substance therein or micro-
Little carbon granule aoxidizes, and does not in fact remove hydrocarbons (macromolecule alkene, alkadienes, the alkyl sulphur in Waste Sulfuric Acid
Acid, sulfuric ester and dissolve the materials such as hydrogen sulfide therein, mercaptan).And this processing method needs to carry out at 150 DEG C ~ 250 DEG C
Redox reaction, the material of reactor is selected from tantalum material, titanium material, inner lining glass fiber reinforced plastic or quartz glass, but inventor is in test
During find, under the oxidizing temperature of 150-250 DEG C, a lot of materials all bear the corrosion of concentrated sulphuric acid under incessantly high temperature, as
Tantalum material: tantalum material can be corroded in the concentrated sulphuric acid of heat, and below 150 DEG C, tantalum will not be corroded by concentrated sulphuric acid, only higher than this temperature
Degree just can respond, in the concentrated sulphuric acid of 175 DEG C 1 year, and the thickness being corroded is 0.0004 millimeter；Tantalum is put into the sulfur of 200 DEG C
Soaking 1 year in acid, top layer only damages 0.006 millimeter；When 250 DEG C, corrosion rate increased, for the thickness being corroded every year
Degree is 0.116 millimeter；When 300 DEG C, the speed being corroded the most more is accelerated, and soaks 1 year, and surface is corroded 1.368 millimeters；And for example
Titanium material: titanium material has certain corrosion resistance to the sulfuric acid concentration of low-temperature and low-concentration, at 0 DEG C, is resistant to concentration and reaches the sulphuric acid corruption of 20%
Erosion, along with concentration and the rising of temperature of acid, rate of corrosion increases, therefore titanium material poor stability in sulphuric acid, is even dissolving
Under oxygen room temperature, titanium material can only resistance to 5% sulfuric acid corrosion, at 100 DEG C, titanium material can only resistance to 0.12% concentration corrosion；For another example: liner
It is about 35% that glass-reinforced plastic material is resistant to sulfuric acid concentration, and temperature is the corrosion of 80-100 DEG C, and temperature raises, corrosion aggravation；
Concentrated sulphuric acid has strong oxidizing property and dewatering by fiberglass carbonization, and after using a period of time, glass steel material can deliquescing, logical leakage；
Therefore use above material to carry out redox reaction at the pressure that 150-250 DEG C and normal pressure～5.0MPa are the biggest, easily make
The damage of forming apparatus, has had a strong impact on the normal operation of equipment, so, has not only resulted in acid leakage, add unsafe factor,
It is also desirable to thrown in people's production by substantial amounts of human and material resources, affect the efficiency of factory further, improve production cost.
Summary of the invention
In order to overcome the technological deficiency of above-mentioned existence, inventor provides a kind of waste sulfuric acid from alkylation resource recycle method,
The method, with relatively low temperature and pressure, utilizes dehydration property and the oxidisability of concentrated sulphuric acid, by the carbon granule in Waste Sulfuric Acid and organic
Thing condensation, carbonization, obtain carbide, after carbide is carried out repeatedly countercurrent washing, reclaims, for fuel or adds further
The Viability charcoal of work；And the filtrate after carbide is scrubbed uses decolouring and deodorizing agent to carry out decolouring and deodorizing, decompose being harmful in filtrate
After material, obtain the sulphuric acid of regeneration, for producing sulfate or for preparing the sulphuric acid of less than 93% concentration.
In order to realize the purpose of the present invention, technical scheme is as follows:
A kind of waste sulfuric acid from alkylation resource recycle method, comprises the following steps:
(1) hybrid infusion: according to Waste Sulfuric Acid with condensation carburization agent solvent and solute weight ratio be 1:1-10:1 hybrid infusion under room temperature
3-10 minute；
(2) condensation carburizing reagent: the Waste Sulfuric Acid after hybrid infusion is 95-145 DEG C and pressure is with being condensed carburization agent in temperature
Normal pressure-0.05MPa carries out being condensed carburizing reagent 1-10 minute, obtains carbide and waste liquid；
(3) washing: by carbide repeatedly countercurrent washing, after being separated by filtration, finally give purer carbide and acid concentration
The highest filtrate；
(4) decolouring and deodorizing: the 1-10% of the weight of the filtrate that the acid concentration that obtains according to step (3) is the highest adds decolouring and deodorizing agent
After temperature is 50-100 DEG C of decolouring and deodorizing, reclaim, obtain the sulphuric acid of regeneration, be used for producing sulfate or for gas washing in SA production mistake
Journey, absorbs sulfur trioxide, generates high concentration (more than 98%) sulphuric acid or the sulphuric acid for preparation less than 93% concentration.
