CN106366066B - A kind of compression/condensing recovery sulfur dioxide method in sulfolane production process - Google Patents
A kind of compression/condensing recovery sulfur dioxide method in sulfolane production process Download PDFInfo
- Publication number
- CN106366066B CN106366066B CN201610712136.4A CN201610712136A CN106366066B CN 106366066 B CN106366066 B CN 106366066B CN 201610712136 A CN201610712136 A CN 201610712136A CN 106366066 B CN106366066 B CN 106366066B
- Authority
- CN
- China
- Prior art keywords
- sulfur dioxide
- pressure
- butadiene
- compression
- sulfolane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/46—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom
- C07D333/48—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom by oxygen atoms
-
- 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
- C01B17/48—Sulfur dioxide; Sulfurous acid
- C01B17/50—Preparation of sulfur dioxide
- C01B17/56—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of compression/condensing recovery sulfur dioxide methods in sulfolane production process, in sulfolane production, it is depressured using intermediate product cyclobufene sultone reactor overbottom pressure, with the unreacted sulfur dioxide of step by step compression condensing mode recycling sulfolane production process and 1,3 butadiene；No matter for interval production technology or continuous sulfolane production technology, all reached good desulfurization effect, reduced sulfur dioxide emissioning concentration, reach national requirements for environmental protection.
Description
Technical field
The present invention relates to the methods in sulfolane production process, recycling sulfur dioxide using compression/condensation process.
Background technique
Extractant of the sulfolane as Aromatics Extractive Project, has important application in petrochemical industry.Currently, synthesis sulfolane
There are three types of methods, and one is thiophane oxidizing process, and using potassium permanganate or hydrogen peroxide as oxidant, oxidation product is extracted with benzene
Afterwards, it is fractionated, the sulfolane close to 100% can be obtained.Second method is ethylene and sulfur dioxide synthetic method.The third side
Method is cyclobufene sultone hydrogenization method, i.e., is reacted in the presence of polymerization inhibitor using 1,3 butadiene of liquid with sulfur dioxide and generate cyclobutane
Sulfone, then by cyclobufene sultone it is hydrogenated after, produce sulfolane.First two method is due in Technological Economy, up to the present
Not yet realize really industrialization, cyclobufene sultone hydrogenization method is the currently the only industrialized method of realization.
Four parts, (1) composite part, using liquid 1,3 can be divided into mostly for cyclobufene sultone hydrogenization method technical process
Butadiene reacts in the presence of polymerization inhibitor with sulfur dioxide generates cyclobufene sultone；(2) disengagement section, removing synthetic reaction process is not
The sulfur dioxide and butadiene of reaction, and the concentration of sulfur dioxide in liquid phase is down to 50ppm hereinafter, in favor of hydrogenation reaction
It goes on smoothly；(3) it is added after adding hydrogen partial, desulfurization qualified plus hydrogen solvent is configured to cyclobufene sultone solution, in the presence of a catalyst
Hydrogenation reaction is carried out with hydrogen, generates sulfolane；(4) product purification part adds the coarse sulfolane product obtained after hydrogen at
Become finished product sulfolane after reason.
In cyclobufene sultone synthesis technology, since reaction is that 1,3 butadiene react generation ring fourth with excessive sulfur dioxide
Alkene sulfone, excessive sulfur dioxide will lead to the catalyst poisoning of cyclobufene sultone hydrogenation, so excessive sulfur dioxide is necessary
Removing.Disengagement section has obtained more and more concerns at present, and chief reason derives from two o'clock., reduce material consumption at first point.Cause
For sulfur dioxide inherently reactant, so if can be superfluous sulfur dioxide recovery, so that it may save material consumption, reduce life
Produce cost.Used desulfurization both at home and abroad all refers to chemical absorbing, such as Shell technology, Philips's technique and Jinzhou at present
The sulfolane production technology of petrochemical industry, is all made of sodium hydroxide solution and sulfur dioxide chemically reacts, and reaches removing titanium dioxide
The purpose of sulphur.Second point is the requirement based on environmental protection.Current sulfolane production mostly uses batch production process, due to
Sulfur dioxide is excessive, and after the reaction was completed, sulfur dioxide surplus is larger, after Dilution air purges, discharge initial stage due to
Moment sulfur dioxide concentration is excessively high, it is difficult to all reach the standard of environmental emission at whole moment of discharge.With both at home and abroad to big
The attention in compression ring border, especially China propose the control standard being increasingly stringenter to sulfur dioxide (SO2) emissions recently, lead to ring fourth
Sulfone manufacturer is faced with huge survival pressure.Therefore desulfurization is carried out using new process route, it is ensured that enterprise's sulfur dioxide
Atmosphere discharge meets national standard, is very urgent task.In view of sulfur dioxide and 1,3 butadiene are all reactants, institute
With the new thinking of sulfur removal technology, it should be that can on the one hand recycle unreacted material to pass through simultaneously to reduce material consumption
It recycles unreacted sulfur dioxide and reduces the emission reduction of subsequent sulfur dioxide.The present invention be under such thinking, it is right
Desulfurization has carried out new technological design in sulfolane production.
Summary of the invention
Goal of the invention:
It cannot be guaranteed that whole periods reach for sulfur dioxide emissioning concentration in sulfur removal technology in interval sulfolane production technology
Target situation, the present invention redesign sulfur removal technology, pass through innovative compression/condensation process, one side maximum
Recycling reactant sulfur dioxide, reduce the material consumption of reaction, while reducing the pressure of subsequent caustic wash desulfuration, it is ensured that sulfur dioxide exists
Concentration in discharge gas meets the discharge standard of current atmospheric environment；And to the sweetening process of continuous sulfolane production process,
It also proposed compression/condensation process program, to reach environmental protection and reduce the dual purpose of cost.
