CN106976896A - A kind of utilization waste sulfuric acid from alkylation produces the method and system of epsom salt - Google Patents
A kind of utilization waste sulfuric acid from alkylation produces the method and system of epsom salt Download PDFInfo
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- CN106976896A CN106976896A CN201710345627.4A CN201710345627A CN106976896A CN 106976896 A CN106976896 A CN 106976896A CN 201710345627 A CN201710345627 A CN 201710345627A CN 106976896 A CN106976896 A CN 106976896A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/40—Magnesium sulfates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention provides the method and system that a kind of utilization waste sulfuric acid from alkylation produces epsom salt.Contain organic matter and with oxidisability using waste sulfuric acid from alkylation, the characteristics of occurring thermochemical reduction and pyrolytic reaction at high temperature, the present invention is at 500~600 DEG C, by waste sulfuric acid from alkylation is with vaporific penetrating pyrolytic system and is thermally decomposed into the sour gas based on sulfur trioxide, in the process, high temperature carbonization formation carbon black can occur for the organic matter in waste sulfuric acid from alkylation, be reacted generation sulfur dioxide while having part organic matter or carbon black and sulfuric acid.The systems such as high-temperature acidic gas absorbs, is separated by filtration by dedusting, flue gas heat exchange, acid gas, crystallisation by cooling and drying, in the case where neutralizing the effect of conversion medium light calcined magnesia, obtained epsom salt product.The present invention is produced without waste water, and white residue is used to produce building materials, and tail gas qualified discharge realizes the recycling of waste sulfuric acid from alkylation, is a typical greenization cleaning new technology.
Description
Technical field
The invention belongs to the environmental technology field of changing rejected material to useful resource, it is related to one kind and produces seven water using waste sulfuric acid from alkylation
The method and system of magnesium sulfate.
Background technology
Sulfuric acid is one of most basic chemicals, enjoys the good reputation of " mother of industry ", chemical fertilizer, synthetic fibers,
The sector applications such as titanium dioxide, petroleum refining, dyestuff, medical drugs, pesticide producing are extensive.However, in process of production, because various
The introducing of impurity, the reason such as concentration reduction, produces a large amount of Waste Sulfuric Acids.Alkylation is to be introduced alkyl using addition or displacement reaction
It is alkylated for increasing octane number to improve gasoline quality, sulfuric acid process in course of reaction in organic molecule, petroleum refining
Alkylation is using 89~98% sulfuric acid as catalyst, and liquid phase reactor generates high octane gasoline component under low temperature, and the technique is because of behaviour
Make comparatively safe, the alkylate oil quality of generation is high, is widely adopted.But, current sulfuric acid process alkylation process is often given birth to
1 ton of alkylate oil of production will discharge 80~100kg Waste Sulfuric Acids, wherein containing 85~90% sulfuric acid, 7~10% or so organic matter and
3~5% water, organic matter pbz polymer alkene, alkadienes, alkyl sulfonic acid, sulfuric ester and sulfide etc..Waste sulfuric acid from alkylation face
Color depth, quality are sticky, Odor stimulation, and organic impurities are very difficult to remove, and the processing of waste sulfuric acid from alkylation turns into industry problem.
At present, Waste Sulfuric Acid processing method both domestic and external can be roughly divided into three major types, that is, recycle, and comprehensively utilize and neutralize
Processing.Numerous researchers have carried out system introduction and elaboration to Waste Sulfuric Acid treatment technology, for the processing of waste sulfuric acid from alkylation
It it is also proposed many new methods, new technology and new system.
(1) pyrolysismethod, Que Tieshun, Zhang Zhenru, Lv Tianbao etc. is alkylated spent acid pyrolysis furnace to China and thermal cracking handles useless
The practice of sulfuric acid is set forth.Patent CN100537416C describes a kind of waste sulfuric acid from alkylation and produces sulfuric acid through Pintsch process
Handling process, the technique, at 1000~1100 DEG C, Waste Sulfuric Acid is cracked into the single waste sulfuric acid from alkylation of content 85~90%
SO2, it is then converted into SO3, then absorb into the concentrated sulfuric acid with water or dilute sulfuric acid.This method sulfur waste acid recovering rate reaches 90%.But,
The investment of pyrolysismethod is big, and operating cost is high, and sulfuric acid product cost is high, and equipment requirement is harsh, and general enterprises are difficult to bear.
(2) conversion method, Wang strong determined persons etc., which describe, utilizes alkyl plant spent acid and deposed ammonia Sulphuric acid ammonium.Patent CN
104628012A describes the production method that a kind of alkylation spent acid prepares ammonium sulfate.Both of which is to utilize to be alkylated spent acid
Ammonium sulfate is generated with ammonia reaction, then ammonium sulfate is obtained through de-oiling, decolouring, mother liquor crystallization.The advantage of this method is that equipment is simple, work
Skill relative maturity；Have the disadvantage that the price of ammoniacal liquor is higher, wastewater flow rate is big, and the quality of ammonium sulfate is difficult to be guaranteed, activated carbon is present
Secondary pollution problems.
