CN109200769A - The processing method of tail gas during butane oxidation cis-butenedioic anhydride - Google Patents
The processing method of tail gas during butane oxidation cis-butenedioic anhydride Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
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Abstract
The processing method of tail gas during butane oxidation cis-butenedioic anhydride separates tail gas by membrane reactor, and the film in membrane reactor is cellulose acetate film, and membrane aperture is 0.1um ~ 0.5um, internal diameter 0.2mm ~ 1.0mm, wall thickness 0.1mm ~ 1.0mm；Passing through low-carbon alcohols immersion treatment using preceding, and through three phases inert gas or nitrogen treatment.The membrane reactor of specially treated is utilized in exhaust gas treating method of the invention, eliminate the molecular weight polymers impurity in membrane module, keep membrane module pore-size distribution more uniform, active principle and impurity in tail gas can be efficiently separated, is more advantageous to the enrichment for seeping butane-component in residual air；The present invention also has the advantages that equipment investment expense is low, service life is long, easy to operate, low energy consumption.
Description
Technical field
The present invention relates to the processing methods of tail gas generated during butane oxidation cis-butenedioic anhydride.
Background technique
Maleic anhydride (cis-butenedioic anhydride, MA) also known as maleic anhydride are a kind of particularly important Organic Chemicals, consumption figure
It is only second to phthalic anhydride and aceticanhydride.Cis-butenedioic anhydride is very widely used, mainly for the production of unsaturated polyester resin (UPR), 1,4-butanediol
(BDO), the series such as coating resin, span polyimides, tetrahydrofuran (THF), gamma-butyrolacton, maleic acid and tetrahydro acid anhydrides essence
The raw material of thin chemicals and textile auxiliary, lube oil additive, medicine, food additives etc..Wherein, cis-butenedioic anhydride is maximum
Purposes be production UPR and BDO, account for about the 41.7% and 17.4% of total quantity consumed respectively.Cis-butenedioic anhydride 2012 annual output in China's reaches about
800kt increased 5 times than 2000.The nearly 400kt/a of production capacity will be increased newly to the end of the year 2014.
The production process route of cis-butenedioic anhydride can be divided into phthalic anhydride by-product method, benzene oxidatoin method, C by its raw material4Olefin oxidation method, just
4 kinds of butane oxidation method.The maleic anhydride yield of phthalic anhydride plant by-product is very limited, only accounts for the 5% of phthalic anhydride by-product yield, 60 years 20th century
Before generation, cis-butenedioic anhydride is produced through catalysis oxidation as raw material using benzene and is in the great majority.But since benzene catalytic oxidation technique generates sternly environment
Heavily contaminated, the utilization rate of benzene is low in addition and price is higher and higher, is ground with raw material cheap, that pollution is small to produce the technique of cis-butenedioic anhydride
Hair becomes hot spot concerned by people.
In the early 1960s, starting with the C of low cost4Fraction (mainly containing n-butene) is that raw material produces the new of cis-butenedioic anhydride
Technical study, but since certain embodiments belong to the endothermic reaction and by-product is more, cause technology development to delay.1974, beauty
On original benzene method process units, it is raw for raw material to use normal butane instead in succession for Monsanto company of state and Texas oil company
It produces cis-butenedioic anhydride and obtains success, then, U.S. Ha Kang (Halcon) company and scientific design technology (SD) company have developed jointly just
The new catalyst and production technology of butane oxidation cis-butenedioic anhydride so that preparing cis-anhydride by n-butane oxidation new technology obtain it is more rapid
Development.
The rate constant of the reaction of preparing cis-anhydride by n-butane oxidation is K=11.44 × 105exp (- 7180/T), studies have shown that
(VO) in the catalyst2P2O7A V atom and ligand hole on (020) crystal face of object phase, another V atom and offer alkene
The active O atom bonding of propyl forms (VO) since V2O2 and P2OX is combined2P2O7When, an O atom is lacked in structure and is caused
(VO)2P2O7(020) malformation of crystal face forces the position V-O to reverse or adjust bond strength, is formed by coordination chemistry
High activity V-V ion pair.V-V bond length is 0.333nm, exactly corresponds to C in normal butane1And C3Bond length between atom and H original,
To illustrate in catalyst (VO)2P2O7Effect of the object with respect to normal butane and V2O5-P2OXBetween interaction.