(5) material with carbon element reclaims: the purer carbide that step (3) obtains can be used for fuel or is further processed into
Activated carbon.
Condensation carburization agent described in step (1) is biological material, including powder of straw, bagasse, wood bran, leaf powder and open country
One in grass meal or a combination thereof thing.
In condensation carburizing reagent described in step (2), liner material used is Hastelloy, high manganese stainless steel, Gao Meng
Any one in cast iron and cupric rustless steel.
The method of the repeatedly countercurrent washing described in step (3) is: first, uses filter to filter carbide and waste liquid, profit
Wash carbide with clear water, filter with filter and separate, obtain filtrate, merge waste liquid；With filtrate and waste liquid as washing liquid, use and filter
Carbide is washed by machine again, obtains liquor B；Again with liquor B as washing liquid, filter is used again carbide to be washed
Wash, obtain liquor C；The filtrate utilizing upper level is again repeated 1-7 countercurrent washing to carbide, divides through repeatedly washing and filtering
From rear, finally give purer carbide and the highest filtrate of acid concentration.
Decolouring and deodorizing agent described in step (4) is value Mn compound, hydrogen peroxide, ozone, nitric acid and nitrate and nitrogen
Any one in oxide.
The biological material used includes the one in powder of straw, bagasse, wood bran, leaf powder and weeds powder or its group
Compound, is carbon compound in these biological materials, and internal void is flourishing, and specific surface area is big, has excellent absorption
Performance.Powder of straw, bagasse, wood bran, leaf powder and weeds powder these be all Organic substance, when contacting with concentrated sulphuric acid, utilize dense
Hydrogen, oxygen element in high dehydrated Organic substance of sulphuric acid are sloughed by the ratio of components (2:1) of water, leave the carbon of black, thus send out
Raw carbonization phenomenon.Therefore, these biological materials not only have excellent absorption property, also act as certain carbonization, warp
Activated carbon can be further processed into after carbonization.
A part in Organic substance is carried out in carburizing reagent, and Waste Sulfuric Acid by Waste Sulfuric Acid and condensation carburization agent at normal temperatures
H2SO4Mass fraction be 82%～90%, when being heated to temperature 95-145 DEG C, there is stronger oxidisability and dehydration property, make to be left
Organic substance generation carburizing reagent and redox reaction；Carburizing reagent equation is:
CnH2nOnNC+n H2O
Redox reaction is as follows:
Organic substance+2H2SO4(dense) CO2↑+2SO2↑+2H2O
Utilize the filtrate of upper level, as the cleaning mixture of next stage, carbide is carried out countercurrent washing the most repeatedly, have two mesh
, first purpose is to reclaim the valuable filtrate of residual in carbide, and removes the soluble impurity in filter cake, makes
Separate more thorough, to improve the purity of carbide；Another purpose is that the filtrate constantly utilizing upper level is as next stage
Cleaning mixture, gets rid of the acid ion in carbide, applies mechanically the most forward, and in filtrate, the concentration of sulphuric acid steps up.This
Bright employing countercurrent washing, uses less amount of clear water, obtains satisfied clean result.
Filtrate carries out decolouring and deodorizing, and described decolouring and deodorizing agent is value Mn compound, hydrogen peroxide, ozone, nitric acid
With the one in nitrate and nitrogen oxides or a combination thereof thing.If with nitric acid as decolouring and deodorizing agent, reaction equation being:
Organic substance+HNO3(dense) → CO2 ↑+NOX+ H2O (X=1 or 2 in formula)
C+HNO3(dense) → CO2↑+NO2 ↑+H2O
Compared with prior art, the positive effect of the present invention is:
1, the inventive method can be (normal in relatively low temperature (95-145 DEG C) and less pressure when processing waste sulfuric acid from alkylation
Pressure-0.05MPa) under carry out, and the response time is short, and whole course of reaction operating condition is gentle, and organic removal rate is higher, useless
Acid need not be through dilution；Plant running energy consumption is low, and maintenance cost is low.