(3) original production sulphur is gone back.Patent CN 104229746B describe a kind of alkylation spent acid sulphur new method.Should
Method, can be to be alkylated spent acid as raw material production sulphur still based on high-temperature cracking method.The shortcoming of this method is cracking temperature
In 1100 DEG C of even more highs, equipment requirement is higher, and investment and operating cost are larger, and to have H 2 S-containing gas supporting, adapts to
Property is not strong.
In addition, also having using the method processing waste sulfuric acid from alkylation such as concentration, neutralization, concentration method high energy consumption, equipment requirement is severe
Carve, investment operating cost is high；Simple lime or light burnt powder are neutralized, and it is exceeded that obtained byproduct still has organic matter, outside waste water
The shortcomings of row, do not tackle the problem at its root.
The alkylate oil of China is in great demand, result in the increase year by year of waste sulfuric acid from alkylation.By 2016, China
Sulfuric acid alkylation unit annual capacity produces waste sulfuric acid from alkylation per year more than 2,000,000 tons more than 20,000,000 tons, and becomes in increase year by year
Gesture.
The content of the invention
For problem present in above-mentioned existing waste sulfuric acid from alkylation treatment technology, alkyl is utilized the invention provides one kind
Change the method and system that Waste Sulfuric Acid produces epsom salt.Contain organic matter using waste sulfuric acid from alkylation and there is oxidisability,
The characteristics of high temperature issues heat producing chemical reduction reaction and pyrolytic reaction, the present invention is at 500~600 DEG C, by waste sulfuric acid from alkylation
Sour gas based on sulfur trioxide and is thermally decomposed at pyrolytic system with vaporific penetrating, in the process, alkylation is useless
High temperature carbonization formation carbon black can occur for the organic matter in sulfuric acid, be reacted production while having part organic matter or carbon black and sulfuric acid
Raw sulfur dioxide.High-temperature acidic gas absorbs, is separated by filtration by dedusting, flue gas heat exchange, acid gas, crystallisation by cooling and drying etc. are
System, in the case where neutralizing the effect of conversion medium light calcined magnesia, is made epsom salt product.The present invention is produced without waste water, and white residue is used
In production building materials, tail gas qualified discharge realizes the recycling of waste sulfuric acid from alkylation, is that a typical greenization cleaning is new
Technique.
Main reaction equation includes in the present invention：
H2SO4=H2O+SO3 (1)
2H2SO4+ C=2H2O+2SO2+CO2 (2)
MgO+H2O=Mg (OH)2 (3)
Mg(OH)2+H2SO4=MgSO4+2H2O (4)
Mg(OH)2+SO3=MgSO4+H2O (5)
Mg(OH)2+SO2=MgSO3+H2O (6)
2MgSO3+O2=2MgSO4 (7)
(1) with (2) belong to heat classification and redox reaction, (3) be light calcined magnesia hydration reaction, (4), (5) and
(6) to neutralize absorbing reaction, (7) are oxidation reaction.
For up to the purpose, the present invention uses following technical scheme：
On the one hand, the invention provides a kind of method that waste sulfuric acid from alkylation produces epsom salt, it is characterised in that institute
The method of stating comprises the following steps：
A. waste sulfuric acid from alkylation is decomposed at high temperature, obtains the high-temperature flue gas containing sour gas；
B. the high-temperature flue gas containing sour gas obtained in step a carries out dedusting, removes the charcoal carried secretly in high-temperature flue gas
It is black；
C. the high-temperature flue gas after carbon black is removed in step b to carry out carrying out acid after heat exchange, flue gas cool-down with pure air
Aspiration, the thermal source that the pure air after being heated is dried as magnesium sulfate；
D. light calcined magnesia slurry is made into desalted water and light calcined magnesia, is used as the nertralizer for absorbing acid gas；
E. sour gas reacts with nertralizer after being exchanged heat in step c, and tail gas qualified discharge, absorbing liquid carries out air oxidation；
F. the containing magnesium sulfate slurry that step e is obtained carries out high temperature filtration separation, obtains Adlerika and white residue, and white residue is used
In production building materials；
G. the Adlerika that step f is obtained first carries out crystallisation by cooling, then is centrifuged and obtains magnesium sulfate crystals；
H. the obtained magnesium sulfate crystals of step g are dried the hot pure air after step c heat exchange, obtain seven water sulfuric acid
Magnesium products.
In the present invention, in step a the concentration of waste sulfuric acid from alkylation be 85~90wt%, such as 85wt%, 88wt% or
90wt% etc.；In waste sulfuric acid from alkylation COD concentration be 50000~150000mg/L, such as 50000mg/L, 80000mg/L,
100000mg/L, 120000mg/L or 150000mg/L etc.；
Preferably, waste sulfuric acid from alkylation feeding temperature is 20~40 DEG C, such as 20 DEG C, 30 DEG C or 40 DEG C etc. in step a；
Preferably, step a high temperatures pyrolysis furnace pyrolysis temperature is 500~600 DEG C, such as 500 DEG C, 550 or 600 DEG C etc.；
Preferably, the time that step a high temperatures are decomposed is 6~12s, such as 6s, 8s, 10s or 12s；
Preferably, cyclone dust collectors high-temperature flue gas import temperature is 300~400 DEG C, such as 300 DEG C, 350 DEG C in step b
Or 400 DEG C etc.；
Preferably, sack cleaner high-temperature flue gas import temperature is 200~300 DEG C, such as 200 DEG C, 250 DEG C in step b
Or 300 DEG C etc.；
Preferably, the temperature of pure air is 10~30 DEG C, such as 10 DEG C, 20 DEG C or 30 DEG C etc. before being exchanged heat in step c.Change
The temperature of pure air after heat is 60~80 DEG C, such as 60 DEG C, 70 DEG C or 80 DEG C etc..