In butane oxidation cis-anhydride production process, the conversion ratio of normal butane about 82% is unreacted containing 18% in tail gas
Normal butane is said from angle of cutting down the consumption of raw materials is recycled, and unreacted normal butane should be isolated from tail gas, is recycled to reaction system
System recycles.But also containing carbon monoxide, acrylic acid, acetic acid, solvent etc., at belonging to, toxic, burn into is inflammable in tail gas
Explosive medium.If tail gas is not handled well, into blower inlet, it is recycled, is situated between in tail gas containing water, acid etc.
Matter, it will the leaf of the air blower equipment such as fall are caused to corrode, drastically influence the operational safety of device.
In butane oxidation maleic anhydride production, the method for tail gas separation recycling normal butane has absorption process, condensation method and absorption
Method etc.: 1) absorption process: absorption process is that the characteristic of special solvent (or solution of addition chemical agent) is dissolved in using a certain tail gas
A kind of method handled；2) condensation method: condenser can be made it through for high-content tail gas, available gas is dropped
As low as boiling point hereinafter, condensing into liquid with recycling and reusing；3) absorption method: absorption method is that have using certain from gas phase mixture
In adsorb the porous solid (adsorbent) of certain component abilities selectively to remove a kind of method of impurity in tail gas.At present
To handle the active charcoal of the most common adsorbent of impurity in tail gas and activated carbon fiber, device used is valve transfer formula two
Bed (or more) absorber.
" chemical industry and engineering technology " the 4th phase of volume 23 in 2006 reports n butane oxidation production cis-butenedioic anhydride vent gas treatment
Technology, with the tail gas of flame combustion formula oxidator method processing butane oxidation cis-butenedioic anhydride, main body is incinerator, including burning
Device, mixing section, burning zone and exhaust section generate steam equipped with waste heat boiler recycling heat.Such method is to butane oxidation system
A kind of processing method of cis-butenedioic anhydride tail gas, and do not achieve the purpose that recycling.
" petrochemical technology and application " the 1st phase of volume 32 in 2014 reports n butane oxidation method maleic anhydride production work
Skill tail gas recycles, and the principle of exhaust gas circulation process is by processes such as cooling, separation, washings by reactive absorption tower tail gas
The impurity such as solvent, acrylic acid, acetic acid, the water of middle entrainment separation, to recycle the complete normal butane of wherein unreacted.The method work
Skill process complexity and high production cost, in addition can generate a large amount of scrub raffinate, pollute environment.
To sum up, the generally existing complex technical process of method in the prior art and the shortcomings that high production cost, and butane is pure
Rate is low, in the prior art without using film come the technical solution of separating treatment butane oxidation cis-butenedioic anhydride tail gas.
Summary of the invention
To solve butane oxidation cis-butenedioic anhydride tail gas in the prior art, there are complex treatment process, at high cost and vent gas treatment effect
Fruit problem not up to standard, the present invention is quasi- to provide a kind of processing method of butane oxidation cis-butenedioic anhydride tail gas, with limited means process film
Component simultaneously controls operating condition to tail gas progress separating treatment, and the isolated higher butane-component of purity can direct circulation benefit
With.
