A kind of reactive distillation prepares MTBE and its wastewater treatment method
Technical field
The present invention relates to catalytic reaction rectification technical field and field of waste water treatment in chemical field, and in particular to a kind of anti-
Rectifying is answered to prepare the processing method of MTBE and its waste water.
Technical background
MTBE (methyl tertiary butyl ether(MTBE)) is a kind of high octane gasoline component, be excellent gasoline high-octane rating additive and
Anti-knock agent can be used for decomposing and make high-purity isobutene.
Document report it is more be to use isobutene and methanol as raw material, by acidic catalyst synthesis MTBE, wherein urging
It is resin catalyst that agent is industrially with the most use, different according to the source of isobutene and form different synthesis roads
Line.If patent CN102701919A is reported, the technique for reacting generation MTBE with methanol using the mixing C4 of low in isobutene content;Specially
Sharp CN104876785A report generates MTBE using with methanol react by the remaining C4 that Butadiene Extraction comes;Patent
After CN104945228A reports are using butane is mixed by the way that the series of steps such as hydrogen, dehydrogenation, isomery is added to generate isobutene, with
Methanol is etherified.The purpose of above-mentioned patent is for improving the utilization ratio of mixing C4, increases economic value.
But since 2012, the process units of cooxidation legal system propylene oxide is gone into operation successively at home, the tertiary fourth of by-product
The yield of alcohol (TBA) will also increase, tert-butyl alcohol excess capacity, so the exploitation tert-butyl alcohol and the technique of methanol etherification generation MTBE have
Better prospect.Cooxidation propylene oxide unit is produced mostly using piston flow reactor at present, since MTBE is etherified
It reacts for balanced reaction, unreacted alcohol can be caused largely to recycle, energy consumption is big needed for alcohol-water separation, recycles in alcohol that there are heavy constituents
The problems such as accumulation;And COD high can be caused, it is difficult to biochemical treatment there are a large amount of organic matter in waste water.Pass through reaction rectification technique
The conversion ratio of the tert-butyl alcohol can be not only improved, reduces energy consumption, the residual of useless Organic substance in water can also be reduced, improving waste water can give birth to
The property changed.
The reaction rectification technique of document report MTBE is common using isobutene as raw material.If patent CN204625508U is using anti-
Rectifying column is answered to prepare MTBE, device includes several major parts such as pre-reactor, rectifying column, catalytic rectifying tower, realizes to isobutyl
The deep conversion of alkene, but the presence of catalytic rectifying tower can not still break away from traditional reactive distillation process and be difficult to replace there are catalyst
The problem of.Patent CN102423539A reports the reactive distillation process that a kind of conversion zone is detached with rectifying section, which lays particular stress on section
It can lower consumption, there is no the physical differences for considering the tert-butyl alcohol and isobutene, are unable to reach the high of the tert-butyl alcohol using the equipment and convert
Rate.
There are many impurity in the by-product tert-butyl alcohol obtained by cooxidation legal system propylene oxide, using the above-mentioned tert-butyl alcohol as raw material system
Impurity can enter in waste water during MTBE.Residual of the light component in waste water can be reduced, but for micro- by reaction rectification technique
The toxic heavy constituent organic matter of biology is remained in waste water, it is necessary to by could be into after the means regulating water quality index such as water distribution
Row biochemical treatment, the biodegradability of waste water not be improved significantly.
The processing method of industrial wastewater mainly has absorption method, burning method, ion-exchange, steam blow-off method, chemical oxidation
Method etc..Fenton oxidation waste water treatment process, such as Chinese patent as disclosed in Chinese patent CN202898099U, CN103755007B
The disclosed diatomite base adsorbents for being used for wastewater treatment of CN103432986A, are used as disclosed in Chinese patent CN103272654A
In the anion exchange resin of wastewater treatment, handled as disclosed in Chinese patent CN102320671B with stripping mode containing acid and ammonia
The method of waste water.Advanced oxidation processes type is more, can reduce tail water COD, but the validity reacted and place to a certain extent
Reason efficiency is all relatively low, and processing cost is higher;Membrane separation technique is a kind of more ripe Tailwater Depth processing and reuse technology, but single
It is single not only to invest big, operating cost height by film device, and film concentrate easily causes secondary pollution;Adsorption technology is applicable to
Most industrial organic waste water advanced treating requirements, but there are the problems such as processing cost is high, recyclability is poor.Solvent extraction technique
Simply, operation is easy, extraction efficiency is high, and the common extractant of extraction has dichloromethane, Di Iso Propyl Ether, methyl-isobutyl
Ketone, petroleum ether, n-hexane etc..Application of the solvent extraction in recent years in coal chemical industry phenolic wastewater treatment field is more, such as China
Oil-containing disclosed in method for extracting and dephenolizing coal chemical industry wastewater disclosed in patent CN101913718B and Chinese patent CN104829025A
The method of coal chemical industrial waste water extraction oil removing, but solvent extraction also rarely has report in the application of processing MTBE etherificate field of wastewater
Road.