2, in the present invention, the part in Organic substance is carried out carburizing reagent by Waste Sulfuric Acid and condensation carburization agent at normal temperatures,
And H in Waste Sulfuric Acid2SO4Mass fraction be 82%～90%, when being heated to temperature 95-145 DEG C, have stronger oxidisability and
Dehydration property, makes remaining Organic substance continue carburizing reagent and redox reaction, generates carbide and the CO of porous2、
SO2Deng oxycarbide or sulphur oxide gas, get rid of most of hydrocarbons ((macromolecule alkene, the diene in Waste Sulfuric Acid
Hydrocarbon, alkyl sulfonic acid, sulfuric ester and dissolve the materials such as hydrogen sulfide therein, mercaptan), carbide is carried out repeatedly countercurrent washing
After, reclaim, for fuel or be further processed into activated carbon；And the filtrate after carbide is scrubbed uses decolouring and deodorizing agent
Carry out decolouring and deodorizing, after decomposing the harmful substance in filtrate, reclaim, obtain the sulphuric acid of regeneration, be used for producing sulfate or being used for
Sulphuric acid process, absorbs sulfur trioxide, generates high concentration (more than 98%) sulphuric acid or the sulphuric acid for preparation less than 93% concentration.
3, using the waste sulfuric acid from alkylation resource recycle method of the present invention, the carbon response rate in Waste Sulfuric Acid is up to 80-
90%, the carbide reclaimed can be used for fuel or is further processed into activated carbon.
4, using the waste sulfuric acid from alkylation resource recycle method of the present invention, the Waste Sulfuric Acid response rate is up to 80-90%, finally
The sulfuric acid concentration reclaimed is up to 70-80%, and the sulphuric acid of gained can be used for producing sulfate or for preparing the sulfur of less than 93% concentration
Acid.
5, the waste sulfuric acid from alkylation resource recycle method of the present invention, reduced investment, instant effect are used.
Detailed description of the invention
Embodiment 1
A kind of waste sulfuric acid from alkylation resource recycle method, comprises the following steps:
(1) hybrid infusion: according to Waste Sulfuric Acid with condensation carburization agent solvent and solute weight ratio be 1:1 hybrid infusion 3 minutes under room temperature；
(2) condensation carburizing reagent: the Waste Sulfuric Acid after hybrid infusion and condensation carburization agent are 95 DEG C and pressure is normal pressure in temperature
Carry out being condensed carburizing reagent 1 minute, obtain carbide and waste liquid；
(3) washing: by carbide repeatedly countercurrent washing, after being separated by filtration, finally give purer carbide and acid concentration
The highest filtrate；
(4) decolouring and deodorizing: 1% addition decolouring and deodorizing agent of the weight of the filtrate that the acid concentration that obtains according to step (3) is the highest is in temperature
After degree is 50 DEG C of decolouring and deodorizings, reclaim, obtain the sulphuric acid of regeneration, be used for producing sulfate or for sulphuric acid process, absorb
Sulfur trioxide, generates the 98% above sulphuric acid of concentration or for preparing the sulphuric acid of less than 93% concentration；
(5) material with carbon element reclaims: the purer carbide that step (3) obtains can be used for fuel or is processed further Viability
Charcoal.
Condensation carburization agent described in step (1) is powder of straw.
In condensation carburizing reagent described in step (2), liner material used is Hastelloy.
The method of the repeatedly countercurrent washing described in step (3) is: first, uses filter to filter carbide and waste liquid, profit
Wash carbide with clear water, filter with filter and separate, obtain filtrate, merge waste liquid；With filtrate and waste liquid as washing liquid, use and filter
Carbide is washed by machine again, obtains liquor B；Again with liquor B as washing liquid, filter is used again carbide to be washed
Wash, obtain liquor C；The filtrate utilizing upper level is again repeated 1 countercurrent washing to carbide, separates through repeatedly washing and filtering
After, finally give purer carbide and the highest filtrate of acid concentration.
Decolouring and deodorizing agent described in step (4) is value Mn compound.