To realize the above-mentioned technical purpose, the present invention uses following technological means:
The present invention provides a kind of processing methods of tail gas during butane oxidation cis-butenedioic anhydride, comprising the following steps: takes off tail gas
UF membrane, the operating condition of UF membrane are as follows: pressure 0.5MPa~1.5MPa, temperature 50 C are carried out by membrane reactor after water dedusting
~100 DEG C, intake velocity 0.5m/s~3.0m/s, obtain the infiltration gas for being rich in carbon monoxide, propionic acid, acetic acid, solvent, vapor
With the infiltration residual air rich in butagas, nitrogen；
Wherein, the film in the membrane reactor be cellulose acetate film, membrane aperture be 0.1um ~ 0.5um, internal diameter 0.2mm ~
1.0mm, wall thickness 0.1mm ~ 1.0mm；
The membrane reactor is handled in the following manner using preceding:
4h~for 24 hours is first impregnated at 50 DEG C~200 DEG C with low-carbon alcohols, three phases is then divided to be passed through inert gas or nitrogen, the
The condition that one stage was passed through inert gas or nitrogen is pressure 0.5MPa-1.0MPa, -80 DEG C of temperature 50 C, flow velocity 1m3/h-
5m3/h；The condition that second stage is passed through inert gas or nitrogen is pressure 0.8MPa-1.0MPa, -80 DEG C of temperature 60 C, flow velocity
For 3m3/h-5m3/h；The condition that phase III is passed through inert gas or nitrogen is pressure 1.0MPa-1.5MPa, 90 DEG C -100 of temperature
DEG C, flow velocity 6m3/h-8m3/h。
In above-mentioned processing method, it will be apparent to a skilled person that in the butane oxidation cis-butenedioic anhydride tail gas
Containing the complete butylene of unreacted, recoverable carries out reproduction, but wherein also containing water, carbon monoxide, nitrogen, oxygen,
The impurity such as carbon dioxide, acetic acid, propionic acid, cis-butenedioic anhydride, each component content is different because of respective process distinction in tail gas, to make
Those skilled in the art are more fully understood by the present invention, and processing method of the present invention is particularly suitable for following impurity content
Exhaust gas treating method: by weight, water content 1.5%-5.0%, carbon monoxide content 0.1%-5.0%, nitrogen content is
60.0%-75.0%, oxygen content 5.0%-20.0%, carbon dioxide content 0.5%-5.5%, acetic acid content 0.001%-
0.5%, propionic acid content 0.001%-0.10%, cis-butenedioic anhydride content are 0.001%-0.1%, and surplus is butane.It is wherein more preferably: pressing
Poidometer, water content 1.5%-3.0%, carbon monoxide content 0.5%-3.0%, nitrogen content 65.0%-70.0%, oxygen contain
Amount is 10.0%-15.0%, carbon dioxide content 0.5%-3.5%, acetic acid content 0.001%-0.30%, and propionic acid content is
0.001%-0.02%, cis-butenedioic anhydride content are 0.001%-0.05%, and surplus is butane.And it should be strongly noted that above-mentioned composition
Tail gas is handled using method of the invention, available more preferably separating resulting, and butane contains in the gas after making separation
Amount meets the requirement as feedstock circulation reproduction, and impurity therein is substantially achieved removal, will not influence technological reaction, and not
It is to say that the tail gas except this composition is unsuitable for being handled with the method.
In above-mentioned processing method, the dehydration dedusting is to remove all diameters the consolidating greater than 0.02 μm carried secretly in tail gas
Body particle, water mist and aerosol, micronic dust content≤0.02mg/Nm in the tail gas that makes that treated3, water content≤3PPm.Processing side
Method is known to the skilled person, such as inertial dust collection method, wet dedusting method, Cottrell process, filtering type process of cleaning, monotubular rotation
Wind process of cleaning, multi-cyclone process of cleaning, centrifugal force separate, gravitational settling, baffling separation, silk screen separation, ultra-filtration and separation and filler
Separation etc., preferably centrifugal force separate, filtering type process of cleaning.
In above-mentioned processing method, tail gas can make tail by Pneumatic booster pump or gas-booster before being passed through membrane separator
Gas is pressurized to required pressure；Exhaust temperature is set to be down to required temperature by heat exchange mode, heat exchange mode includes various hybrid, storages
Hot type or dividing wall type heat exchanger, preferably dividing wall type heat exchanger, wherein dividing wall type heat exchanger can be jacket type, tubular type, it is board-like or
The custom design heat exchanger of various abnormal shape heat-transfer area compositions；The type of flow of the cold fluid and hot fluid in heat exchanger include fair current, adverse current,
Hand over stream, mixed flow again, preferably adverse current.
