CN104177217B - The removal methods of methanol in a kind of material containing isobutene. - Google Patents
The removal methods of methanol in a kind of material containing isobutene. Download PDFInfo
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- CN104177217B CN104177217B CN201310192422.9A CN201310192422A CN104177217B CN 104177217 B CN104177217 B CN 104177217B CN 201310192422 A CN201310192422 A CN 201310192422A CN 104177217 B CN104177217 B CN 104177217B
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Abstract
The present invention provides the removal methods of methanol in a kind of material containing isobutene., including first water being mixed in static mixer with the material containing isobutene., mixture is re-fed in water scrubber methanol is separated with oil phase material, wherein water is carried out in the presence of ultrasound wave with the mixed process in static mixer of the material containing isobutene., and the power of described ultrasound wave is 0.01～100KW, frequency is 10～1000KHZ.Specifically, the described for example, MTBE of the material containing isobutene. cracking prepares.In the present invention, by ul-trasonic irradiation in static mixer, washing efficiency can be improved, reduce washing ratio, have and reduce the operation easier of device, reduction energy consumption and the effect of material consumption；The present invention does not introduce other impurity simultaneously, has pollution-free, simple to operate, the highest to equipment requirements advantage.
Description
Technical field
The present invention relates to the removal methods of methanol in a kind of material containing isobutene., especially relate to a kind of material containing isobutene.
The washing removal methods of middle methanol.
Background technology
At MTBE(methyl tertiary butyl ether(MTBE)) cracking preparing isobutene production process in, methanol is accompanied by the reaction of isobutene.
One of product, industrial often utilizes methanol soluble in water, and the water-fast feature of isobutene., general uses water scrubber washing
Mode by methanol stripper.Specifically, in the water scrubber of continuous operation, aqueous phase is dispersion phase, the isobutene. thing containing methanol
Material (being called for short oil) is continuous phase, and the oil containing methanol feeds from water scrubber bottom, and wash water feeds from water scrubber top, two liquid phases
The most reverse contact, oil phase rises, and aqueous phase settles, and the methanol in oil is dissolved in aqueous phase, at the amplifier section on water scrubber top,
Oil and moisture are biphase；Extract is the wash water absorbing methanol, and from extraction continuous at the bottom of tower, raffinate is to be stripped of methanol
Oil, from the continuous extraction of tower top；Separate biphase and obtain being stripped of the oil of methanol and the wash water containing methanol.Afterwards, containing methanol
Wash water reclaims methanol through rectificating method again, as described in Chinese patent CN1242969C.
Wash tower removing methanol therein with water to be also easier to constant, but if produce polyisobutylene or butyl rubber monomer
With isobutene., in product, methanol requires typically at below weight content 5ppm, and the difficulty of methanol removal to trace is greatly increased,
Need to adjust water scrubber process conditions, increase equipment and washing ratio, methanol content in oil just can be made up to standard.
Above-mentioned method for washing Shortcomings of the prior art, it is by bigger for water consumption during methanol stripper to finite concentration,
If water-oil factor (weight ratio) selects 1.5:1, the then commercial plant producing 10000 tons of products per year to consume 1.5 ten thousand every year during extraction
Ton water, because China's water resource is the most in short supply, resource contradiction problem seems especially prominent；Meanwhile, because of washing containing methanol after washing
Water also to reclaim methanol through the method for rectification, then extraction hourly water consumption conference needs to expend bigger during causing follow-up rectification
Heat, the energy consumption of device is the biggest.
In the water scrubber of continuous operation, in order to improve washing rate, industrial static mixer also can be used to tie mutually with water scrubber
The mode closed removes containing the methanol in isobutene. material.The method specifically can use two ways to realize: the first is first will
Oil and water send into static mixer by a certain percentage, carry out mixing for the first time contact, more jointly enter water scrubber bottom slowly on
Rise, carry out second time through washing column plate or packing layer and mix contact, to water scrubber top amplifier section, logistics speed step-down,
Profit is layered, and oil phase, by overhead extraction, absorbs the aqueous phase of methanol by tower reactor extraction；The second way is that wash water is divided into two
Part, Part I enters static mixer together with oil, and remaining wash water still feeds from water scrubber napex, further to oil phase
Carry out drip washing, to obtain more preferable water washing effect.
But the washing removal efficiency of methanol still needs to be improved further in the above-mentioned material containing isobutene..