Preferably, in step d in light calcined magnesia slurry magnesia content be 20~30wt%, such as 20wt%,
25wt% or 30wt% etc.；
Preferably, it is 80~90 DEG C, such as 80 DEG C, 85 DEG C or 90 DEG C etc. that neutral temperature is absorbed in step e.Three oxygen in tail gas
Change sulphur and sulfur dioxide concentration is less than 100ppm.Air oxidation is that slurry sulfite magnesium is changed into magnesium sulfate；
Preferably, the filtration temperature of the containing magnesium sulfate slurry obtained in step f be 70~85 DEG C, such as 70 DEG C, 80 DEG C or
85 DEG C etc.；
Preferably, crystallisation by cooling temperature is 15~30 DEG C, such as 15 DEG C, 20 DEG C, 25 DEG C or 30 DEG C etc. in step g.Cooling
Crystallization time is 18~36h, such as 18h, 24h, 30h or 36h etc.；
Preferably, drying temperature is 40~60 DEG C, such as 40 DEG C, 50 DEG C or 60 DEG C etc. in step h；Drying time be 30~
60min, such as 30min, 40min, 50min or 60min etc.；In obtained product the content of epsom salt be 98.5~
99.8wt%, such as 98.5wt%, 99.0wt%, 99.5wt% or 99.8wt%.
On the other hand, the invention provides the system that a kind of waste sulfuric acid from alkylation produces epsom salt, the system bag
Include pyrolytic, dedusting, flue gas heat exchange, nertralizer dispensing, acid gas absorb, be separated by filtration, the system such as crystallisation by cooling and drying.
Wherein, the gaseous phase outlet of pyrolytic system is connected with dust pelletizing system；The gaseous phase outlet of dust pelletizing system is changed with flue gas
Hot systems are connected；The gaseous phase outlet of smoke heat exchanging system, slurry outlet and the compressed air inlet difference of nertralizer feed proportioning system
It is connected with acid gas absorption system；The liquid-phase outlet of acid gas absorption system is connected with being separated by filtration system；It is separated by filtration the liquid of system
Mutually outlet is connected with crystallisation by cooling system；The solid-phase outlet of crystallisation by cooling system is connected with drying system.
On the one hand above-mentioned smoke heat exchanging system reduces acid gas temperature, is easy to the operation of acid gas absorption system；On the one hand by height
The heat that warm decomposing system is produced is heated for air, and then for the drying of magnesium sulfate, is realized the cascade utilization of heat, played
Energy consumption is saved, the effect of cost is reduced.
Preferably, the pyrolytic system is high-temperature cracking furnace (1), using clean fuel as thermal source, waste sulfuric acid from alkylation
Entered with the vaporific side lower part from high-temperature cracking furnace.
Preferably, the dust pelletizing system includes cyclone dust collectors (2) and sack cleaner (3), and high-temperature flue gas first passes through rotation
Wind deduster, by cloth bag deduster.
Preferably, the smoke heat exchanging system is flue gas heat-exchange unit (4), and wherein heat transferring medium is pure air.
Preferably, the acid gas absorption system include acid gas absorption tower (5), circulating slot (9), absorption tower circulating pump (6) and
Exhaust fan (7)；Wherein acid gas self-absorption tower side lower part enters；Nertralizer is drawn in the circulating pump self-loopa groove of absorption tower,
Absorption tower upper lateral part spray carries out neutralization absorption to acid gas, neutralizes absorbing liquid self-absorption tower bottom and returns to circulating slot, tail gas self-priming
Top of tower is received to be drawn by exhaust fan；Slurry is aoxidized under compressed air effect in circulating slot.
Preferably, the nertralizer feed proportioning system is light calcined magnesia dosage bunker (8), and desalted water and light calcined magnesia are light
Slurry is made into burned magnesium oxide dosage bunker.
Preferably, the system that is separated by filtration is white residue filter press (10).
Preferably, the crystallisation by cooling system includes cooler crystallizer (11), air cooling tower (12), air cooling pump (13) and centrifugation
Machine (14)；Desalted water after air-cooled tower cooler as cooler crystallizer cooling medium, by air cooling pump air cooling tower and cooling tie
Circulated between brilliant device；Cooler crystallizer discharging enters centrifuge, and the discharging of centrifuge solid phase enters drying system.
Preferably, the drying system is drier (15), is situated between by the pure air from flue gas heat-exchange unit as dry
Matter.