Technical solution:
A kind of compression/condensing recovery sulfur dioxide method in sulfolane production process, it is characterised in that: raw in sulfolane
It in production, is depressured using intermediate product cyclobufene sultone reactor overbottom pressure, sulfolane production process is recycled with step by step compression condensing mode
Unreacted sulfur dioxide and 1,3 butadiene.
Sulfolane production is divided into two kinds of production methods of continuous production and Batch Process.
Referred to using the overbottom pressure decompression of sulfolane reactor: the material for going out cyclobufene sultone reactor is born greater than 0.6MPa's
Pressure is depressured this partial high pressure material, and when pressure drops to 0.6MPa or less, gasification takes place in liquid phase material.
Compression condensation refers to: gradually pressure drop stage is carried out to the cyclobufene sultone reacting rear material greater than 0.6MPa, from initial pressure
When power is reduced to 0.6MPa or less, cyclobufene sultone liquid mixture gasifies, when material is dropped to from the pressure to gasify
When this pressure stage of 0.4MPa, vaporized gas is directly entered condenser, is condensed, and is mainly titanium dioxide in condensate liquid
Sulphur and 1,3 butadiene and a small amount of cyclobufene sultone, then material continues to be depressured, when material pressure is lower than 0.4MPa or less
When, after vaporized gas will boost after compressor compresses, then through condensing recovery sulfur dioxide and 1,3 butadiene.
Compression condensation refers to: gradually pressure drop stage is carried out to the cyclobufene sultone reacting rear material greater than 0.6MPa, from initial pressure
When power is reduced to 0.6MPa or less, cyclobufene sultone liquid mixture gasifies, when material is dropped to from the pressure to gasify
When this pressure stage of 0.4MPa, vaporized gas is directly entered condenser, is condensed, and is mainly titanium dioxide in condensate liquid
Sulphur and 1,3 butadiene and a small amount of cyclobufene sultone, then material continues to be depressured, when material pressure is lower than 0.4MPa or less
When, after vaporized gas will boost after compressor compresses, then through condensing recovery sulfur dioxide and 1,3 butadiene.
Step by step compression condensation refers to, when material reacted in cyclobufene sultone reaction kettle is after pressure reduction gasifies, when
For pressure in 0.4MPa or more, gas is directly entered condenser, is condensed, and is mainly sulfur dioxide and 1,3 in condensate liquid
Butadiene and a small amount of cyclobufene sultone, and when material is depressurized to lower than 0.4MPa or less, the gas for being flashed out will be through
After the compression of overcompression machine, then condensing recovery sulfur dioxide and 1,3 butadiene.
Reacted material is between 90-110 DEG C in the temperature condition in pressure reduction in cyclobufene sultone reaction kettle.
Most liquid sulfur dioxide and 1 are recycled in decompression, compression condensation sulfur removal technology, after 3 butadiene, then with it is subsequent
Alkali washing process combines, and controls tail gas sulphur dioxide concentration of emission.
Advantage and effect:
The invention proposes a kind of compression/condensing recovery sulfur dioxide methods in sulfolane production process, have following
Advantage:
The present invention carries out decompression processing, is down to liquid phase object to the reaction mass in the sulfolane reactor that subject high pressure
The state of gasification takes place in material, and when pressure is in 0.4MPa or more, the gas of gasification is directly entered condenser, by all cold
It is solidifying, it is mainly sulfur dioxide and 1,3 butadiene and a small amount of cyclobufene sultone in condensate liquid, and when pressure is lower than 0.4MPa or less
When, gas will pass through compressor compresses, then be condensed again, and sulfur dioxide and 1,3 butadiene, the sulfur dioxide of recycling are recycled
Reactant is re-used as with 1,3 butadiene to be utilized.The present invention increases compression/condensation work by producing sweetening process in sulfolane
Skill has recycled most sulfur dioxide, reduces the pressure of the subsequent desulfurization of device, compression/condensation desulfurization recovery process is with after
Continuous alkali washing process combines, and can control the emission request that sulfur dioxide in tail gas concentration of emission reaches National Environmental atmosphere.
Currently, being engaged in corporate boss's technology to be used of sulfolane production both at home and abroad has Britain's Philips's technique, shell
Board technique, SUMITOMO CHEMICAL technique, Chinese Jinzhou Petrochemical Company technique.These technical process all include sweetening process.Philips's technique is adopted
It is that Vacuum Desulfurization and lye desulfurization combine, Sumitomo technique uses air stripping and lye desulfurization, the use of Jinzhou Petrochemical Company
Be that warm air blowoff and lye desulfurization combine, the above technique is all not carried out the recycling to raw material sulfur dioxide,
And a large amount of lye sulfur dioxide absorption is used, cost is on the one hand increased, ring caused by sulfur dioxide (SO2) emissions is on the one hand caused
Border pollution.Only have Shell technology to carry out cycling and reutilization to sulfur dioxide in prior art, which passes through absorption-rectifying
Desorption process realizes the recycling of sulfur dioxide, but due to absorption and desorption cyclic process, feed liquid is largely recycled, so energy consumption is very
It is high.And the present invention relates to the compression condensation method mentioned, and using original overbottom pressure, carries out step by step compression condensation, and energy consumption is down to
It is minimum, while by the most sulfur dioxide of recycling, the pressure of subsequent lye is reduced, the consumption of lye has not only been reduced, but also
The emission reduction of sulfur dioxide is realized, is had and is saved the energy, saves material consumption and more environmentally friendly triple advantages.
Detailed description of the invention
Fig. 1 is mass fraction of the different pressures condition sulfur dioxide in gas phase mixture at 100 DEG C.