Summary of the invention
Inventor finds, by ul-trasonic irradiation water scrubber in the isobutene. material containing methanol, to improve washing efficiency, reduces
Washing ratio, has and reduces the operation easier of device, reduction energy consumption and the effect of material consumption；The present invention does not introduce other impurity simultaneously,
There is pollution-free, simple to operate, the highest to equipment requirements advantage.Further, the present inventors have additionally discovered that, containing isobutyl
In alkene material during continuous methanol removal, not by ul-trasonic irradiation in water scrubber, but before being acted on water scrubber
The static mixer for water phase and an oil phase mixing in face, the most also can solve above-mentioned reduction washing and compare problem；And the method is not
With transformation water scrubber itself, its difficulty declines further, and equipment investment is less, it addition, the two is compared, reaches same water
When washing effect, the latter can also use more low power ultrasound wave, saves operating cost.
Therefore, the present invention provides the removal methods of methanol in a kind of material containing isobutene., including first by water and containing isobutene.
Material mixes in static mixer, and mixture is re-fed in water scrubber methanol is separated with oil phase material, wherein water with contain
The material of isobutene. mixed process in static mixer is carried out in the presence of ultrasound wave, and the merit of described ultrasound wave
Rate is 0.01～100KW, and frequency is 10～1000KHZ.Split and specifically, it is preferable to the described material containing isobutene. is MTBE
Solution prepares.
In the present invention, can be that in the described material containing isobutene., the content of isobutene. is 10～80wt%, the content of methanol
It is 2～50wt%；Namely the present invention be applicable to material containing magnanimity methanol time by methanol stripper.In the present invention, it is possible to
To be that in the described material containing isobutene., the content of isobutene. is 95～99.999wt%, the content of methanol is 0.001～0.2%,
I.e. 10～2000ppm；Namely the present invention be applicable to material containing Trace Methanol time by methanol stripper.Certainly, the most excellent
Choosing, removes magnanimity methanol under the material of MTBE cracking preparing isobutene ul-trasonic irradiation the most in the present invention, obtains
Trace Methanol is removed so that the methanol content in isobutene. product reaches 5ppm under product ul-trasonic irradiation the most in the present invention
Or below.
In the present invention, the frequency of further preferred described ultrasound wave is 20～80KHZ.
Ultrasound wave of the present invention can be with continuous action in static mixer but it also may be that ultrasound wave interruption acts on static mixing
Clutch.When ultrasound wave interruption effect, it is less than or equal to material the interval time of the most described ul-trasonic irradiation at static mixer
In the time of staying, more preferably the 1/10～1/2 of the material time of staying in static mixer.It addition, ultrasound wave is every
Secondary action time can be 1～120 minute, preferably 5～30 minutes.
In the present invention, the total water used in described water-washing process is 0.1～25:1 with the weight ratio of the material containing isobutene.,
Washing temperature is 0～100 DEG C, and washing pressure is 0～15MPa；The most total water with the weight ratio of the material containing isobutene. is
0.2～5:1, washing temperature is 10～50 DEG C, and washing pressure is 0～3MPa.In the present invention, containing different in continuous print water scrubber
The Feed space velocities LHSV of the material of butylene is 0.5～20h-1, preferably 2～10h-1。
Detailed description of the invention
Below it is only presently preferred embodiments of the present invention, it is impossible to limit the scope of the present invention with this；The most every according to the present patent application model
Enclose made change and modification, all should still remain within the scope of the patent.
Below in conjunction with concrete example, the present invention is described further.
Embodiment 1
Water washing device used by the present embodiment is the static mixer and a water scrubber connected；Static mixer is one
Setting the stainless steel pressure tank of plate washer in traverse, volume is 2L, water scrubber be stainless steel helices tower, bottom and top be amplify
Part, top amplifier section has visual window, it is simple to observing oil-water interfaces, its internal diameter is 33mm, and filler is's
Porcelain ring, packed height is 2m.By ul-trasonic irradiation in static mixer, control ultrasonic frequency is 35KHZ, power
Being 0.6MPa for 50KW, static mixer and water scrubber pressure, temperature is 25 DEG C.
The material that need to be separated off methanol is the material after MTBE cracks, consisting of: isobutene. 56.19wt%, methanol
32.81wt%, MTBE are 10.19wt%, dimethyl ether 0.37wt%, water 0.24wt%, and other is 0.20wt%, below letter
Claim material A.