In the present invention, when carrying out methods described technological process using the system and device, comprise the following steps：
I. high-temperature cracking furnace (1) is preheated first, treats that its bottom rises to required temperature, by waste sulfuric acid from alkylation from height
The side lower part of warm pyrolysis furnace (1) is sprayed into and reacted, and obtains the high-temperature flue gas containing sour gas.Wherein, high-temperature cracking furnace
Pyrolysis temperature is 500~600 DEG C, and waste sulfuric acid from alkylation feeding temperature is 20~40 DEG C, the concentration of waste sulfuric acid from alkylation for 85~
COD contents are 50000~150000mg/L in 90wt%, waste sulfuric acid from alkylation, the pyrolysis time in high-temperature cracking furnace for 6~
12s；
II. high-temperature flue gas enters the import of cyclone dust collectors (2) after being left from high-temperature cracking furnace (1) top exit, then
The import of sack cleaner (3) is exited into from the outlet of cyclone dust collectors (2), then is left from the outlet of sack cleaner (3).
Carbon black is removed from the outlet at bottom of cyclone dust collectors (2) and sack cleaner (3).The wherein gas feed of cyclone dust collectors (2)
Temperature is 300~400 DEG C, and the gas inlet temperature of sack cleaner (3) is 200~300 DEG C；
III. high-temperature gas the entering into the high-temperature gas of flue gas heat-exchange unit (4) left is exported from sack cleaner (3)
Mouthful, the pure air progress heat exchange with entering the hot device of smoke gasification (4) from cryogenic gas import.Wherein, pure air exchanges heat
Preceding temperature is 10~30 DEG C, and temperature is 60~80 DEG C after heat exchange；
IV. light calcined magnesia and desalted water are configured to slurry in light calcined magnesia dosage bunker (8), and wherein magnesia contains
Measure as 20~30wt%；
V. the slurry in light calcined magnesia dosage bunker (8) is through circulating slot (9) its top feed mouthful addition circulating slot (9), from following
Annular groove (9) bottom discharge mouth enters after leaving through absorption tower circulating pump (6) charging aperture, the discharging opening from absorption tower circulating pump (6)
Leave, enter acid gas absorption tower (5) through acid gas absorption tower (5) upper lateral part slurry spray inlet.Flue gas heat-exchange unit (4) is left containing acid
Gas enters from acid gas absorption tower (5) side lower part entrance, and neutralization suction is carried out with the spray slurry from absorption tower circulating pump (6)
Receive, tail gas by exhaust fan (7) from acid gas absorption tower (5) Base top contact discharge, slurry from acid gas absorption tower (5) outlet at bottom from
Drive into circulating slot (9), the compressed air generation oxidation reaction with being passed through circulating slot (9).Wherein, in acid gas absorption tower (5)
It it is 80~90 DEG C with temperature is absorbed, tail gas qualified discharge, sulfur dioxide and sulfur trioxide concentration are less than 100ppm；
V. the slurry in circulating slot (9) after neutralizing and absorbing and aoxidize delivers to white residue press filtration through absorption tower circulating pump (6)
Machine (10) carries out separation of solid and liquid.Wherein, the filtration temperature of white residue filter press (10) is 70~85 DEG C；
VII. the desalted water cooled down through air cooling tower (12) is delivered to cooler crystallizer (11) by air cooling pump (13), and backwater is returned
Air cooling tower (12).The solution that white residue filter press (10) press filtration is obtained enter cooler crystallizer (11) decrease temperature crystalline, subsequently into from
Scheming (14) carries out separation of solid and liquid, obtains magnesium sulfate crystals.Wherein, crystallisation by cooling temperature is 15~30 DEG C, crystallisation by cooling time
For 18~36h；
VIII. the magnesium sulfate crystals that centrifuge (14) is obtained enter drier (15), are changed using from flue gas heat-exchange unit (4)
Pure air after heat is dried, and obtains epsom salt product.Wherein, the drying temperature in drier (15) is 40~60
DEG C, drying time be 30~60min, on this condition, in obtained product the content of epsom salt be 98.5~
99.8wt%.
Brief description of the drawings
Fig. 1 is a kind of process chart of the method for waste sulfuric acid from alkylation production epsom salt of the present invention；
Fig. 2 is the schematic device that a kind of waste sulfuric acid from alkylation of the present invention produces epsom salt system；
Wherein：(1) high-temperature cracking furnace；(2) cyclone dust collectors；(3) sack cleaner；(4) flue gas heat-exchange unit；(5) acid gas
Absorption tower；(6) absorption tower circulating pump (7) exhaust fan；(8) light calcined magnesia dosage bunker；(9) circulating slot；(10) white residue press filtration
Machine；(11) cooler crystallizer；(12) air cooling tower；(13) air cooling pump；(14) centrifuge；(15) drier.
Embodiment
For the present invention is better described, technical scheme is readily appreciated, below to the present invention further specifically
It is bright.But following embodiments is only the simple example of the present invention, the scope of the present invention is not represented or limits, this
Invention protection domain is defined by claims.
The specific embodiment of the invention uses technological process as shown in Figure 1 and system and device as shown in Figure 2.
Light calcined magnesia comes from Liaoning Yingkou Dashiqiao, and content of magnesia is more than 85%.Waste sulfuric acid from alkylation comes from Shandong
Qingdao.
Embodiment 1：
Device designed capacity：20,000 tons of waste sulfuric acid from alkylation of year processing, production time 8000h.
By 2.5t/h waste sulfuric acid from alkylation (temperature is 20 DEG C, and sulfuric acid concentration is that 85%, COD contents are 50000mg/L)
Sprayed into from the side lower part using natural gas as the high-temperature cracking furnace of thermal source with vaporific, wherein, bottom temperature is 600 DEG C, and Waste Sulfuric Acid exists
Pyrolysis time in pyrolysis furnace is 6s, and pyrolysis furnace Outlet Gas Temperature is 400 DEG C, and high-temperature flue gas is via cyclone separator and cloth bag
Carbon black 35kg/h is obtained after deduster；Flue gas heat-exchange unit pure air intake is 5500m3/ h, 20 DEG C, temperature is 70 after heat exchange
DEG C, high-temperature flue gas temperature after heat exchange is reduced to 180 DEG C and enters acid gas absorption tower side lower part.Added in light calcined magnesia dosage bunker
Light calcined magnesia and water are configured to slurry, and the addition of light calcined magnesia is 1030Kg/h, and the addition of water is 2400Kg/h, gently
The concentration of burned magnesium oxide slurry is 30wt%；Light calcined magnesia slurry enters circulating slot with 3430Kg/h, and is circulated through absorption tower
Upper lateral part of the pump on acid gas absorption tower is sprayed into, and neutralization absorption is carried out with acid gas, is obtained neutralization absorbing liquid and is returned to circulating slot, and is passed through
Magnesium sulfate growing amount is 2600Kg/h in air oxidation, circulating slot, and temperature reaches 90 DEG C；Tails assay shows, sulfur dioxide and
The total amount of sulfur trioxide is 58ppm, less than 100ppm, qualified discharge.Containing magnesium sulfate slurry in circulating slot is circulated with absorption tower
It is pumped into white residue filter press and carries out separation of solid and liquid, filtration temperature is 85 DEG C, and obtained white residue amount is 330Kg/h, wherein aqueous be
160Kg/h, obtains filtrate and enters cooler crystallizer progress crystallisation by cooling for 5600Kg/h, enter crystallisation by cooling from air cooling tower
The temperature of the desalted water of device is 15 DEG C, and the temperature for returning to air cooling tower is 40 DEG C；The crystallisation by cooling time be 24h, after crystallization enter from
Scheming is separated, and is obtained magnesium sulfate crystals amount for 5420Kg/h, is dried into drier；Drying temperature is 50 DEG C in drier,
Drying time is 40min, obtains sulfuric acid magnesium products for 5200Kg/h, is computed, and the yield of epsom salt is 97.69%, production
Quality is analyzed as follows shown in table：
Embodiment 2：
Device designed capacity：20,000 tons of waste sulfuric acid from alkylation of year processing, production time 8000h.
By 2.5t/h waste sulfuric acid from alkylation (temperature is 30 DEG C, and sulfuric acid concentration is that 90%, COD contents are 100000mg/L)
Sprayed into from the side lower part using natural gas as the high-temperature cracking furnace of thermal source with vaporific, wherein, bottom temperature is 550 DEG C, and Waste Sulfuric Acid exists
Pyrolysis time in pyrolysis furnace is 8s, and pyrolysis furnace Outlet Gas Temperature is 380 DEG C, and high-temperature flue gas is via cyclone separator and cloth bag
Carbon black 50kg/h is obtained after deduster；Flue gas heat-exchange unit pure air intake is 5000m3/ h, 10 DEG C, temperature is 60 after heat exchange
DEG C, high-temperature flue gas temperature after heat exchange is reduced to 145 DEG C and enters acid gas absorption tower side lower part.Added in light calcined magnesia dosage bunker
Light calcined magnesia and water are configured to slurry, and the addition of light calcined magnesia is 1100Kg/h, and the addition of water is 3300Kg/h, gently
The concentration of burned magnesium oxide slurry is 25wt%；Light calcined magnesia slurry enters circulating slot with 4400Kg/h, and is circulated through absorption tower
Upper lateral part of the pump on acid gas absorption tower is sprayed into, and neutralization absorption is carried out with acid gas, is obtained neutralization absorbing liquid and is returned to circulating slot, and is passed through
Magnesium sulfate growing amount is 2760Kg/h in air oxidation, circulating slot, and temperature reaches 80 DEG C；Tails assay shows, sulfur dioxide and
The total amount of sulfur trioxide is 55ppm, less than 100ppm, qualified discharge.Containing magnesium sulfate slurry in circulating slot is circulated with absorption tower
It is pumped into white residue filter press and carries out separation of solid and liquid, filtration temperature is 70 DEG C, and obtained white residue amount is 370Kg/h, wherein aqueous be
180Kg/h, obtains filtrate and enters cooler crystallizer progress crystallisation by cooling for 6530Kg/h, enter crystallisation by cooling from air cooling tower
The temperature of the desalted water of device is 25 DEG C, and the temperature for returning to air cooling tower is 48 DEG C；The crystallisation by cooling time be 18h, after crystallization enter from
Scheming is separated, and is obtained magnesium sulfate crystals amount for 5550Kg/h, is dried into drier；Drying temperature is 40 DEG C in drier,
Drying time is 60min, obtains sulfuric acid magnesium products for 5320Kg/h, is computed, and the yield of epsom salt is 95.38%, production
Quality is analyzed as follows shown in table：
Embodiment 3：
Device designed capacity：20,000 tons of waste sulfuric acid from alkylation of year processing, production time 8000h.