Show that when the material of cyclobufene sultone reaction kettle out be 100 DEG C in temperature from Fig. 1, pressure is 0.1-0.5MPa range
It is interior, sulfur dioxide gas phase mass fraction with pressure variation tendency.According to Phase Diagram Analysis, only pressure is lower than 0.6MPa
When, liquid material could gasify at existing temperature, therefore it is 0.1- that the effective pressure of compression/condensation process, which adjusts section,
Between 0.5MPa.Fig. 1 shows the reduction with pressure, and content of sulfur dioxide increases in gas phase, this is conducive to recycle more two
Sulfur oxide.But it is depressurized to which kind of degree is limited by condenser liquid-phase outlet temperature, after pressure is as low as certain degree, to handle
Gas is condensed into liquid phase, needs to condense to lower temperature, to use cooling water as cooling medium, condensation temperature is cooled down
The limitation of coolant-temperature gage cannot be below 20 DEG C.So to design reasonable compression/condensation scheme, the operating condition for meeting actual production is wanted
It asks.
Fig. 2 Batch Process sulfur dioxide removal/compression/condensation process flow chart.
1,3 butadiene and sulfur dioxide drain into devulcanizing pan 2 after completion of the reaction in reactor 1, then start to system
Decompression.When discharge pressure is higher, the gaseous mixture of gasification directly passes through condenser 4 and condenses, and condensed liquid enters dioxy
Change sulphur and 1, in the measuring tank 5 of 3 butadiene, when discharging pressure reduction to 0.4MPa or less, opens diaphragm type compressor 6, pass through
The sulfur dioxide and 1 of high concentration is compressed, 3 butadiene mixed gas enter measuring tank 5 into condenser after condensation.Pass through dioxy
Change the liquidometer on sulfur recovery measuring tank 5, measures the recuperable sulfur dioxide of above-mentioned two step and 1,3 butadiene.Solution
In remaining sulfur dioxide and 1,3 butadiene into air reservoir 8, then are passed through after 7 compressed air stripping of air compressor
It crosses air heater 9 mixed gas is cooling, remaining sulfur dioxide is then absorbed by absorption tower lye.
Compression condensation desulfurization flow chart in Fig. 3 continuous production process.
1,3 butadiene and sulfur dioxide drain into devulcanizing pan 2 after completion of the reaction in reactor 1, excessive in devulcanizing pan
High temperature and pressure high-concentration sulfur dioxide gas first passes around the condensation of condenser 4, subsequently into measuring tank 5, there is gas-liquid two herein
Phase, liquid phase be recycling sulfur dioxide and 1,3 butadiene, uncooled gas again through diaphragm type compressor 6 compression after, pass through condensation
Device enters measuring tank 5 after condensation, further recycle sulfur dioxide and 1,3 butadiene.Pass through sulfur dioxide recovery measuring tank 5
On liquidometer, measure the recuperable sulfur dioxide of above-mentioned two step and 1,3 butadiene.Remaining sulfur dioxide in solution
With 1,3 butadiene first pass around condenser, mixed gas are cooled to 20 after 7 compressed air stripping of air compressor
DEG C, then absorbed by absorption tower lye.
The equilibrium of ternary system within the scope of 1 pressure 0.1-0.5MPa of table.
Table 1 lists the equilibrium that pressure is respectively the ternary system under 0.1MPa, 0.3MPa and 0.5MPa.Left side
First is classified as different pressure, and second is classified as different temperatures corresponding under different pressures, behind several column represent different temperatures and
Under pressure, sulfur dioxide/1,3 butadiene/cyclobufene sultone ternary system mass fraction in gas phase and liquid phase respectively.From table 1
Know, the content of cyclobufene sultone in the gas phase is seldom, can ignore substantially, so being mainly sulfur dioxide and 1,3 fourths two in gas phase
Alkene；With the reduction of pressure, the mass fraction of sulfur dioxide in the gas phase increases；At the same pressure, temperature is higher, titanium dioxide
The mass fraction of sulphur in the gas phase is bigger.
2 step by step compression of table/condensation scheme condensing recovery amount and condensation temperature.
The variation of condensing recovery amount and condensation temperature under step pressure reducing scheme given in table 2.The decompression side provided in table
Case is, when the temperature of charge that devulcanizing pan comes out is 110 DEG C, to be first once depressurized to 0.5MPa, be then depressurized to 0.4MPa again, so
It is down to 0.3MPa again afterwards, is finally down to 0.2MPa.After pressure is down to 0.4MPa, condensed cooling temperature can be lower than cooling
Water, therefore pressure increased to gas phase and then condensed, so gas will enter compressibility and boost, complete after pressure is 0.4MPa
At condensing recovery process.Secondary series in table 2 lists sulfur dioxide, 1, the amount of 3 butadiene and cyclobufene sultone, this tittle difference
It is to have had the recycling of liquid phase output after being depressured each time, so the raw material of next decompression system because reducing pressure step by step
Composition will do corresponding subtraction, subtract the material condensed, remaining material is depressurized generation gas phase again, and then gas phase passes through again
The liquid phase that compression/condensation is recycled.After every grade of decompression, or adjoint compression, condensed sulfur dioxide, 1,3 fourths two are obtained
Alkene and cyclobufene sultone are listed in table 2 to be come, by the decompression of whole process, compression/condensation, the total each substance finally obtained
Yield listed in table 2.Every grade of condensed liquidus temperature is also listed in table, by data it is found that condenser out
Temperature is all larger than 20 DEG C.Can be with the rate of recovery of calculated sulfur dioxide for 65.5% from table 2, the rate of recovery of 1,3 butadiene is
90.6%, overall recovery 68.5%.
Description of symbols:
1, reactor, 2, devulcanizing pan, 3, coil heat exchanger, 4, condenser, 5, measuring tank, 6, diaphragm type compressor, 7, air
Compressor, 8, air reservoir, 9, air heater.