In conclusion it needs to seek a kind of new side for preparing MTBE using the tert-butyl alcohol as raw material by reaction rectification technique
Method solves the problems, such as catalyst change, improves the conversion ratio of the tert-butyl alcohol and is etherified waste water to it and is effectively treated.
Invention content
The purpose of the present invention is to provide a kind of reactive distillations to prepare MTBE and its wastewater treatment method, solves tradition reaction
Rectifying column is due to catalyst life, and during especially with resin catalyst, usage time only has 6~8 months, frequently replaces catalysis
Device parking problem caused by agent and the conversion ratio for improving TBA.By reactive distillation and the means of extraction, reduce organic in waste water
The content of object makes waste water reach the water quality requirement of biochemical treatment.
To achieve the above objectives, technical scheme is as follows:
A kind of reactive distillation prepares the processing method of MTBE and its waste water, includes the following steps:
(1) using the tert-butyl alcohol and methanol as raw material of etherification, the ratio of the tert-butyl alcohol and methanol is 0.5~1:1 (wt.),
The middle tert-butyl alcohol comes from cooxidation legal system propylene oxide by-product;Traditional reactive distillation column is divided into conversion zone and two portions of rectifying section
Point, material benzenemethanol, TBA are fed in rectifying midsection, and conversion zone is carried on outside rectifying column in the form of side reaction device, can carried
One or more, preferably 1-3 side reaction device, are attached by compressor and heat exchanger.The tert-butyl alcohol and methanol are through rectifying column
Approaching side reactor carries out etherification reaction in the presence of a catalyst;Reaction product enters rectifying column and is detached, and tower top obtains
MTBE, isobutene and unreacted methanol, tower reactor obtain etherificate waste water (COD value of waste water is 30000~40000mg/L).
According to boiling point difference, methanol feed entrance point carries out material mixing under tert-butyl alcohol feed entrance point, by rectifying.Tower
Stage casing extraction is one or more strands of, and preferably one respectively enters side reaction device, the discharging of side reaction device returns to rectifying column to three strands of materials
Stage casing is detached.It is preferred that the feed entrance point of side reaction device is separated by 10~20 blocks of theoretical trays, side reaction device with tower bottom of rectifying tower
Unloading position and rectifying column tower top be separated by 10~20 blocks of theoretical trays, ensure that TBA will not fall after rise to tower bottom of rectifying tower or be pressed from both sides
Take tower top to.Side reaction device feed entrance point refers to the logistics approaching side reactor of rectifying column from the position that rectifying column goes out, side reaction
The unloading position of device refer to the logistics of side reaction device enter rectifying column from rectifying column into position.
(2) etherificate waste water is divided into water-oil phase by extraction, and extractant reuse is realized in oil phase rectifying, water phase take off gently obtain it is low
COD waste water, wastewater treatment mode are biochemical treatment.
Alcohol, aldehyde, ketone, acid and alkanes impurity, preferably institute there are many containing in the method for the present invention, in the TBA described in step (1)
Impurity is including but not limited to isopropanol, isobutanol, acetaldehyde, acetone, isobutyric acid and isooctane in the TBA stated.
In the method for the present invention, the theoretical number of plates of rectifying tower described in step (1) is 40~80, and tower top operating pressure is 0.1
~1MPa (absolute pressure), bottom temperature is 80~180 DEG C, tower top temperature is 40~90 DEG C, and reflux ratio is 5~30.
Further, the theoretical number of plates of rectifying tower described in step (1) is preferably 50~70, and tower top operating pressure is preferably
0.2~0.5MPa (absolute pressure), bottom temperature are preferably 120~160 DEG C, and tower top temperature is preferably 50~80 DEG C, and reflux ratio is preferred
It is 10~20.
In the method for the present invention, methanol feed entrance point is under TBA feed entrance points in rectifying column, it is preferable that the first
Alcohol feed entrance point is at the 40th~60 block of theoretical tray, TBA feed entrance points (theoretical cam curve at the 20th~30 block of theoretical tray
It counts from top to bottom).
In the method for the present invention, the side reaction device number is 1~3, preferably 2~3, temperature of reactor for 90~
200 DEG C, reaction pressure is 0.1~5MPa (absolute pressure), and temperature of reactor is preferably 100~150 DEG C, reaction pressure is preferably 2~
4MPa (absolute pressure).
In the method for the present invention, the catalyst is acid resin catalyst, metal oxide, metal salt, zeolite molecules
It is one or more in sieve, solid super-strong acid etc., preferably ROHM AND HAAS A-35, A-45 resins, Al2O3, AlPO4, H-ZSM-5,
SO4 2-/ZrO2It is one or more;Air speed of the material in side reaction device is 1.5~2.5h-1。
Preferably, the side reaction device entry/exit discharge position is located between the 20th~60 block of theoretical tray of rectifying column.
In the method for the present invention, the preferably described side reaction device and rectifying column by compressor, heat exchanger carry out pressure with
The matching of temperature;Can reaction by adjusting the type of catalyst, be made according to side reaction device and rectifying column Different matching position simultaneously
The coupling of temperature and pressure is realized with rectifying.
In the method for the present invention, the extraction taking device described in step (2) can be extraction tower, mixer-settler extractor, static mixing
It is one or more in device, oil water separator, it is preferably one or more in extraction tower, mixer-settler extractor, oil water separator;Extraction
The theoretical stage for taking device is 1~10, preferably 1~5.Extractant can be methanol, dichloromethane, methyl tertiary butyl ether(MTBE), two different
One or more compoundings in propyl ether, methyl iso-butyl ketone (MIBK);It is preferred that in dichloromethane, methyl tertiary butyl ether(MTBE), Di Iso Propyl Ether
One or more compoundings.The mass ratio of extractant and waste water is 0.1:1~2:1, the mass ratio of preferably extractant and waste water is
0.3:1~1:1.The COD value of processed waste water is 10000~13000mg/L.
In the method for the present invention, oil phase is sent to solvent recovery tower, solvent recovery tower heavy bottom oil after the extraction described in step (2)
It is delivered to incinerator burning disposal, solvent recovery top of tower extractant reuse;Water phase is sent to waste water lightness-removing column after extraction, and waste water takes off
Light tower bottom waste water is delivered to water treatment unit and carries out biochemical treatment, and light component is delivered to solvent recovery at the top of waste water lightness-removing column
Tower.Preferably, the theoretical cam curve of the waste water lightness-removing column is 10~40,0.01~0.2MPa of operating pressure (absolute pressure), tower
It is 50~110 DEG C to push up temperature, and bottom temperature is 80~120 DEG C.The theoretical cam curve of solvent recovery tower is 10~50, operating pressure
0.01~0.2MPa (absolute pressure), tower top temperature are 30~80 DEG C, and bottom temperature is 60~150 DEG C.
The positive effect of the present invention is:
1st, the present invention carries out MTBE etherificates by raw material of the tert-butyl alcohol, can solve tert-butyl alcohol problem of excess production capacity, and raw material comes
Source is more economical.
2nd, conversion zone of the present invention is equipped in the form of side reaction device outside rectifying column, can be by adjusting the quantity of side reaction device
Reach the high conversion of TBA;The form of side reaction device can also facilitate the replacement of catalyst;Side reaction device passes through temperature with rectifying column
Degree and the coupling of pressure make reaction and separation under its optimal operating condition, can increase the efficiency of reaction and rectifying.
3rd, the present invention synthesizes MTBE using reactive distillation mode, compared with current conjugated oxidation PO/MTBE techniques, solves
The problems such as conversion per pass is low, feedstock circulation amount is big, heavy constituent accumulation.Can be reduced in waste water using the form of reactive distillation is had
The content of machine object avoids it from entering in waste water;And it during using extraction processing, does not need to adjusting PH with base be added to be demulsified waste water, simplify
Technique has saved cost.Waste water COD can be effectively reduced by the form of extraction, rectifying, significantly improve the biochemical of waste water
Property, the cost of wastewater treatment is saved, realizes qualified discharge or the reuse of waste water, ensure that the continuous and steady operation of device.
4th, the present invention can adjust the type of catalyst using multiple side reaction devices, realize between reaction and rectifying temperature and
The coupling of pressure.
Description of the drawings
Fig. 1 is the process flow chart of the present invention.
Specific embodiment
Embodiments of the present invention are described in further detail with reference to the accompanying drawings and examples, all embodiments are equal
It is operated by the operating condition of above-mentioned technical proposal, the purpose is to contents for a better understanding of the present invention.Therefore it is lifted
Example is not intended to limit protection scope of the present invention.
Embodiment quantifies raw material and reaction solution using Agilent gas-chromatography, using Agilent HP-5ms chromatographies
Column;Temperature programming:50 DEG C of holding 2min, are warming up to 60 DEG C with 5 DEG C/min, keep 1min, 100 DEG C are warming up to 40 DEG C/min,
1min is kept, 200 DEG C is warming up to 10 DEG C/min, keeps 1min, 280 DEG C is warming up to 40 DEG C/min, keeps 5min.Hash
BOD/COD Water Test Kits detects waste water BOD/COD values.
Embodiment 1
As shown in Figure 1, using theoretical cam curve as 68 pieces of rectifying column, 2 side reaction devices of arranging in pairs or groups pass through heat exchanger and pressure
Contracting machine connects.It is fed at the tert-butyl alcohol and methanol respectively the 27th, the 57 block of theoretical tray in rectifying column, the tert-butyl alcohol comes from cooxidation
Legal system propylene oxide by-product, wherein there is about 1wt.% impurity, predominantly isobutyric acid, isobutanol, isopropanol etc..Reactor -2 is by essence
It evaporates and one material is drawn at the 35th block of theoretical tray of tower as charging, unloading position is at the 20th block of theoretical tray;Reactor-
1 draws one material as charging by the 54th block of theoretical tray of rectifying column, and unloading position is at the 40th block of theoretical tray.
Using ROHM AND HAAS A-35 resin catalysts in two reactors, reactor pressure is 2MPa, and temperature uses 100
℃.The charge-mass ratio of the tert-butyl alcohol and methanol is 1:1, residence time of the material in each reactor is 30min.Rectifying column
Tower top pressure is 0.2MPa, and tower reactor pressure is 0.25MPa, and it is 125 DEG C to maintain bottom temperature, and tower top temperature is 60 DEG C, reflux ratio
It is 15, overhead extraction compares D/F=0.875.
Device is sampled rectifying column tower top and tower reactor after stablizing analysis, and water content is 99.27wt%, tertiary fourth in tower reactor
Alcohol is 0.42wt%, methanol 0.27wt%;In tower top isobutene content be 4.31wt%, MTBE content be 60.65wt%, first
Alcohol content be 34.75wt%, TBA content be 0.11wt%, water content 0.08wt%.TBA conversion ratios are 99.70%, isobutyl
Alkene is selectively that 9.96%, MTBE selectivity is 89.85%.
The COD value of waste water of generation is 30000mg/L, and the ratio between biological oxygen consumption and chemical oxygen consumption (COC) B/C values are 0.1.Extraction
Device is extraction tower, and extraction theory series is 2, and the mass ratio of extractant MTBE and waste water is 0.3:1.The bottom of extraction equipment obtains
To aqueous phase extracted, into waste water lightness-removing column, the theoretical cam curve of waste water lightness-removing column is 10, operating pressure 0.1MPa (absolute pressure), tower
98.8 DEG C of temperature, 103.0 DEG C of bottom temperature are pushed up, waste water lightness-removing column bottom waste water is delivered to water treatment unit and carries out biochemical treatment,
Light component is delivered to solvent recovery tower at the top of waste water lightness-removing column;Extraction oil phase is obtained at the top of extraction equipment, with waste water lightness-removing column
Rectification process in solvent recovery tower is delivered to after the light component mixing of top, the theoretical cam curve of solvent recovery tower is 10, operation pressure
Power 0.1MPa (absolute pressure), 53.3 DEG C of tower top temperature, 101.0 DEG C of bottom temperature, solvent recovery tower heavy bottom oil is delivered to incinerator
Burning disposal, solvent recovery top of tower extractant are back to waste water extraction tower and are extracted.
Detection:It is detected using Hash BOD/COD Water Test Kits, treated COD value of waste water is 12000mg/L, B/C values
It is 0.5.
Embodiment 2
On the basis of embodiment 1, the charge-mass ratio for changing the tert-butyl alcohol and methanol is 3:4, remaining is respectively reacted and rectifying
Parameter constant, D/F=0.86.
Device is sampled rectifying column tower top and tower reactor after stablizing analysis, and water content is 99.13wt%, tertiary fourth in tower reactor
Alcohol is 0.51wt%, methanol 0.28wt%;In tower top isobutene content be 8.46wt%, MTBE content be 65.17wt%, first
Alcohol content be 25.83wt%, TBA content be 0.31wt%, water content 0.10wt%.TBA conversion ratios are 99.41%, isobutyl
Alkene is selectively that 16.94%, MTBE selectivity is 82.79%.
Generation COD value of waste water is 35000mg/L, and B/C values are 0.15.Extraction equipment is multistage oil water separator, extraction dress
The theoretical stage put is 1, and the mass ratio of extractant and waste water is 1:1;The theoretical cam curve of waste water lightness-removing column is 20, operating pressure
0.1MPa (absolute pressure), 99.1 DEG C of tower top temperature, 103.0 DEG C of bottom temperature;The theoretical cam curve of solvent recovery tower is 20, operation pressure
Power 0.1MPa (absolute pressure), 52.8 DEG C of tower top temperature, 105.0 DEG C of bottom temperature.
Detection:COD value of waste water after detection process is 11000mg/L, and B/C values are 0.5.
Embodiment 3
On the basis of embodiment 1, it is H-ZSM-5 to replace the catalyst in reactor -1, while adjusts -1 temperature of reactor
It is 150 DEG C to spend, pressure 3MPa.Remaining each reaction and rectification parameters are constant, D/F=0.875.
Device is sampled rectifying column tower top and tower reactor after stablizing analysis, and water content is 99.32wt%, tertiary fourth in tower reactor
Alcohol is 0.19wt%, methanol 0.23wt%;In tower top isobutene content be 6.48wt%, MTBE content be 57.17wt%, first
Alcohol content be 35.93wt%, TBA content be 0.09wt%, water content 0.11wt%.TBA conversion ratios are 99.80%, isobutyl
Alkene is selectively that 15.07%, MTBE selectivity is 84.68%.
Generation COD value of waste water is 38000mg/L, and B/C values are 0.13.Extraction equipment is multistage mixer-settler extractor, extraction dress
The theoretical stage put is 2, and the mass ratio of extractant and waste water is 0.5:1;The theoretical cam curve of waste water lightness-removing column is 15, operation pressure
Power 0.1MPa (absolute pressure), 99.0 DEG C of tower top temperature, 104.0 DEG C of bottom temperature;The theoretical cam curve of solvent recovery tower is 20, operation
Pressure 0.1MPa (absolute pressure), 53.0 DEG C of tower top temperature, 108.0 DEG C of bottom temperature.
Detection:COD value of waste water after detection process is 13000mg/L, and B/C values are 0.6.
Embodiment 4
On the basis of embodiment 1, after continuous operation 1000h, analysis, tower reactor are sampled to rectifying column tower top and tower reactor
Middle water content is 99.11wt%, tert-butyl alcohol 0.57wt%, methanol 0.19wt%;Isobutene content is in tower top
4.57wt%, MTBE content are 60.16wt%, methanol content 34.88wt%, TBA content is 0.17wt%, water content is
0.07wt%.TBA conversion ratios are 99.56%, selective isobutene 10.65%, and MTBE is selectively 89.28%.
After long period continuous operation, catalyst still has greater activity.
The waste water of generation through extracting, after de- light processing, stablize in 10000~13000mg/L, B/C 0.5 by COD value stabilization
~0.6.