By 2.5t/h waste sulfuric acid from alkylation (temperature is 40 DEG C, and sulfuric acid concentration is that 88%, COD contents are 150000mg/L)
Sprayed into from the side lower part using natural gas as the high-temperature cracking furnace of thermal source with vaporific, wherein, bottom temperature is 500 DEG C, and Waste Sulfuric Acid exists
Pyrolysis time in pyrolysis furnace is 12s, and pyrolysis furnace Outlet Gas Temperature is 390 DEG C, and high-temperature flue gas is via cyclone separator and cloth
Carbon black 75kg/h is obtained after bag dust collector；Flue gas heat-exchange unit pure air intake is 5300m3/ h, 30 DEG C, temperature is after heat exchange
80 DEG C, high-temperature flue gas temperature after heat exchange is reduced to 165 DEG C and enters acid gas absorption tower side lower part.Add in light calcined magnesia dosage bunker
Enter light calcined magnesia and water be configured to slurry, the addition of light calcined magnesia is 1060Kg/h, and the addition of water is 4200Kg/h,
The concentration of light calcined magnesia slurry is 20wt%；Light calcined magnesia slurry enters circulating slot with 5260Kg/h, and is followed through absorption tower
Upper lateral part of the ring pump on acid gas absorption tower is sprayed into, and neutralization absorption is carried out with acid gas, is obtained neutralization absorbing liquid and is returned to circulating slot, and leads to
It is 2700Kg/h to enter magnesium sulfate growing amount in air oxidation, circulating slot, and temperature reaches 85 DEG C；Tails assay shows, sulfur dioxide
Total amount with sulfur trioxide is 50ppm, less than 100ppm, qualified discharge.Containing magnesium sulfate slurry in circulating slot is followed with absorption tower
Ring is pumped into white residue filter press and carries out separation of solid and liquid, and filtration temperature is 75 DEG C, and obtained white residue amount is 350Kg/h, wherein aqueous
For 170Kg/h, obtain filtrate and enter cooler crystallizer progress crystallisation by cooling for 7410Kg/h, entering cooling from air cooling tower ties
The temperature of the desalted water of brilliant device is 30 DEG C, and the temperature for returning to air cooling tower is 52 DEG C；The crystallisation by cooling time is 36h, is entered after crystallization
Centrifuge is separated, and is obtained magnesium sulfate crystals amount for 5500Kg/h, is dried into drier；Drying temperature is 60 in drier
DEG C, drying time is 30min, obtains sulfuric acid magnesium products for 5380Kg/h, is computed, and the yield of epsom salt is 97.29%,
Product quality analysis is as shown in the table：
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and being open.
Claims (7)
1. a kind of method that utilization waste sulfuric acid from alkylation produces epsom salt, it is characterised in that comprise the following steps：
A. waste sulfuric acid from alkylation is decomposed at high temperature, obtains the high-temperature flue gas containing sour gas；
B. the high-temperature flue gas containing sour gas obtained in step a carries out dedusting, removes the carbon black carried secretly in high-temperature flue gas；
C. the high-temperature flue gas after carbon black is removed in step b to carry out carrying out acid gas suction after heat exchange, flue gas cool-down with pure air
Receive, the thermal source that the pure air after being heated is dried as magnesium sulfate；
D. light calcined magnesia slurry is made into desalted water and light calcined magnesia, is used as the nertralizer for absorbing acid gas；
E. sour gas reacts with nertralizer after being exchanged heat in step c, and tail gas qualified discharge, absorbing liquid carries out air oxidation；
F. the containing magnesium sulfate slurry that step e is obtained carries out high temperature filtration separation, obtains Adlerika and white residue, and white residue is used to give birth to
Produce building materials；
G. the Adlerika that step f is obtained first carries out crystallisation by cooling, then is centrifuged and obtains magnesium sulfate crystals；
H. the obtained magnesium sulfate crystals of step g are dried the hot pure air after step c heat exchange, obtain epsom salt production
Product.
2. the method that a kind of utilization waste sulfuric acid from alkylation according to claim 1 produces epsom salt, it is characterised in that
The concentration of waste sulfuric acid from alkylation is 85~90wt% in step a, in waste sulfuric acid from alkylation COD concentration for 50000~
150000mg/L；
And/or, waste sulfuric acid from alkylation feeding temperature is 20~40 DEG C in step a；
And/or, step a high temperature pyrolysis furnaces pyrolysis temperature is 500~600 DEG C；
And/or, the time that step a high temperatures are decomposed is 6~12s；
And/or, cyclone dust collectors high-temperature flue gas import temperature is 300~400 DEG C in step b；
And/or, sack cleaner high-temperature flue gas import temperature is 200~300 DEG C in step b；
And/or, the temperature of pure air is 10~30 DEG C before being exchanged heat in step c, the temperature of the pure air after heat exchange for 60~
80℃；
And/or, the content of magnesia is 20~30wt% in light calcined magnesia slurry in step d；
And/or, it is 80~90 DEG C that neutral temperature is absorbed in step e, and sulfur trioxide and sulfur dioxide concentration are less than in tail gas
100ppm, air oxidation is that slurry sulfite magnesium is changed into magnesium sulfate；
And/or, the filtration temperature of the containing magnesium sulfate slurry obtained in step f is 70~85 DEG C；
And/or, crystallisation by cooling temperature is 15~30 DEG C in step g；The crystallisation by cooling time is 18~36h；
And/or, drying temperature is 40~60 DEG C in step h, and drying time is seven water sulfuric acid in 30~60min, obtained product
The content of magnesium is 98.5~99.8wt%.