Specific embodiment
For in sulfolane production technology, the sulfur dioxide emissioning concentration after desulfurization cannot be guaranteed all the period of time feelings up to standard
Condition, the present invention are designed for the sulfur removal technology in interval sulfolane and the production of continuous sulfolane, pass through innovative pressure
Contracting/condensation process, on the one hand can the maximum amount of recycling reactant sulfur dioxide, the material consumption of reaction is reduced, simultaneously because part
The recycling of sulfur dioxide reactant reduces the pressure of subsequent caustic wash desulfuration, so that it is guaranteed that concentration of the sulfur dioxide in discharge gas
The discharge standard for meeting current atmospheric environment reaches environmental protection and reduces the dual purpose of cost.
Compression/condensing recovery sulfur dioxide method in sulfolane production process proposed by the present invention is raw in sulfolane
It in production, is depressured using intermediate product cyclobufene sultone reactor overbottom pressure, sulfolane production process is recycled with step by step compression condensing mode
Unreacted sulfur dioxide and 1,3 butadiene.
Sulfolane production is divided into two kinds of production methods of continuous production and Batch Process.
Referred to using the overbottom pressure decompression of sulfolane reactor: the material for going out cyclobufene sultone reactor is born greater than 0.6MPa's
Pressure is depressured this partial high pressure material, and when pressure drops to 0.6MPa or less, gasification takes place in liquid phase material.
Compression condensation refers to: gradually pressure drop stage is carried out to the cyclobufene sultone reacting rear material greater than 0.6MPa, from initial pressure
When power is reduced to 0.6MPa or less, cyclobufene sultone liquid mixture gasifies, when material is dropped to from the pressure to gasify
When this pressure stage of 0.4MPa, vaporized gas is directly entered condenser, is condensed, and is mainly titanium dioxide in condensate liquid
Sulphur and 1,3 butadiene and a small amount of cyclobufene sultone, then material continues to be depressured, when material pressure is lower than 0.4MPa or less
When, after vaporized gas will boost after compressor compresses, then through condensing recovery sulfur dioxide and 1,3 butadiene.
Step by step compression condensation refers to, when material reacted in cyclobufene sultone reaction kettle is after pressure reduction gasifies, when
For pressure in 0.4MPa or more, gas is directly entered condenser, is condensed, and is mainly sulfur dioxide and 1,3 in condensate liquid
Butadiene and a small amount of cyclobufene sultone, and when material is depressurized to lower than 0.4MPa or less, the gas for being flashed out will be through
After the compression of overcompression machine, then condensing recovery sulfur dioxide and 1,3 butadiene.
The principle of step by step compression condensation refers to that during implementing compression condensation, as needed, pressure change can be divided into
Multistage, the final value after first order decompression is 0.4MPa, and in this stage, the gas phase of generation is directly entered subsequent condensing unit,
Then continue to be depressured, subsequent decompression can there are many decompression selections.A variety of decompressions selection refers to: the first order, to liquid phase material,
0.4MPa is dropped to by the pressure of cyclobufene sultone reactor outlet, under this pressure, the gas after liquid-phase vaporization is directly entered cold
Condenser is condensed into liquid phase, realizes recycling.The second level continues liquid phase material to be depressured, and first pressing 0.4MPa, end of a period pressure can be
Value between 0.4MPa to 0.2MPa send again to compressor the gas phase generated after decompression and boosts, it is cold then to enter back into condenser
It is solidifying, the liquid phase recycled.Thus there was only two stages of compression condensation.Because the range of final pressure is 0.4MPa since the second level
To between 0.2MPa, so according to practice in factory, any pressure value that can choose this section does final pressure, so selection can
With diversity.
If continuing to be depressured to liquid phase material since 0.4MPa, final pressure can be the pressure between 0.4MPa to 0.2MPa
Power, under the pressure of material in this stage, will continue to gasification is gas, then compresses and boost to this portion gas, and boosting to can
Pressure under condensing this portion gas all realizes the purpose of compression condensation recycling gas phase.
Also it can choose three-level scheme, material pressure dropped to 0.3MPa as the second level from 0.4MPa, is down to 0.3MPa
The gas phase that process generates is sent to compressor and carries out compression boosting, then enters condenser and condenses, the liquid phase recycled.So
Next the third level just being had, pressure is down to 0.2MPa by 0.3MPa, and the gas phase generated after decompression is sent again to compressor and is boosted,
Then condenser condensation, the liquid phase recycled are entered back into.
Reacted material is between 90-110 DEG C in the temperature condition in pressure reduction in cyclobufene sultone reaction kettle.
Most liquid sulfur dioxide and 1 are recycled in decompression, compression condensation sulfur removal technology, after 3 butadiene, then with it is subsequent
Alkali washing process combines, and controls tail gas sulphur dioxide concentration of emission.
When using Batch Process mode, the method for recycling sulfur dioxide is as follows:
Using step by step compression/condensation process, 1,3 butadiene and sulfur dioxide drain into de- after completion of the reaction in reactor 1
In sulphur kettle 2, excessive high temperature and pressure high-concentration sulfur dioxide gas is after decompression in devulcanizing pan, under a certain pressure, liquid phase
It can vaporize, be the sulfur dioxide and 1 of high-content, 3 butadiene in gas phase.It is direct when gas phase is when elevated pressures are discharged
It is condensed into condenser 4, recycles sulfur dioxide and 1,3 butadiene.When discharging pressure reduction to 0.4MPa or less, diaphragm is opened
Compressor 6 recycles the sulfur dioxide under low-pressure vapor phase using compression/condensation process.By on sulfur dioxide recovery measuring tank 5
Liquidometer, measure the recuperable sulfur dioxide of above-mentioned two step and 1,3 butadiene account for about unreacted residue sulfur dioxide
With the 55-70% of 1,3 butadiene amounts.Remaining sulfur dioxide and 1 in solution, 3 butadiene compress sky by air compressor 7
It is using air heater 9 that mixed gas is cooling into air reservoir 8 after air-blowing is de-, then absorbed by absorption tower lye
Remaining sulfur dioxide.