Embodiment 2
A kind of waste sulfuric acid from alkylation resource recycle method, comprises the following steps:
(1) hybrid infusion: according to Waste Sulfuric Acid with condensation carburization agent solvent and solute weight ratio be 3:1 hybrid infusion 5 minutes under room temperature；
(2) condensation carburizing reagent: the Waste Sulfuric Acid after hybrid infusion and condensation carburization agent are 105 DEG C and pressure is normal pressure in temperature
Carry out being condensed carburizing reagent 3 minutes, obtain carbide and waste liquid；
(3) washing: by carbide repeatedly countercurrent washing, after being separated by filtration, finally give purer carbide and acid concentration
The highest filtrate；
(4) decolouring and deodorizing: 3% addition decolouring and deodorizing agent of the weight of the filtrate that the acid concentration that obtains according to step (3) is the highest is in temperature
After degree is 60 DEG C of decolouring and deodorizings, reclaim, obtain the sulphuric acid of regeneration, be used for producing sulfate or for sulphuric acid process, absorb
Sulfur trioxide, generates the 98% above sulphuric acid of concentration or for preparing the sulphuric acid of less than 93% concentration；
(5) material with carbon element reclaims: the purer carbide that step (3) obtains can be used for fuel or is processed further Viability
Charcoal.
Condensation carburization agent described in step (1) is bagasse.
In condensation carburizing reagent described in step (2), liner material used is high manganese stainless steel.
The method of the repeatedly countercurrent washing described in step (3) is: first, uses filter to filter carbide and waste liquid, profit
Wash carbide with clear water, filter with filter and separate, obtain filtrate, merge waste liquid；With filtrate and waste liquid as washing liquid, use and filter
Carbide is washed by machine again, obtains liquor B；Again with liquor B as washing liquid, filter is used again carbide to be washed
Wash, obtain liquor C；The filtrate utilizing upper level is again repeated 2 countercurrent washings to carbide, separates through repeatedly washing and filtering
After, finally give purer carbide and the highest filtrate of acid concentration.
Decolouring and deodorizing agent described in step (4) is hydrogen peroxide.
Embodiment 3
A kind of waste sulfuric acid from alkylation resource recycle method, comprises the following steps:
(1) hybrid infusion: according to Waste Sulfuric Acid with condensation carburization agent solvent and solute weight ratio be 5:1 hybrid infusion 6 minutes under room temperature；
(2) condensation carburizing reagent: the Waste Sulfuric Acid after hybrid infusion is 115 DEG C and pressure is with being condensed carburization agent in temperature
0.01MPa carries out being condensed carburizing reagent 5 minutes, obtains carbide and waste liquid；
(3) washing: by carbide repeatedly countercurrent washing, after being separated by filtration, finally give purer carbide and acid concentration
The highest filtrate；
(4) decolouring and deodorizing: 5% addition decolouring and deodorizing agent of the weight of the filtrate that the acid concentration that obtains according to step (3) is the highest is in temperature
After degree is 70 DEG C of decolouring and deodorizings, reclaim, obtain the sulphuric acid of regeneration, be used for producing sulfate or for sulphuric acid process, absorb
Sulfur trioxide, generates the 98% above sulphuric acid of concentration or for preparing the sulphuric acid of less than 93% concentration；
(5) material with carbon element reclaims: the purer carbide that step (3) obtains can be used for fuel or is processed further Viability
Charcoal.
Condensation carburization agent described in step (1) is wood bran.
In condensation carburizing reagent described in step (2), liner material used is high maganese cast iron.
The method of the repeatedly countercurrent washing described in step (3) is: first, uses filter to filter carbide and waste liquid, profit
Wash carbide with clear water, filter with filter and separate, obtain filtrate, merge waste liquid；With filtrate and waste liquid as washing liquid, use and filter
Carbide is washed by machine again, obtains liquor B；Again with liquor B as washing liquid, filter is used again carbide to be washed
Wash, obtain liquor C；The filtrate utilizing upper level is again repeated 3 countercurrent washings to carbide, separates through repeatedly washing and filtering
After, finally give purer carbide and the highest filtrate of acid concentration.
Decolouring and deodorizing agent described in step (4) is ozone.