3. a kind of system that utilization waste sulfuric acid from alkylation produces epsom salt, the system includes pyrolytic, dedusting, flue gas
Heat exchange, nertralizer dispensing, acid gas absorb, are separated by filtration, crystallisation by cooling and drying system.
4. the system that utilization waste sulfuric acid from alkylation according to claim 3 produces epsom salt, it is characterised in that high temperature
The gaseous phase outlet of decomposing system is connected with dust pelletizing system；The gaseous phase outlet of dust pelletizing system is connected with smoke heat exchanging system；Flue gas is changed
The gaseous phase outlet of hot systems, the slurry outlet and compressed air inlet of nertralizer feed proportioning system respectively with acid gas absorption system phase
Even；The liquid-phase outlet of acid gas absorption system is connected with being separated by filtration system；It is separated by filtration the liquid-phase outlet and crystallisation by cooling of system
System is connected；The solid-phase outlet of crystallisation by cooling system is connected with drying system；
And/or, the pyrolytic system is high-temperature cracking furnace (1), and using clean fuel as thermal source, waste sulfuric acid from alkylation is with vaporific
Enter from the side lower part of high-temperature cracking furnace；
And/or, the dust pelletizing system includes cyclone dust collectors (2) and sack cleaner (3), and high-temperature flue gas first passes through cyclone dust removal
Device, by cloth bag deduster；
And/or, the smoke heat exchanging system is flue gas heat-exchange unit (4), and wherein heat transferring medium is pure air；
And/or, the acid gas absorption system includes acid gas absorption tower (5), circulating slot (9), absorption tower circulating pump (6) and tail gas wind
Machine (7)；Wherein acid gas self-absorption tower side lower part enters；Nertralizer is drawn in the circulating pump self-loopa groove of absorption tower, on absorption tower
Upper lateral part spray carries out neutralization absorption to acid gas, neutralizes absorbing liquid self-absorption tower bottom and returns to circulating slot, tail gas self-absorption tower top
Drawn by exhaust fan in portion；Slurry is aoxidized under compressed air effect in circulating slot；
And/or, the nertralizer feed proportioning system is light calcined magnesia dosage bunker (8), and desalted water and light calcined magnesia are in light-burned oxygen
Change in magnesium dosage bunker and be made into slurry；
And/or, the system that is separated by filtration is white residue filter press (10)；
And/or, the crystallisation by cooling system includes cooler crystallizer (11), air cooling tower (12), air cooling pump (13) and centrifuge
(14)；Desalted water after air-cooled tower cooler as cooler crystallizer cooling medium, by air cooling pump in air cooling tower and crystallisation by cooling
Circulated between device；Cooler crystallizer discharging enters centrifuge, and the discharging of centrifuge solid phase enters drying system；
And/or, the drying system is drier (15), and dried medium is used as by the pure air from flue gas heat-exchange unit.
5. the system that utilization waste sulfuric acid from alkylation according to claim 4 produces epsom salt, it is characterised in that production
Method comprises the following steps：
I. high-temperature cracking furnace (1) is preheated first, treats that its bottom rises to required temperature, by waste sulfuric acid from alkylation from high anneal crack
The side lower part of solution stove (1) is sprayed into and reacted, and obtains the high-temperature flue gas containing sour gas；
II. high-temperature flue gas enters the import of cyclone dust collectors (2) after being left from high-temperature cracking furnace (1) top exit, then from rotation
The outlet of wind deduster (2) exits into the import of sack cleaner (3), then is left from the outlet of sack cleaner (3)；
III. the import that the high-temperature gas left enters the high-temperature gas of flue gas heat-exchange unit (4) is exported from sack cleaner (3), with
The pure air for entering the hot device of smoke gasification (4) from cryogenic gas import carries out heat exchange；
IV. light calcined magnesia and desalted water are configured to slurry in light calcined magnesia dosage bunker (8)；
V. the slurry in light calcined magnesia dosage bunker (8) is through circulating slot (9) its top feed mouthful addition circulating slot (9), from circulating slot
(9) bottom discharge mouth enters after leaving through absorption tower circulating pump (6) charging aperture, is left from the discharging opening of absorption tower circulating pump (6),
Enter acid gas absorption tower (5) through acid gas absorption tower (5) upper lateral part slurry spray inlet；Flue gas heat-exchange unit (4) is left containing acid gas
Enter from acid gas absorption tower (5) side lower part entrance, neutralization absorption, tail are carried out with the spray slurry from absorption tower circulating pump (6)
Gas is discharged by exhaust fan from acid gas absorption tower (5) Base top contact, and slurry is exited into from acid gas absorption tower (5) outlet at bottom and followed
Annular groove (9), the compressed air generation oxidation reaction with being passed through circulating slot (9)；
VI. the slurry in circulating slot (9) after neutralizing and absorbing and aoxidize delivers to white residue filter press through absorption tower circulating pump (6)
(10) separation of solid and liquid is carried out；
VII. the desalted water cooled down through air cooling tower (12) is delivered to cooler crystallizer (11) by air cooling pump (13), and backwater returns to air cooling
Tower (12)；The solution that white residue filter press (10) press filtration is obtained enters cooler crystallizer (11) decrease temperature crystalline, subsequently into centrifuge
(14) separation of solid and liquid is carried out, magnesium sulfate crystals are obtained；
VIII. the magnesium sulfate crystals that centrifuge (14) is obtained enter drier (15), using after flue gas heat-exchange unit (4) heat exchange
Pure air be dried, obtain epsom salt product.
6. the system for producing epsom salt according to any described utilization waste sulfuric acid from alkylation of claim 4-5, its feature exists
In using light calcined magnesia as conversion medium is neutralized, with alkylation spent acid production epsom salt；
And/or, the feeding temperature of waste sulfuric acid from alkylation is 20~40 DEG C；
And/or, sulfuric acid content is 85~90wt% in waste sulfuric acid from alkylation；
And/or, COD contents are 50000~150000mg/L in waste sulfuric acid from alkylation；
And/or, high-temperature cracking furnace bottom pyrolysis temperature is 500~600 DEG C；
And/or, the pyrolysis time in high-temperature cracking furnace is 6~12s；
And/or, the gas inlet temperature of cyclone dust collectors is 300~400 DEG C；
And/or, the gas inlet temperature of sack cleaner is 200~300 DEG C；
And/or, temperature is 10~30 DEG C before pure air heat exchange, and temperature is 60~80 DEG C after heat exchange；
And/or, the content of magnesia is 20~30wt% in light calcined magnesia dosage bunker；
And/or, it is 80~90 DEG C that the neutralization on acid gas absorption tower, which absorbs temperature,；
And/or, tail gas qualified discharge, sulfur dioxide and sulfur trioxide concentration are less than 100ppm；
And/or, the filtration temperature of white residue filter press is 70~85 DEG C；
And/or, crystallisation by cooling temperature is 15~30 DEG C, and the crystallisation by cooling time is 18~36h；
And/or, the drying temperature in drier is 40~60 DEG C, and drying time is 30~60min.
7. the system for producing epsom salt according to any described utilization waste sulfuric acid from alkylation of claim 4-5, its feature exists
In, by pyrolytic waste sulfuric acid from alkylation into sour gas, reacted with light calcined magnesia, produce epsom salt, institute
The content for obtaining epsom salt in product is 98.5~99.8wt%.
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| CN107555453A (en) * | 2017-09-25 | 2018-01-09 | 山东垚石化工科技有限公司 | A kind of technique of alkylate oil Waste Sulfuric Acid production anhydrous magnesium sulfate or/and high purity magnesium oxide |
| CN107827130A (en) * | 2017-12-13 | 2018-03-23 | 青岛锐丰源化工有限公司 | Utilize the production line for being alkylated spent acid and preparing magnesium sulfate |
| CN107986305A (en) * | 2017-12-13 | 2018-05-04 | 青岛锐丰源化工有限公司 | Utilize the production technology for being alkylated spent acid and preparing magnesium sulfate |
| CN108310935A (en) * | 2018-04-23 | 2018-07-24 | 焦作市雾神化工设备有限公司 | A kind of magnesium oxide method desulfurizing and drying all-in-one machine and construction method |
| CN109574044A (en) * | 2018-11-20 | 2019-04-05 | 盘锦泓实环保科技有限公司 | A kind of production technology using alkylation spent acid production sulfate |
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| CN107555453A (en) * | 2017-09-25 | 2018-01-09 | 山东垚石化工科技有限公司 | A kind of technique of alkylate oil Waste Sulfuric Acid production anhydrous magnesium sulfate or/and high purity magnesium oxide |
| CN107555453B (en) * | 2017-09-25 | 2019-11-12 | 山东垚石化工科技有限公司 | A kind of technique that alkylate oil Waste Sulfuric Acid produces anhydrous magnesium sulfate or/and high purity magnesium oxide |
| CN107827130A (en) * | 2017-12-13 | 2018-03-23 | 青岛锐丰源化工有限公司 | Utilize the production line for being alkylated spent acid and preparing magnesium sulfate |
| CN107986305A (en) * | 2017-12-13 | 2018-05-04 | 青岛锐丰源化工有限公司 | Utilize the production technology for being alkylated spent acid and preparing magnesium sulfate |
| CN107827130B (en) * | 2017-12-13 | 2024-04-02 | 青岛锐丰源化工有限公司 | Production line for preparing magnesium sulfate by using alkylated waste acid |
| CN108310935A (en) * | 2018-04-23 | 2018-07-24 | 焦作市雾神化工设备有限公司 | A kind of magnesium oxide method desulfurizing and drying all-in-one machine and construction method |
| CN109574044A (en) * | 2018-11-20 | 2019-04-05 | 盘锦泓实环保科技有限公司 | A kind of production technology using alkylation spent acid production sulfate |
| CN109574044B (en) * | 2018-11-20 | 2021-01-26 | 盘锦泓实环保科技有限公司 | Production process for producing sulfate by using alkylated waste acid |
| CN113440993A (en) * | 2020-03-24 | 2021-09-28 | 中国科学院过程工程研究所 | Purification system and purification method for organic silicon acid-containing waste gas |
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