When using continuous production mode, the method for recycling sulfur dioxide is as follows:
For the material come out from cyclobufene sultone devulcanizing pan, using the compression condensation desulfurization program of secondary recovery, level-one is straight
Condensing recovery sulfur dioxide and 1,3 butadiene were connected, second level is used first to compress and be condensed again, realizes recycling two to the greatest extent
Sulfur oxide and 1,3 butadiene.1,3 butadiene and sulfur dioxide drain into devulcanizing pan 2 after completion of the reaction in reactor 1, by drop
After pressing 0.2MPa, the high temperature and pressure high-concentration sulfur dioxide gas in devulcanizing pan first passes around condenser 4 and is cooled to 25 DEG C, returns
Receiving portions liquid phase sulfur dioxide and 1,3 butadiene enter storage tank 5, and uncooled gas is compressed to through diaphragm type compressor 6
After 0.4MPa, then 25 DEG C are cooled to by condenser condensation 4 and further recycles sulfur dioxide and 1,3 butadiene.Secondary recovery mistake
Cheng Lianxu stable state carries out.By on sulfur dioxide recovery measuring tank 5 liquidometer, above-mentioned two step recuperable two is measured
Sulfur oxide and 1,3 butadiene, yield account for about reaction total surplus sulfur dioxide and 1, the 55-70% of 3 butadiene amounts.It is remained in solution
Remaining sulfur dioxide and 1,3 butadiene, after 7 compressed air stripping of air compressor, into air reservoir 8, using sky
Hot-air heater 9 is cooling by mixed gas, then absorbs remaining sulfur dioxide by absorption tower lye.
Below with reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not implemented
The limitation of example.
Embodiment 1
For a batch production process, become into reaction kettle material liquid group, 1,3 butadiene 1070kg of liquid, liquid two
Sulfur oxide 1400kg enters reaction kettle together, produces cyclobufene sultone using hydrogen is added, rectifying obtains sulfolane product.Cyclobutane
After sulfone fully reacting, become from the kettle material group that goes out of reactor, cyclobufene sultone 2290.411kg, reacting remaining sulfur dioxide is
158.064kg, 1,3 butadiene are 21.4kg, and sulfur dioxide and 1,3 butadiene are dissolved in cyclobufene sultone liquid phase.Reactor out
Material pressure be 1.0MPa, temperature be 110 DEG C.Kettle material is gone out to the composition, carries out step pressure reducing.Depressurization step: to liquid
Phase materials directly drop to 0.4MPa, pass through condensing recovery part sulfur dioxide and 1,3 butadiene, then again to remaining liquid phase material
It is depressured to 0.2MPa, for the gas constantly generated, after diaphragm type compressor is compressed to 0.4MPa, then using condenser
Condensation, obtain being compressed/condensation process after the sulfur dioxide and 1 that recycles, 3 butadiene.The sulfur dioxide recycled is
104.597kg, 1,3 butadiene are 18.895kg, and the rate of recovery 66.17% of sulfur dioxide, the rate of recovery of 1,3 butadiene is
88.13%, yield, which accounts for, reacts total surplus sulfur dioxide and 1, and the 68.81% of 3 butadiene amounts.
Embodiment 2:
For a batch production process, become into reaction kettle material liquid group, 1,3 butadiene 1070kg of liquid, liquid two
Sulfur oxide 1400kg enters reaction kettle together, produces cyclobufene sultone using hydrogen is added, rectifying obtains sulfolane product.Cyclobutane
After sulfone fully reacting, become from the kettle material group that goes out of reactor, cyclobufene sultone 2290.411kg, reacting remaining sulfur dioxide is
158.064kg, 1,3 butadiene are 21.4kg, and sulfur dioxide and 1,3 butadiene are dissolved in cyclobufene sultone liquid phase.Reactor out
Material pressure be 1.0MPa, temperature be 110 DEG C.Kettle material is gone out to the composition, carries out step pressure reducing, depressurization step: to liquid
Phase materials directly drop to 0.5MPa, pass through condensing recovery part sulfur dioxide and 1,3 butadiene, then again to remaining liquid phase material
It is depressured to 0.4MPa, then by condensing recovery part sulfur dioxide and 1,3 butadiene, then remaining liquid phase material is depressured to and is down to
0.2MPa, for the gas constantly generated, after diaphragm type compressor compressor compresses to 0.4MPa, then again into condenser excessively
Condensation, obtains the sulfur dioxide recycled after compression/condensation process and 1,3 butadiene.The sulfur dioxide of obtained recycling is
103.5kg, 1,3 butadiene are 19.3kg, and the rate of recovery 65.5% of sulfur dioxide, the rate of recovery of 1,3 butadiene is 90.6%, is returned
Receipts amount accounts for the 68.5% of reaction total surplus sulfur dioxide and 1,3 butadiene amounts.
Embodiment 3
For a batch production process, become into reaction kettle material liquid group, 1,3 butadiene 1070kg of liquid, liquid two
Sulfur oxide 1400kg enters reaction kettle together, produces cyclobufene sultone using hydrogen is added, rectifying obtains sulfolane product.Cyclobutane
After sulfone fully reacting, become from the kettle material group that goes out of reactor, cyclobufene sultone 2290.411kg, reacting remaining sulfur dioxide is
158.064kg, 1,3 butadiene are 21.4kg, and sulfur dioxide and 1,3 butadiene are dissolved in cyclobufene sultone liquid phase.Reactor out
Material pressure be 1.0MPa, temperature be 90 DEG C.Kettle material is gone out to the composition, carries out step pressure reducing, depressurization step: to liquid phase
Material is directly depressurized to 0.4MPa, passes through condensing recovery part sulfur dioxide and 1,3 butadiene, then again to remaining liquid phase material
It is depressured to 0.2MPa, for the gas constantly generated, after diaphragm type compressor is compressed to 0.4MPa, then again into condenser excessively
Condensation, obtains the sulfur dioxide recycled after compression/condensation process and 1,3 butadiene.The sulfur dioxide of obtained recycling is
82.414kg, 1,3 butadiene are 17.27kg, and the rate of recovery 52.14% of sulfur dioxide, the rate of recovery of 1,3 butadiene is
80.7%, yield, which accounts for, reacts total surplus sulfur dioxide and 1, and the 55.55% of 3 butadiene amounts.