Embodiment 4
A kind of waste sulfuric acid from alkylation resource recycle method, comprises the following steps:
(1) hybrid infusion: according to Waste Sulfuric Acid with condensation carburization agent solvent and solute weight ratio be 7:1 hybrid infusion 7 minutes under room temperature；
(2) condensation carburizing reagent: the Waste Sulfuric Acid after hybrid infusion is 125 DEG C and pressure is with being condensed carburization agent in temperature
0.03MPa carries out being condensed carburizing reagent 7 minutes, obtains carbide and waste liquid；
(3) washing: by carbide repeatedly countercurrent washing, after being separated by filtration, finally give purer carbide and acid concentration
The highest filtrate；
(4) decolouring and deodorizing: 7% addition decolouring and deodorizing agent of the weight of the filtrate that the acid concentration that obtains according to step (3) is the highest is in temperature
After degree is 80 DEG C of decolouring and deodorizings, reclaim, obtain the sulphuric acid of regeneration, be used for producing sulfate or for sulphuric acid process, absorb
Sulfur trioxide, generates the 98% above sulphuric acid of concentration or for preparing the sulphuric acid of less than 93% concentration；
(5) material with carbon element reclaims: the purer carbide that step (3) obtains can be used for fuel or is processed further Viability
Charcoal.
Condensation carburization agent described in step (1) is leaf powder.
In condensation carburizing reagent described in step (2), liner material used is cupric rustless steel.
The method of the repeatedly countercurrent washing described in step (3) is: first, uses filter to filter carbide and waste liquid, profit
Wash carbide with clear water, filter with filter and separate, obtain filtrate, merge waste liquid；With filtrate and waste liquid as washing liquid, use and filter
Carbide is washed by machine again, obtains liquor B；Again with liquor B as washing liquid, filter is used again carbide to be washed
Wash, obtain liquor C；The filtrate utilizing upper level is again repeated 4 countercurrent washings to carbide, separates through repeatedly washing and filtering
After, finally give purer carbide and the highest filtrate of acid concentration.
Decolouring and deodorizing agent described in step (4) is nitric acid.
Embodiment 5
A kind of waste sulfuric acid from alkylation resource recycle method, comprises the following steps:
(1) hybrid infusion: according to Waste Sulfuric Acid with condensation carburization agent solvent and solute weight ratio be 8:1 hybrid infusion 8 minutes under room temperature；
(2) condensation carburizing reagent: the Waste Sulfuric Acid after hybrid infusion is 135 DEG C and pressure is with being condensed carburization agent in temperature
0.04MPa carries out being condensed carburizing reagent 9 minutes, obtains carbide and waste liquid；
(3) washing: by carbide repeatedly countercurrent washing, after being separated by filtration, finally give purer carbide and acid concentration
The highest filtrate；
(4) decolouring and deodorizing: 8% addition decolouring and deodorizing agent of the weight of the filtrate that the acid concentration that obtains according to step (3) is the highest is in temperature
After degree is 90 DEG C of decolouring and deodorizings, reclaim, obtain the sulphuric acid of regeneration, be used for producing sulfate or for sulphuric acid process, absorb
Sulfur trioxide, generates the 98% above sulphuric acid of concentration or for preparing the sulphuric acid of less than 93% concentration；
(5) material with carbon element reclaims: the purer carbide that step (3) obtains can be used for fuel or is processed further Viability
Charcoal.
Condensation carburization agent described in step (1) is weeds powder.
In condensation carburizing reagent described in step (2), liner material used is Hastelloy.
The method of the repeatedly countercurrent washing described in step (3) is: first, uses filter to filter carbide and waste liquid, profit
Wash carbide with clear water, filter with filter and separate, obtain filtrate, merge waste liquid；With filtrate and waste liquid as washing liquid, use and filter
Carbide is washed by machine again, obtains liquor B；Again with liquor B as washing liquid, filter is used again carbide to be washed
Wash, obtain liquor C；The filtrate utilizing upper level is again repeated 5 countercurrent washings to carbide, separates through repeatedly washing and filtering
After, finally give purer carbide and the highest filtrate of acid concentration.
Decolouring and deodorizing agent described in step (4) is nitrate.
Embodiment 6
A kind of waste sulfuric acid from alkylation resource recycle method, comprises the following steps:
(1) hybrid infusion: according to Waste Sulfuric Acid with condensation carburization agent solvent and solute weight ratio be 10:1 hybrid infusion 10 points under room temperature
Clock；
(2) condensation carburizing reagent: the Waste Sulfuric Acid after hybrid infusion is 145 DEG C and pressure is with being condensed carburization agent in temperature
0.05MPa carries out being condensed carburizing reagent 10 minutes, obtains carbide and waste liquid；
(3) washing: by carbide repeatedly countercurrent washing, after being separated by filtration, finally give purer carbide and acid concentration
The highest filtrate；
(4) decolouring and deodorizing: 10% addition decolouring and deodorizing agent of the weight of the filtrate that the acid concentration that obtains according to step (3) is the highest in
After temperature is 100 DEG C of decolouring and deodorizings, reclaim, obtain the sulphuric acid of regeneration, be used for producing sulfate or for sulphuric acid process, inhale
Receive sulfur trioxide, generate the 98% above sulphuric acid of concentration or for preparing the sulphuric acid of less than 93% concentration；
(5) material with carbon element reclaims: the purer carbide that step (3) obtains can be used for fuel or is processed further Viability
Charcoal.