In above-mentioned processing method, as a further preference, the operating condition of the UF membrane are as follows: pressure 0.5MPa~
1.0MPa, temperature 50 C~90 DEG C, more preferably 50 DEG C~80 DEG C；Intake velocity is 0.5m/s~2.0m/s, wherein air inlet speed
Degree is more preferably 0.5m/s~1.5m/s.
In above-mentioned processing method, as a further preference, the low-carbon alcohols are selected from C1-C7N-alkanol or isomery alcohol
At least one of, preferably C1-C4N-alkanol or at least one of isomery alcohol, more preferable C1-C3N-alkanol or isomery
At least one of alcohol.
It the use of the condition that low-carbon alcohols are impregnated is preferably 50 DEG C -150 as a further preference in above-mentioned processing method
Soaking 12h-24h at a temperature of DEG C.
In above-mentioned processing method, immersion of the present invention is subject to liquid and there completely was not membrane module.
In above-mentioned processing method, the membrane reactor includes shell and membrane module, and membrane module is arranged in shell, in shell
One end of body and membrane module are equipped with gas inlet parallel, are equipped with parallel in the other end and membrane module of shell and seep residual air outlet, shell
Body side surface, which is equipped with, seeps vent outlet.
After above-mentioned vent gas treatment, obtain rich in carbon monoxide, propionic acid, acetic acid, solvent, vapor infiltration gas and
Infiltration residual air rich in butagas, nitrogen seeps residual air and returns to the butane oxidation stage as raw material, and permeating gas can further recycle respectively
Component.
Compared with prior art, butane oxidation maleic anhydride unit exhaust gas treating method of the invention has the advantage that
1. the present invention is impregnated membrane reactor, stage by stage with inert gas or nitrogen progress with low-carbon alcohols under given conditions
The mode of processing eliminates the molecular weight polymers impurity in membrane module, keeps membrane module pore-size distribution more uniform, be more advantageous to
Seep the enrichment of butane-component in residual air.
2. butane oxidation cis-butenedioic anhydride exhaust gas treating method of the invention has equipment investment expense compared with other techniques
Low, the advantages of service life is long, easy to operate, low energy consumption；Membrane reactor gas separation selectivity after specially treated is good,
Separative efficiency is high, effectively excludes impurity acetic acid, propionic acid, cis-butenedioic anhydride and the moisture in tail gas, active principle butane contains in tail gas
Amount is promoted to 1.60% or more by 1.1, fully meets the requirement that direct circulation is used as raw material, and entire technique does not produce
Raw secondary pollution.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The concrete technology flow process figure of butane oxidation cis-butenedioic anhydride tail gas is handled used in Fig. 1 embodiment；
The structural schematic diagram of Fig. 2 membrane reactor；
Wherein 1. gas centrifuge, 2. gas-boosters I, 3. high pressure storage tanks, 4. active carbon filters, 5. contra-flow heat exchangers, 6.
Accurate filter, 7. membrane reactors, 8. gas-boosters II, 9. gas inlets, 10. seep vent outlet, 11. membrane modules, 12. shells
Body, 13. seep residual air outlet, 14. pipelines I, 15. pipelines II, 16. pipelines III.
Specific embodiment
Following non-limiting embodiments can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.
In the examples below, be all made of technological process device shown in FIG. 1 to butane oxidation cis-butenedioic anhydride tail gas at
Reason, the room temperature tail gas from butane oxidation technique first passes through gas centrifuge 1, it is preliminary remove the solid particle carried in tail gas and
Water, then 0.5MPa~1.0Mpa is pressurized to by gas-booster I 2, it is further through active carbon filter 4 into high pressure storage tank 3
It is dehydrated dedusting, then makes exhaust temperature up to 50 DEG C~80 DEG C after the heat exchange of counter-current pipe exchanger 5, again through accurate filter 6
Micronic dust content≤0.01mg/Nm is obtained after removing solid particle of all diameters greater than 0.01 μm3, water content≤2PPm enters film
It is anti-to enter film under conditions of pressure 0.5MPa~1.0MPa, temperature 50 C~80 DEG C, intake velocity 0.5m/s~3.0m/s for gas
Device 7 is answered, purified infiltration residual air is isolated and concentrates the infiltration gas of impurity.Residual air is wherein seeped from residual air outlet is seeped through pipeline II
15 draw return butane oxidation device, and partial penetration gas returns to activity by gas-booster II 8 and pipeline III 16 through pipeline I 14
Carbon filter 4, another part permeate the recycling that gas carries out acrylic acid, acetic acid, solvent.
Fig. 2 is membrane reactor structural schematic diagram used in the embodiment of the present invention.Membrane reactor has shell 12, in shell
Equipped with membrane module 11, it is equipped with gas inlet 9 parallel in one end of shell 12 and membrane module 11, in the other end and film group of shell 12
Part 11 is equipped with parallel seeps residual air outlet 13, and housing side, which is equipped with, seeps vent outlet 10.Tail gas is in membrane module internal flow, as slow
The butane-component of gas walks membrane module tube side and is seeped 13 discharge of residual air outlet, and the impurity gas as fast gas appears membrane module through permeating gas
10 discharge of outlet.The material that the membrane module uses is cellulose acetate film, membrane aperture 0.1um-0.3um, internal diameter 0.4mm-
0.8mm, wall thickness 0.1mm-0.3mm.
Film parameters used in embodiment are shown in Table 1, and the composition of used butane oxidation device exhaust is listed in table 2.
Table 1
Table 2
% in following embodiment is weight percentage unless otherwise specified.
Embodiment 1
Using butane oxidation device exhaust listed by table 2 as raw material, the solid carried in tail gas is tentatively removed through gas centrifuge 1
After grain and water, enter high pressure storage tank 3 after being pressurized to 0.5MPa by gas-booster I 2；It is further taken off through active carbon filter 4
Water dedusting, micronic dust content is 0.005mg/Nm in treated tail gas3, water content 1PPm, then through counter-current pipe exchanger 5
Make exhaust temperature up to 60 DEG C after heat exchange, membrane reactor 7, separation are entered under conditions of pressure 0.8MPa, intake velocity 1.0m/s
Infiltration residual air rich in butane and the infiltration gas containing acetic acid, propionic acid, cis-butenedioic anhydride and moisture out.It seeps residual air and is sent into butane oxidation device work
For the raw material for synthesizing cis-butenedioic anhydride；Gas is permeated after different adsorbents adsorb laggard one-step removal butane therein as backflow gas pressurization
Membrane separator 7 is returned to continue to purify；Another part permeates the recycling that gas carries out acetic acid, propionic acid, cis-butenedioic anhydride.Residual air composition result is seeped to see
Table 3.
Embodiment 2
According to the method for embodiment 1, high pressure storage tank 3 will be only entered after gas boosting to 0.6MPa；Through active carbon filter 4 into
One step is dehydrated dedusting, and micronic dust Content is 0.01mg/Nm in treated tail gas3, water content 2.5PPm, through counterflow heat exchange
Device 5 makes exhaust temperature up to 80 DEG C after exchanging heat, and membrane reactor 7 is entered under conditions of pressure 1.0MPa, intake velocity 1.5m/s, point
Separate out the infiltration residual air rich in butane and the infiltration gas containing acetic acid, propionic acid, cis-butenedioic anhydride and moisture.It seeps residual air and is sent into butane oxidation device
Raw material as synthesis cis-butenedioic anhydride；It permeates gas and adsorbs laggard one-step removal butane therein as backflow gas pressurization through different adsorbents
Membrane separator 7 is returned afterwards to continue to purify；Another part permeates the recycling that gas carries out acetic acid, propionic acid, cis-butenedioic anhydride.It seeps residual air and forms result
It is shown in Table 3.
Embodiment 3
According to the method for embodiment 1, high pressure storage tank 3 will be only entered after gas boosting to 1.0MPa；Make through active carbon filter 4
Obtaining micronic dust content in tail gas is 0.02mg/Nm3, water content is that 3PPm enters film gas, makes tail gas temperature after the heat exchange of contra-flow heat exchanger 5
Degree enters membrane reactor 7 under conditions of pressure 0.8MPa, intake velocity 3.0m/s, isolates the infiltration rich in butane up to 80 DEG C
Residual air and the infiltration gas containing acetic acid, propionic acid, cis-butenedioic anhydride and moisture.It seeps residual air and is sent into original of the butane oxidation device as synthesis cis-butenedioic anhydride
Material；It permeates gas and returns to membrane separator 7 after different adsorbents adsorb laggard one-step removal butane therein as backflow gas pressurization
Continue to purify；Another part permeates the recycling that gas carries out acetic acid, propionic acid, cis-butenedioic anhydride.Seeping residual air composition the results are shown in Table 3.
Embodiment 4
Following processing has been carried out to membrane module 11: membrane module 11 being impregnated into 12h with isopropanol at 50 °C, then divides three
Stage is passed through nitrogen, and the condition that the first stage is passed through nitrogen is pressure 0.5MPa, and 80 DEG C of temperature, flow velocity 5m3/h；Second stage
The condition for being passed through nitrogen is pressure 0.8MPa, temperature 60 C, flow velocity 3m3/h；The condition that phase III is passed through nitrogen is pressure
1.5MPa, 100 DEG C of temperature, flow velocity 8m3/ h, after treatment are used for butane oxidation tail gas clean-up.
According to the method for embodiment 1, with treated above, membrane module is used for vent gas treatment.Seeping residual air composition the results are shown in Table
3。
Embodiment 5
According to the method for embodiment 4, isopropanol is only changed to ethyl alcohol, seeping residual air composition the results are shown in Table 3.
Embodiment 6
According to the method for embodiment 4, isopropanol is only changed to n-butanol, seeping residual air composition the results are shown in Table 3.
Embodiment 7
According to the method for embodiment 4, isopropanol is only changed to octanol, seeping residual air composition the results are shown in Table 3.
Embodiment 8
Following processing has been carried out to membrane module 11: membrane module being impregnated into 12h at a temperature of 80 DEG C with ethyl alcohol, then divides three phases
It is passed through nitrogen, the condition that the first stage is passed through nitrogen is pressure 1.0MPa, 80 DEG C of temperature, flow velocity 5m3/h；Second stage is passed through
The condition of nitrogen is pressure 0.8MPa, temperature 60 C, flow velocity 3m3/h；The condition that phase III is passed through nitrogen is pressure
1.5MPa, 100 DEG C of temperature, flow velocity 6m3/ h, after treatment are used for butane oxidation tail gas clean-up.
According to the method for embodiment 1, with treated above, membrane module is used for vent gas treatment.Seeping residual air composition the results are shown in Table
3。
Embodiment 9
According to the method for embodiment 8, ethyl alcohol is only changed to sec-butyl alcohol, seeping residual air composition the results are shown in Table 3.
Embodiment 10
According to the method for embodiment 8, ethyl alcohol is only changed to methanol, seeping residual air composition the results are shown in Table 3.
Embodiment 11
Following processing has been carried out to membrane module 11: membrane module being impregnated for 24 hours at 50 °C with methanol, then divides three phases
It is passed through nitrogen, the condition that the first stage is passed through nitrogen is pressure 1.0MPa, 80 DEG C of temperature, flow velocity 5m3/h；Second stage is passed through
The condition of nitrogen be pressure 0.8MPa, 80 DEG C of temperature, flow velocity 3m3/h；The condition that phase III is passed through nitrogen is pressure
1.5MPa, 100 DEG C of temperature, flow velocity 8m3/ h, after treatment are used for butane oxidation tail gas clean-up.
According to the method for embodiment 1, with treated above, membrane module is used for vent gas treatment.Seeping residual air composition the results are shown in Table
3。
Embodiment 12
According to the method for embodiment 11, methanol is only changed to ethyl alcohol, seeping residual air composition the results are shown in Table 3.
Embodiment 13
According to the method for embodiment 11, methanol is only changed to isopropanol, seeping residual air composition the results are shown in Table 3.
Embodiment 14
According to the method for embodiment 11, methanol is only changed to butanol, seeping residual air composition the results are shown in Table 3.
From table 3 it can be seen that butane oxidation device exhaust is after not pretreated membrane separator purification, it is effective in tail gas
Component butane content still contains the impurity such as a small amount of acetic acid, propionic acid and cis-butenedioic anhydride 1.1% or so, and passes through pretreated film
After separator purification, impurity acetic acid, propionic acid, cis-butenedioic anhydride and moisture in tail gas have obtained effective exclusion, active principle in tail gas
Butane content is 1.60% or more, can be used as the raw material of synthesis cis-butenedioic anhydride workshop section completely, has reached the requirement being recycled.
Table 3
Claims (8)
1. the processing method of tail gas during butane oxidation cis-butenedioic anhydride, comprising the following steps: pass through film after tail gas is dehydrated dedusting
Reactor carries out UF membrane, the operating condition of UF membrane are as follows: pressure 0.5MPa~1.5MPa, temperature 50 C~100 DEG C, air inlet speed
Spend 0.5m/s~3.0m/s, obtain rich in carbon monoxide, propionic acid, acetic acid, solvent, vapor infiltration gas and rich in butagas,
The infiltration residual air of nitrogen；
Wherein, the film in the membrane reactor be cellulose acetate film, membrane aperture be 0.1um ~ 0.5um, internal diameter 0.2mm ~
1.0mm, wall thickness 0.1mm ~ 1.0mm；
The membrane reactor is handled in the following manner using preceding:
4h~for 24 hours is first impregnated at 50 DEG C~200 DEG C with low-carbon alcohols, three phases is then divided to be passed through inert gas or nitrogen, the
The condition that one stage was passed through inert gas or nitrogen is pressure 0.5MPa-1.0MPa, -80 DEG C of temperature 50 C, flow velocity 1m3/h-
5m3/h；The condition that second stage is passed through inert gas or nitrogen is pressure 0.8MPa-1.0MPa, -80 DEG C of temperature 60 C, flow velocity
For 3m3/h-5m3/h；The condition that phase III is passed through inert gas or nitrogen is pressure 1.0MPa-1.5MPa, 90 DEG C -100 of temperature
DEG C, flow velocity 6m3/h-8m3/h。
2. processing method according to claim 1, which is characterized in that the operating condition of the UF membrane are as follows: pressure
0.5MPa~1.0MPa, temperature 50 C~90 DEG C, intake velocity are 0.5m/s~2.0m/s.
3. processing method according to claim 1, which is characterized in that the low-carbon alcohols are selected from C1-C7N-alkanol or isomery
At least one of alcohol.
4. processing method according to claim 3, which is characterized in that the low-carbon alcohols are selected from C1-C4N-alkanol or isomery
At least one of alcohol.
5. processing method according to claim 3 or 4, which is characterized in that using low-carbon alcohols impregnate condition be 50 DEG C-
Soaking 12h-24h at a temperature of 150 DEG C.
6. processing method according to claim 1, which is characterized in that micronic dust in the dehydration dedusting makes that treated tail gas
Content≤0.02mg/Nm3, water content≤3PPm.
7. processing method according to claim 1, which is characterized in that the composition of the tail gas are as follows: by weight, water content
For 1.5%-5.0%, carbon monoxide content 0.1%-5.0%, nitrogen content 60.0%-75.0%, oxygen content 5.0%-
20.0%, carbon dioxide content 0.5%-5.5%, acetic acid content 0.001%-0.5%, propionic acid content 0.001%-0.10% are suitable
Acid anhydride content is 0.001%-0.1%, and surplus is butane.
8. processing method according to claim 7, which is characterized in that the composition of the tail gas are as follows: by weight, water content
For 1.5%-3.0%, carbon monoxide content 0.5%-3.0%, nitrogen content 65.0%-70.0%, oxygen content 10.0%-
15.0%, carbon dioxide content 0.5%-3.5%, acetic acid content 0.001%-0.30%, propionic acid content 0.001%-0.02%,
Cis-butenedioic anhydride content is 0.001%-0.05%, and surplus is butane.
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