Embodiment 4:
For a tandem reaction sequence, become into reaction kettle material liquid group, 1,3 butadiene 1070kg/hr of liquid, liquid
Sulfur dioxide 1400kg/hr enters reaction kettle together, produces cyclobufene sultone using hydrogen is added, rectifying obtains sulfolane product.Ring
After butylene sulfone fully reacting, become from the kettle material group that goes out of reactor, cyclobufene sultone 2290.411kg/hr, reaction remaining two
Sulfur oxide is 158.064kg/hr, and 1,3 butadiene is 21.4kg/hr, sulfur dioxide and 1, and 3 butadiene are dissolved in cyclobufene sultone liquid
Xiang Zhong.The material pressure of reactor is 1.0MPa out, and temperature is 110 DEG C.Tower material is gone out to this, is directly depressurized to
Then 0.2MPa is condensed by gas phase of the condenser to gasification again, control outlet temperature is 25 DEG C, then passes through one again
Play the measuring tank of flash distillation, liquid phase is recovered, and not solidifying gas phase condenses again after diaphragm type compressor is compressed to 0.4MPa, is recycled
Two parts liquid phase mix.The sulfur dioxide of obtained recycling is 103.5kg/hr, and 1,3 butadiene is 19.3kg/hr,
The rate of recovery 67.63% of sulfur dioxide, the rate of recovery of 1,3 butadiene are 85.02%, and yield accounts for reaction total surplus sulfur dioxide
With the 69.7% of 1,3 butadiene amounts.
Implementation column 5
For a tandem reaction sequence, become into reaction kettle material liquid group, 1,3 butadiene 1070kg/hr of liquid, liquid
Sulfur dioxide 1400kg/hr enters reaction kettle together, produces cyclobufene sultone using hydrogen is added, rectifying obtains sulfolane product.Ring
After butylene sulfone fully reacting, become from the tower material group that goes out of reactor, cyclobufene sultone 290.411kg/hr reacts remaining dioxy
Change sulphur is 158.064kg/hr, and 1,3 butadiene is 21.4kg/hr, they are partially dissolved in cyclobufene sultone liquid phase.Reactor out
Material pressure be 1.0MPa, temperature be 90 DEG C.Kettle material is gone out to the composition, progress is directly depressurized to 0.2MPa, then again
It being condensed by condenser, control outlet temperature is 25 DEG C, then plays the measuring tank of flash distillation by one again, and liquid phase recycles,
Not solidifying gas phase condenses again after diaphragm type compressor is compressed to 0.4MPa, and two parts liquid phase of recycling mixes.It obtains
The sulfur dioxide of recycling be 84.635kg/hr, 1,3 butadiene be 16.684kg/hr, the rate of recovery 53.54%, 1 of sulfur dioxide,
The rate of recovery of 3 butadiene is 77.96%, and yield, which accounts for, reacts total surplus sulfur dioxide and 1, the 56.46% of 3 butadiene amounts.
Embodiment 6
For a batch production process, become into reaction kettle material liquid group, 1,3 butadiene 1670kg of liquid, liquid two
Sulfur oxide 2200kg enters reaction kettle together, produces cyclobufene sultone using hydrogen is added, rectifying obtains sulfolane product.Cyclobutane
After sulfone fully reacting, become from the kettle material group that goes out of reactor, cyclobufene sultone 3581.1kg, reacting remaining sulfur dioxide is
260.39kg, 1,3 butadiene are 33.4kg, they are dissolved in cyclobufene sultone liquid phase.The material pressure of reactor is out
1.0MPa, temperature are 110 DEG C.Kettle material is gone out to the composition, step pressure reducing is carried out, step will be pressed: direct to liquid phase material
0.3MPa, by condensing recovery part sulfur dioxide and 1, then 3 butadiene are depressured to 0.2MPa to remaining liquid phase material again,
For the gas constantly generated, after diaphragm type compressor is compressed to 0.4MPa, then pressed again into condenser condensation is crossed
The sulfur dioxide and 1,3 butadiene recycled after contracting/condensation process.The sulfur dioxide of obtained recycling is 175.89kg, 1,3 fourth two
Alkene is 29.75kg, and the rate of recovery 67.55% of sulfur dioxide, the rate of recovery of 1,3 butadiene is 88.96%, and it is total that yield accounts for reaction
The 69.99% of remaining sulfur dioxide and 1,3 butadiene amounts.
Embodiment 7:
For a tandem reaction sequence, 1,3 butadiene 1670kg/hr of reaction raw materials liquid, liquid sulfur dioxide
2200kg/hr enters reaction kettle together, produces cyclobufene sultone using hydrogen is added, rectifying obtains sulfolane product.Cyclobufene sultone is anti-
After answering completely, become from the kettle material group that goes out of reactor, cyclobufene sultone 3581.1kg/hr, reacting remaining sulfur dioxide is
260.39kg/hr, 1,3 butadiene are 33.4kg/hr, they are dissolved in cyclobufene sultone liquid phase.The material pressure of reactor out
For 1.0MPa, temperature is 110 DEG C.Kettle material is gone out to the composition, progress is directly depressurized to 0.2MPa, then passes through condenser again
Condensation, control outlet temperature are 25, then play the measuring tank of flash distillation, liquid phase recycling by one again, and gas phase passes through diaphragm
It is condensed again after compressor compresses to 0.4MPa, two parts liquid phase of recycling mixes.The sulfur dioxide of obtained recycling is
179.53kg/hr, 1,3 butadiene are 28.85kg/hr, and the rate of recovery 68.95% of sulfur dioxide, the rate of recovery of 1,3 butadiene is
86.37%, yield, which accounts for, reacts total surplus sulfur dioxide and 1, and the 70.92% of 3 butadiene amounts.