The inlet amount of water is 1.08KG/h, and the inlet amount of material A is 0.72KG/h, and water and material A are with weight ratio 1.5:1
Ratio, respectively by being pumped in the static mixer opening ultrasound wave, then sent with the inlet amount of 1.8KG/h by dosing pump
Entering water scrubber bottom, this wash water is all introduced into static mixer and enters back into the water intake mode of water scrubber and be classified as mode a.In advance
Mixed material slowly rises in water scrubber, and at water scrubber top amplifier section, material flow substantially reduces, and profit is layered,
It is stripped of the oil phase of methanol by overhead extraction, absorbs the aqueous phase of methanol by tower reactor extraction.Form with gas chromatographic analysis oil phase,
Result is listed in table 1.
Embodiment 2
With the methanol in method removing isobutene. material same as in Example 1, except for the difference that ultrasound wave is interruption effect,
Action time is 15 minutes every time, and each intermittent time is 10 minutes；Result is listed in table 1.
Embodiment 3
With the methanol in method removing isobutene. material same as in Example 1, except for the difference that wash water uses the entrance of mode b to be somebody's turn to do
Methanol stripper system, mode b refer to the 1/3 of wash water total amount directly drench from water scrubber top without static mixer into, and
The 2/3 of wash water total amount first passes through static mixer and mixes entrance bottom water scrubber again with oil phase.The wash water of 0.36KG/h, i.e.
The wash water of 1/3 is directly entered water scrubber by water scrubber top；And the wash water of the wash water of 0.72KG/h, i.e. 2/3 is to initially enter
Static mixer, then send into water scrubber bottom from static mixer；Material A containing isobutene. is also to initially enter static mixing
Device, then send into water scrubber bottom from static mixer, its charging rate is also 0.72KG/h；The i.e. combined feed of water scrubber bottom
Speed is 1.44KG/h, and in this system, water compares 1.5:1 with the gross weight of material A；In addition the power of ultrasound wave is 40KW；
Result is listed in table 1.
Embodiment 4
With the methanol in method removing isobutene. material same as in Example 3, same wash water uses mode b to enter system,
Except for the difference that total water-oil factor is 1:1.The wash water of the wash water of 0.3KG/h, i.e. 1/3 is directly entered water scrubber by water scrubber top；
And the wash water of the wash water of 0.6KG/h, i.e. 2/3 is to initially enter static mixer, then send into water scrubber from static mixer
Portion；Material A containing isobutene. is also to initially enter static mixer, then sends into water scrubber bottom from static mixer, and it enters
Material speed is 0.9KG/h；The i.e. combined feed speed of water scrubber bottom is 1.50KG/h.It addition, the frequency of ultrasound wave is 50KHZ,
The power of ultrasound wave is 45KW.
Comparative example 1
With the methanol in method removing isobutene. same as in Example 1, except for the difference that not opening ultrasound wave, result is listed in table
1。
Comparative example 2
With the methanol in method removing isobutene. same as in Example 3, except for the difference that not opening ultrasound wave, result is listed in table
1。
Embodiment 5
With the methanol in method removing isobutene. material same as in Example 3, the material containing isobutene. except for the difference that used is
Material B, consisting of isobutene. 99.59wt%, methanol 0.08wt%, MTBE are 0.04wt%, dimethyl ether 0.17wt%,
Water 0.12wt%；Total water-oil factor is 0.3:1.The wash water of the wash water of 0.072KG/h, i.e. 1/3 is directly entered by water scrubber top
Water scrubber；And the wash water of the wash water of 0.144KG/h, i.e. 2/3 is to initially enter static mixer, then send from static mixer
Enter water scrubber bottom；Material A containing isobutene. is also to initially enter static mixer, then sends into water scrubber from static mixer
Bottom, its charging rate is 0.72KG/h；The i.e. combined feed speed of water scrubber bottom is 0.864KG/h.It addition, ultrasound wave
Frequency be 50KHZ, the power of ultrasound wave is 40KW.
Comparative example 3
With the methanol in method removing isobutene. same as in Example 5, except for the difference that do not open ultrasound wave, and wash water uses
Mode a enters this methanol stripper system, and result is listed in table 1.
Comparative example 4
With the methanol in the method removing isobutene. identical with comparative example 3, except for the difference that water and material A weight ratio are 0.6:1,
The inlet amount of water is 0.432KG/h, and the inlet amount of material A is 0.72KG/h, and result is listed in table 1.
Comparative example 5
With the methanol in method removing isobutene. same as in Example 1.Except for the difference that ultrasound wave is not to act on static mixing
Device, but act on the water scrubber after being connected to static mixer, and ultrasonic frequency is 50KHZ, power is 100KW；
Result is listed in table 1.
Table 1
As it can be seen from table 1 by ul-trasonic irradiation in static mixer, compared with being not added with ultrasound wave, washing first can be improved
The efficiency of alcohol；As generated the water elution of isobutene. in MTBE cracking reaction except, in magnanimity methanol, adding ultrasound wave and be not added with surpassing
Sound wave is compared, and the methanol content in isobutene. is in a ratio of about its half.And the isobutene. that removing MTBE is cracked to form
In Trace Methanol the most advantageously, identical washing than under conditions of, add ultrasound wave compared with being not added with ultrasound wave, isobutyl
Methanol content in alkene be only its 1/3；Consider from another angle, if methanol the lowest in isobutene. after reaching washing
Content, water consumption when being not added with ultrasound wave at least must be enhanced about more than once.It addition, ul-trasonic irradiation in water scrubber and will be surpassed
Acoustic wave action is compared in static mixer, and the two can reduce washing ratio equally；The latter need not transform water scrubber itself, and it is difficult
Degree declines further, and equipment investment is less；And the latter can also use the most low power ultrasonic when reaching same water washing effect
Ripple, saves operating cost.
Claims (12)
1. a removal methods for methanol in the material containing isobutene., including first being mixed in static state with the material containing isobutene. by water
Mixing in clutch, mixture is re-fed in water scrubber methanol is separated with oil phase material, wherein water and the material containing isobutene.
Mixed process in static mixer is carried out in the presence of ultrasound wave, and the power of described ultrasound wave is
0.01～100KW, frequency is 10～1000KHZ；
The total water used in water-washing process is 0.1～25:1 with the weight ratio of the material containing isobutene., and washing temperature is
0～100 DEG C, washing pressure is 0～15MPa.
Method the most according to claim 1, it is characterised in that the described material containing isobutene. is MTBE cracking system
?.
Method the most according to claim 1, it is characterised in that the content of isobutene. in the described material containing isobutene.
Being 10～80wt%, the content of methanol is 2～50wt%.
Method the most according to claim 1, it is characterised in that the content of isobutene. in the described material containing isobutene.
Being 95～99.999wt%, the content of methanol is 0.001～0.2%.
5. according to the method described in any one in Claims 1 to 4, it is characterised in that the frequency of ultrasound wave is
20～80KHZ.
6. according to the method described in any one in Claims 1 to 4, it is characterised in that described ultrasound wave is continuous action
In static mixer.
7. according to the method described in any one in Claims 1 to 4, it is characterised in that described ultrasound wave is interruption effect
In static mixer.
Method the most according to claim 7, it is characterised in that the interval time of described ul-trasonic irradiation is less than or equal to
The material time of staying in static mixer.
Method the most according to claim 8, it is characterised in that the interval time of described ul-trasonic irradiation is described thing
The 1/10～1/2 of the material time of staying in static mixer.
10. according to the method described in any one in Claims 1 to 4, it is characterised in that use in water-washing process is total
Water is 0.2～5:1 with the weight ratio of the material containing isobutene., and washing temperature is 10～50 DEG C, and washing pressure is 0～3MPa.
11. according to the method described in any one in Claims 1 to 4, it is characterised in that containing different in continuous print water scrubber
The Feed space velocities LHSV of the material of butylene is 0.5～20h-1。
12. methods according to claim 11, it is characterised in that contain the material of isobutene. in continuous print water scrubber
Feed space velocities LHSV be 2～10h-1。
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6049020A (en) * | 1997-04-02 | 2000-04-11 | Institut Francais Du Petrole | Process for producing an ether and an olefin from a hydrocarbon cut containing at least one tertiary olefin by synthesising then decomposing an ether, comprising a first step for purifying the olefin by fractionation |
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- 2013-05-22 CN CN201310192422.9A patent/CN104177217B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6049020A (en) * | 1997-04-02 | 2000-04-11 | Institut Francais Du Petrole | Process for producing an ether and an olefin from a hydrocarbon cut containing at least one tertiary olefin by synthesising then decomposing an ether, comprising a first step for purifying the olefin by fractionation |
Non-Patent Citations (2)
| Title |
|---|
| 异丁烯制备工艺脱甲醇分离流程的优化;周继东等;《石油化工设计》;20021231;第19卷(第4期);第18-20页 * |
| 超声清洗及功率超声在化工方面的一些应用;林仲茂;《化学清洗》;19991231;第15卷(第6期);第48-49页 * |
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