Condensation carburization agent described in step (1) is powder of straw, bagasse and the mixture of wood bran.
In condensation carburizing reagent described in step (2), liner material used is high maganese cast iron.
The method of the repeatedly countercurrent washing described in step (3) is: first, uses filter to filter carbide and waste liquid, profit
Wash carbide with clear water, filter with filter and separate, obtain filtrate, merge waste liquid；With filtrate and waste liquid as washing liquid, use and filter
Carbide is washed by machine again, obtains liquor B；Again with liquor B as washing liquid, filter is used again carbide to be washed
Wash, obtain liquor C；The filtrate utilizing upper level is again repeated 7 countercurrent washings to carbide, separates through repeatedly washing and filtering
After, finally give purer carbide and the highest filtrate of acid concentration.
Decolouring and deodorizing agent described in step (4) is nitrogen oxides.
Comparative example
East, Nanning and Xin Ying green technology company limited, do not grasped the waste sulfuric acid from alkylation resource of the present invention before 2014
Recovery method, can only use traditional PROCESS FOR TREATMENT Waste Sulfuric Acid, will Waste Sulfuric Acid in 150-200 DEG C of temperature, more than 5.0MPa's
Pressure, reactor linings material be tantalum material reactor in react 1-2 hour, inventor finds aborning, along with temperature
Raising and the increase of pressure, the speed of tantalum material corrosion also speeds, and reactor employs the time of about 1 year, there occurs together
Acid incident of leakage, because processing in time, does not cause the injures and deaths of personnel.After 2014, the said firm has grasped the present invention of the present invention
Waste sulfuric acid from alkylation resource recycle method, by powder of straw, bagasse, wood bran, leaf powder and these biomass materials of weeds powder
Expect to join in Waste Sulfuric Acid as condensation carburization agent, the most just the part in Waste Sulfuric Acid and biological material can be had
Machine thing carries out carburizing reagent, when being heated to temperature 95-145 DEG C, utilizes Waste Sulfuric Acid to have stronger oxidisability and dehydration property, makes
Remaining Organic substance continues carburizing reagent and redox reaction, generates carbide and the CO of porous2、SO2Deng oxidation of coal
Thing or sulphur oxide gas, get rid of most of hydrocarbons in Waste Sulfuric Acid ((macromolecule alkene, alkadienes, alkyl sulfonic acid,
Sulfuric ester and dissolve the materials such as hydrogen sulfide therein, mercaptan), after carbide is carried out repeatedly countercurrent washing, reclaim, be used for firing
Expect or be further processed into activated carbon；And the filtrate after carbide is scrubbed uses decolouring and deodorizing agent to carry out decolouring and deodorizing,
After decomposing the harmful substance in filtrate, reclaim, obtain the sulphuric acid of regeneration, be used for producing sulfate or for sulphuric acid process,
Absorb sulfur trioxide, generate high concentration (more than 98%) sulphuric acid or the sulphuric acid for preparation less than 93% concentration.Use the present invention's
Method, reduces production temperature, reduces pressure required during production, reduces the use of the energy, also can reduce reaction simultaneously
The requirement of device liner material, reduces the input cost of equipment, moreover it is possible to reduce the discharge of waste liquid refuse, it is often more important that, Waste Sulfuric Acid
Recycling be worth be greatly improved.
When ensureing that the final sulfuric acid concentration reclaimed is more than 70%, Waste Sulfuric Acid per ton is saved fuel about 10000 yuan, is reduced
Equipment investment cost about 10000 yuan.Carbide through reclaiming can be used for preparing activated carbon, and carbide recovery value per ton increases
About 8000 yuan, deducting the biological material cost about 3000 yuan of input per ton, Waste Sulfuric Acid per ton adds up to benefit increase about 25000
Unit.The application of the present invention, had both met the industrial policy of country's " energy-saving and emission-reduction ", Enterprise Integrated benefit can be greatly improved again.
Inventor finds in production practices, in two same reactors filling waste sulfuric acid from alkylation, adds
(biological material, including the one in powder of straw, bagasse, wood bran, leaf powder and weeds powder or a combination thereof for condensation carburization agent
Thing) reactor, the part in Organic substance can be carried out carburizing reagent at normal temperatures, and be 95-145 DEG C in temperature, pressure
It is by force under the reaction condition of 0.05MPa, has occurred and that violent carbonization and oxidation reaction, constantly discharge gas, and
The substantial amounts of micropore of Surface Creation of carbide；And another reactor being not added with being condensed carburization agent, it needs 150-250 DEG C of temperature
Just there is violent redox reaction under degree and reaction condition that pressure is normal pressure～3MPa, discharge substantial amounts of gas, but
Carbonizing degree is far away from the reactor adding condensation carburization agent.Inventor also find 150-250 DEG C and normal pressure～5.0MPa that
Big pressure carries out redox reaction, easily causes the damage of equipment, has had a strong impact on the normal operation of equipment, so,
Not only result in acid leakage, add unsafe factor, it is also desirable to thrown in people's production by substantial amounts of human and material resources, enter one
Step ground affects the efficiency of factory, improves production cost.And add condensation carburization agent, can reduce redox reaction temperature and
Pressure, it is not easy to cause the damage of equipment, thus reduce production cost and improve production safety coefficient, and, the carbon of recovery
Can be also used for preparing high-quality material with carbon element.
In the introduction, inventor is it is also mentioned that patent " renovation process of a kind of waste sulfuric acid from alkylation " (documents)
Technical scheme is the most similar to the present invention, and its different point has 2 points, analyzes from reaction condition, and the oxidation of documents 1 is also
Old terms is: temperature 100 DEG C ~ 300 DEG C, preferably 150 DEG C ~ 250 DEG C；Operation pressure is normal pressure～5.0MPa, preferably 3.0
～5.0MPa；The Redox Condition of the present invention is: temperature 95-145 DEG C；Operation pressure is normal pressure-0.05MPa；Response time
1-10 minute；By contrast, the reaction temperature of the present invention and pressure are intended to lower than documents, and the response time is the shortest, joint
Save production cost.Analyzing from mechanism, mainly there is oxidation reaction in documents, its oxidant is H2O2、O3、HNO3With
The mixture of one or more in NOx, recovery is the sulphuric acid regenerated；And the present invention had both occurred carburizing reagent also to aoxidize
Reaction, recovery is the sulphuric acid of carbide and regeneration.The more important thing is, in documents the material of reactor selected from tantalum material,
Titanium material, inner lining glass fiber reinforced plastic or quartz glass, but inventor finds during test, the oxidizing temperature of 150-250 DEG C
Under, a lot of materials all bear the corrosion of concentrated sulphuric acid under incessantly high temperature, easily cause device damage, affect the normal operation of equipment.
Claims (5)
1. a waste sulfuric acid from alkylation resource recycle method, it is characterised in that: comprise the following steps:
(1) hybrid infusion: according to Waste Sulfuric Acid with condensation carburization agent solvent and solute weight ratio be 1:1-10:1 hybrid infusion under room temperature
3-10 minute；
(2) condensation carburizing reagent: the Waste Sulfuric Acid after hybrid infusion is 95-145 DEG C and pressure is with being condensed carburization agent in temperature
Normal pressure-0.05MPa carries out being condensed carburizing reagent 1-10 minute, obtains carbide and waste liquid；
(3) washing: by carbide repeatedly countercurrent washing, after being separated by filtration, finally give purer carbide and acid concentration
The highest filtrate；
(4) decolouring and deodorizing: the 1-10% of the weight of the filtrate that the acid concentration that obtains according to step (3) is the highest adds decolouring and deodorizing agent
After temperature is 50-100 DEG C of decolouring and deodorizing, reclaim, obtain the sulphuric acid of regeneration, be used for producing sulfate or for gas washing in SA production mistake
Journey, absorbs sulfur trioxide, generates the 98% above sulphuric acid of concentration or for preparing the sulphuric acid of less than 93% concentration；
(5) material with carbon element reclaims: the purer carbide that step (3) obtains is for fuel or is processed further Viability
Charcoal.
Waste sulfuric acid from alkylation resource recycle method the most according to claim 1, it is characterised in that: described in step (1)
Condensation carburization agent is biological material, including the one in powder of straw, bagasse, wood bran, leaf powder and weeds powder or a combination thereof
Thing.
Waste sulfuric acid from alkylation resource recycle method the most according to claim 1, it is characterised in that: described in step (2)
In condensation carburizing reagent, liner material used is appointing in Hastelloy, high manganese stainless steel, high maganese cast iron and cupric rustless steel
A kind of.
Waste sulfuric acid from alkylation resource recycle method the most according to claim 1, it is characterised in that: described in step (3)
Repeatedly the method for countercurrent washing is: first, uses filter to filter carbide and waste liquid, utilizes clear water to wash carbide, used
Filter filters and separates, and obtains filtrate, merges waste liquid；With filtrate and waste liquid as washing liquid, filter is used again carbide to be washed
Wash, obtain liquor B；Again with liquor B as washing liquid, use filter again carbide to be washed, obtain liquor C；Utilize upper one
The filtrate of level is again repeated 1-7 countercurrent washing to carbide, after repeatedly washing and filtering separates, finally gives purer
Carbide and the highest filtrate of acid concentration.
Waste sulfuric acid from alkylation resource recycle method the most according to claim 1, it is characterised in that: described in step (4)
Decolouring and deodorizing agent is any one in value Mn compound, hydrogen peroxide, ozone, nitric acid and nitrate and nitrogen oxides.
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| 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 |
| CN108529569A (en) * | 2018-03-22 | 2018-09-14 | 辛集市北方化工有限公司 | A kind of recovery and treatment method of waste sulfuric acid from alkylation |
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| CN108946697A (en) * | 2018-08-02 | 2018-12-07 | 中国科学院过程工程研究所 | A kind of processing method using waste sulfuric acid from alkylation production biomass carbon |
| CN109485021A (en) * | 2019-01-10 | 2019-03-19 | 钦州学院 | A kind of method of thermally conductive resolution process waste sulfuric acid from alkylation |
| CN109573960A (en) * | 2018-12-17 | 2019-04-05 | 江苏诺斯特拉环保科技有限公司 | Waste Sulfuric Acid recycles method of disposal |
| CN110550610A (en) * | 2019-10-18 | 2019-12-10 | 斯瑞尔环境科技股份有限公司 | Regeneration treatment method of alkylation waste sulfuric acid |
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| 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 |
| 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 |
| CN108529569A (en) * | 2018-03-22 | 2018-09-14 | 辛集市北方化工有限公司 | A kind of recovery and treatment method of waste sulfuric acid from alkylation |
| CN108751162A (en) * | 2018-07-05 | 2018-11-06 | 北京中富瑞科环保科技有限公司 | A kind of carbonizing treatment method of antibiotic bacterium dregs |
| CN108910858A (en) * | 2018-07-05 | 2018-11-30 | 北京中富瑞科环保科技有限公司 | A kind of recycling processing method of organic medical waste |
| CN108910858B (en) * | 2018-07-05 | 2023-04-07 | 北京中富瑞科环保科技有限公司 | Resourceful treatment method for organic medical waste |
| CN108751162B (en) * | 2018-07-05 | 2023-03-21 | 北京中富瑞科环保科技有限公司 | Carbonization treatment method of antibiotic fungi residues |
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| CN108893128B (en) * | 2018-08-02 | 2021-03-02 | 北京中富瑞科环保科技有限公司 | Carbonization treatment method of biomass |
| CN108946697A (en) * | 2018-08-02 | 2018-12-07 | 中国科学院过程工程研究所 | A kind of processing method using waste sulfuric acid from alkylation production biomass carbon |
| CN109573960A (en) * | 2018-12-17 | 2019-04-05 | 江苏诺斯特拉环保科技有限公司 | Waste Sulfuric Acid recycles method of disposal |
| CN109485021A (en) * | 2019-01-10 | 2019-03-19 | 钦州学院 | A kind of method of thermally conductive resolution process waste sulfuric acid from alkylation |
| CN110550610A (en) * | 2019-10-18 | 2019-12-10 | 斯瑞尔环境科技股份有限公司 | Regeneration treatment method of alkylation waste sulfuric acid |
| CN111533584A (en) * | 2020-06-12 | 2020-08-14 | 山东鲁北化工股份有限公司 | Preparation method of biomass sulfonated carbon based diammonium phosphate |
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