Embodiment 8:
For a batch production process, become into reaction kettle material liquid group, 1,3 butadiene 1070kg of liquid, liquid two
Sulfur oxide 1400kg enters reaction kettle together, produces cyclobufene sultone using hydrogen is added, rectifying obtains sulfolane product.Cyclobutane
After sulfone fully reacting, become from the kettle material group that goes out of reactor, cyclobufene sultone 2290.411kg, reacting remaining sulfur dioxide is
158.064kg, 1,3 butadiene are 21.4kg, and sulfur dioxide and 1,3 butadiene are dissolved in cyclobufene sultone liquid phase.Reactor out
Material pressure be 1.0MPa, temperature be 100 DEG C.Kettle material is gone out to the composition, carries out step pressure reducing, depressurization step: to liquid
Phase materials are directly depressurized to 0.4MPa, pass through condensing recovery part sulfur dioxide and 1,3 butadiene, then again to remaining liquid phase object
Material is depressured to 0.2MPa, for the gas constantly generated, after diaphragm type compressor is compressed to 0.4MPa, then again into condensation excessively
Device condensation, obtains the sulfur dioxide recycled after compression/condensation process and 1,3 butadiene.The sulfur dioxide of obtained recycling is
94.702kg, 1,3 butadiene are 18.249kg, and the rate of recovery 59.91% of sulfur dioxide, the rate of recovery of 1,3 butadiene is
85.27%, yield, which accounts for, reacts total surplus sulfur dioxide and 1, and the 62.94% of 3 butadiene amounts.
Embodiment 9:
For a tandem reaction sequence, 1,3 butadiene 1670kg/hr of reaction raw materials liquid, liquid sulfur dioxide
2200kg/hr enters reaction kettle together, produces cyclobufene sultone using hydrogen is added, rectifying obtains sulfolane product.Cyclobufene sultone is anti-
After answering completely, become from the kettle material group that goes out of reactor, cyclobufene sultone 3581.1kg/hr, reacting remaining sulfur dioxide is
260.39kg/hr, 1,3 butadiene are 33.4kg/hr, they are dissolved in cyclobufene sultone liquid phase.The material pressure of reactor out
For 1.0MPa, temperature is 100 DEG C.Kettle material is gone out to the composition, progress is directly depressurized to 0.2MPa, then passes through condenser again
Condensation, control outlet temperature are 25, then play the measuring tank of flash distillation, liquid phase recycling by one again, and gas phase passes through diaphragm
It is condensed again after compressor compresses to 0.4MPa, two parts liquid phase of recycling mixes.The sulfur dioxide of obtained recycling is
163.92kg/hr, 1,3 butadiene are 27.74kg/hr, and the rate of recovery 62.95% of sulfur dioxide, the rate of recovery of 1,3 butadiene is
83.05%, yield, which accounts for, reacts total surplus sulfur dioxide and 1, and the 65.23% of 3 butadiene amounts.
The equilibrium of ternary system under 1 0.1~0.5MPa of table
2 batch process procedures step by step compression of table/condensation scheme condensing recovery amount and condensation temperature
Conclusion: the present invention provides better sulfur removal technology to the production of sulfolane and selects, no matter the production for interval
Technique or continuous sulfolane production technology, both provide good sulfur method, keep its sweetening process more perfect, reduce by two
Sulfur oxide emissions concentration, reaches national requirements for environmental protection.
Claims (6)
1. a kind of compression/condensing recovery sulfur dioxide method in sulfolane production process, it is characterised in that: produced in sulfolane
In, it is depressured using intermediate product cyclobufene sultone reactor overbottom pressure, not with step by step compression condensing mode recycling sulfolane production process
The sulfur dioxide of reaction and 1,3 butadiene；
Compression condensation refers to: carrying out gradually pressure drop stage to the cyclobufene sultone reacting rear material greater than 0.6MPa, drops from initial pressure
When as low as 0.6MPa or less, cyclobufene sultone liquid mixture gasifies, when material is dropped to from the pressure to gasify
When this pressure stage of 0.4MPa, vaporized gas is directly entered condenser, is condensed, and is mainly titanium dioxide in condensate liquid
Sulphur and 1,3 butadiene and a small amount of cyclobufene sultone, then material continues to be depressured, when material pressure is lower than 0.4MPa or less
When, after vaporized gas will boost after compressor compresses, then through condensing recovery sulfur dioxide and 1,3 butadiene.
2. compression/condensing recovery sulfur dioxide method, feature exist in sulfolane production process according to claim 1
In: sulfolane production is divided into two kinds of production methods of continuous production and Batch Process.
3. compression/condensing recovery sulfur dioxide method, feature in sulfolane production process according to claim 1 or claim 2
Be: referred to using the overbottom pressure decompression of sulfolane alkene reaction device: the material for going out cyclobufene sultone reactor is born greater than 0.6MPa's
Pressure is depressured this partial high pressure material, and when pressure drops to 0.6MPa or less, gasification takes place in liquid phase material.
4. compression/condensing recovery sulfur dioxide method, feature in sulfolane production process according to claim 1 or claim 2
Be: step by step compression condensation refers to, when material reacted in cyclobufene sultone reaction kettle is after pressure reduction gasifies, works as pressure
In 0.4MPa or more, gas is directly entered condenser, is condensed, and is mainly sulfur dioxide and 1,3 fourths two in condensate liquid
Alkene and a small amount of cyclobufene sultone, and when material is depressurized to lower than 0.4MPa or less, the gas for being flashed out will be through over-voltage
After the compression of contracting machine, then condensing recovery sulfur dioxide and 1,3 butadiene.
5. compression/condensing recovery sulfur dioxide method, feature in sulfolane production process according to claim 1 or claim 2
Be: reacted material is between 90-110 DEG C in the temperature condition in pressure reduction in cyclobufene sultone reaction kettle.
6. compression/condensing recovery sulfur dioxide method, feature in sulfolane production process according to claim 1 or claim 2
Be: most liquid sulfur dioxide and 1 are recycled in decompression, compression condensation sulfur removal technology, after 3 butadiene, then with subsequent alkali
Technique combination is washed, tail gas sulphur dioxide concentration of emission is controlled.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610712136.4A CN106366066B (en) | 2016-08-24 | 2016-08-24 | A kind of compression/condensing recovery sulfur dioxide method in sulfolane production process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610712136.4A CN106366066B (en) | 2016-08-24 | 2016-08-24 | A kind of compression/condensing recovery sulfur dioxide method in sulfolane production process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106366066A CN106366066A (en) | 2017-02-01 |
| CN106366066B true CN106366066B (en) | 2019-07-12 |
Family
ID=57879016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610712136.4A Active CN106366066B (en) | 2016-08-24 | 2016-08-24 | A kind of compression/condensing recovery sulfur dioxide method in sulfolane production process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106366066B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109833637A (en) * | 2017-11-27 | 2019-06-04 | 中国石油天然气股份有限公司 | Recyclable device |
| CN109232522B (en) * | 2018-09-30 | 2023-09-26 | 辽阳辽东精细化工有限公司 | Sulfolane continuous production system and process |
| CN112239454B (en) * | 2019-07-17 | 2022-08-05 | 中国石油天然气股份有限公司 | System and method for producing sulfolane |
| CN112742179A (en) * | 2020-12-11 | 2021-05-04 | 安徽金禾实业股份有限公司 | Method for treating chlorination tail gas in sucralose production |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR8503365A (en) * | 1984-11-05 | 1986-09-16 | Petroquimica Mosconi Ind Comer | DISCONTINUED PROCESS TO PREPARE SULFOLAN AND DEVICE TO PERFORM THIS PROCESS |
| CN102407025A (en) * | 2010-09-20 | 2012-04-11 | 光华化工(营口)有限公司 | Method for recycling sulfur dioxide and butadiene |
| CN204307504U (en) * | 2014-11-21 | 2015-05-06 | 中国石油天然气股份有限公司 | A kind of sulfolane distillation exhaust gas processing device |
| CN204661589U (en) * | 2015-03-16 | 2015-09-23 | 沈阳化工大学 | A kind of thick cyclobufene sultone produces the continuous production device of tetramethylene sulfone |
-
2016
- 2016-08-24 CN CN201610712136.4A patent/CN106366066B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR8503365A (en) * | 1984-11-05 | 1986-09-16 | Petroquimica Mosconi Ind Comer | DISCONTINUED PROCESS TO PREPARE SULFOLAN AND DEVICE TO PERFORM THIS PROCESS |
| CN102407025A (en) * | 2010-09-20 | 2012-04-11 | 光华化工(营口)有限公司 | Method for recycling sulfur dioxide and butadiene |
| CN204307504U (en) * | 2014-11-21 | 2015-05-06 | 中国石油天然气股份有限公司 | A kind of sulfolane distillation exhaust gas processing device |
| CN204661589U (en) * | 2015-03-16 | 2015-09-23 | 沈阳化工大学 | A kind of thick cyclobufene sultone produces the continuous production device of tetramethylene sulfone |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106366066A (en) | 2017-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106366066B (en) | A kind of compression/condensing recovery sulfur dioxide method in sulfolane production process | |
| CN104945224A (en) | Methanol production process | |
| CN101429098B (en) | Method for synthesis of methanol with CO, CO2 and H#[-2] | |
| CN102585951A (en) | Novel process for co-production of liquefied synthesis gas, pure hydrogen and methanol from coke-oven gas | |
| CN111592446A (en) | Rectification system and process for preparing ethylene glycol by dimethyl oxalate hydrogenation | |
| CN101503336B (en) | Improved methane chloride production process | |
| CN111302885B (en) | Method for efficiently synthesizing ethylene and 1,3-butadiene by bioethanol one-pot method | |
| CN115745794A (en) | Process and device for producing vinyl acetate by ethylene method | |
| CN101244970A (en) | Apparatus and technique for producing ethylene with ethyl alcohol | |
| CN103274913A (en) | Method and device for producing methyl isobutyl ketone | |
| CN107089644A (en) | A kind of carbon dioxide discharge-reduction and the apparatus and method of comprehensive utilization | |
| CN114272871A (en) | System and method for preparing NMP (N-methyl pyrrolidone) by taking maleic anhydride as raw material | |
| CN109232166B (en) | Process and equipment for preparing methane chloride from hydrogen chloride gas containing carbon dioxide | |
| CN106278844B (en) | Device and method for reducing raw material consumption in propylene carbonylation process | |
| CN110407725B (en) | Preparation method of 2-mercaptoethanol | |
| CN107266289A (en) | A kind of apparatus and method of utilization carbon dioxide production normal propyl alcohol | |
| CN207451978U (en) | A kind of device using carbon dioxide production n-propyl acetate | |
| CN111333484A (en) | Ultrahigh-purity methane chloride production system and process | |
| CN216756389U (en) | System for use maleic anhydride as raw materials preparation NMP | |
| CN102452925B (en) | Method for separating acetic acid from water | |
| CN215288580U (en) | System for preparing methanol by carbon dioxide hydrogenation | |
| CN106278896B (en) | The method of separating dimethyl carbonate during synthesizing dimethyl oxalate | |
| CN207243457U (en) | A kind of carbon dioxide discharge-reduction and the device of comprehensive utilization | |
| CN207451976U (en) | A kind of device using the positive propionic aldehyde of carbon dioxide production | |
| CN111848401A (en) | Device and process for refining dimethyl carbonate by energy coupling with partition wall tower |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |