CN104177217A - Method for removing methanol in material containing isobutene - Google Patents
Method for removing methanol in material containing isobutene Download PDFInfo
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- CN104177217A CN104177217A CN201310192422.9A CN201310192422A CN104177217A CN 104177217 A CN104177217 A CN 104177217A CN 201310192422 A CN201310192422 A CN 201310192422A CN 104177217 A CN104177217 A CN 104177217A
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- butylene
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Abstract
The invention provides a method for removing methanol in a material containing isobutene. The method comprises the following steps: firstly, water and the material containing isobutene are mixed in a static mixer, and the mixture is then sent into a water scrubber so as to separate methanol from an oil-phase material, wherein the mixing process of water and the material containing isobutene in the static mixer is carried out under the condition of ultrasonic wave, and power of ultrasonic wave is 0.01-100 KW and frequency is 10-100KHz. Specifically, the material containing isobutene is prepared by, for example, MTBE cracking. By ultrasonication on the static mixer, washing efficiency can be raised, and washing ratio is reduced. The method has effects of reducing operation difficulty of equipment and lowering energy consumption and material consumption. Meanwhile, other impurities are not introduced. The method has advantages of no pollution, simple operation and no higher equipment requirement.
Description
Technical field
The present invention relates to a kind of removal methods containing methyl alcohol in the material of iso-butylene, especially relate to a kind of water elution eliminating method containing methyl alcohol in the material of iso-butylene.
Background technology
At MTBE(methyl tertiary butyl ether) in the production process of cracking iso-butylene, methyl alcohol is one of reaction product being accompanied by iso-butylene, the industrial methyl alcohol that often utilizes is soluble in water, and the water-fast feature of iso-butylene generally adopts the mode of water wash column washing by methanol stripper.Particularly, in the water wash column of operate continuously, water is disperse phase, and the iso-butylene material (being called for short oil) that contains methyl alcohol is external phase, contain the oil of methyl alcohol from water wash column underfeed, wash water is from the charging of water wash column top, the continuous reverse contact of two liquid phases, and oil phase rises, water sedimentation, dissolve with methanol in oil is at water, the amplifier section on water wash column top, and oil and moisture are two-phase; Extraction liquid is the wash water that has absorbed methyl alcohol, and from continuous extraction at the bottom of tower, raffinate is the oil that has removed methyl alcohol, from the continuous extraction of tower top; Separated two-phase and obtained removing the oil of methyl alcohol and containing the wash water of methyl alcohol.Afterwards, the wash water that contains methyl alcohol reclaims methyl alcohol through rectificating method again, as described in Chinese patent CN1242969C.
Wash with water tower remove methyl alcohol wherein to constant also than being easier to, but if produce polyisobutene or isoprene-isobutylene rubber monomer iso-butylene, in product, methyl alcohol requires generally below weight content 5ppm, methanol removal to micro-difficulty increases greatly, need to adjust water wash column processing condition, increase equipment and washing ratio, just can make in oil methanol content up to standard.
Above-mentioned method for washing Shortcomings of the prior art, water consumption when it arrives finite concentration by methanol stripper is larger, if water-oil ratio (weight ratio) is selected 1.5:1 during extraction, the full scale plant of producing 10000 tons of products per year will consume 1.5 ten thousand tons of water every year, very in short supply because of China's water resources, it is particularly outstanding that resource contradiction problem seems; Meanwhile, because the wash water containing methyl alcohol after washing also will reclaim methyl alcohol through the method for rectifying, extract hourly water consumption conference and cause needing to expend larger heat in follow-up rectifying, the energy consumption of device is also just larger.
In the water wash column of operate continuously, in order to improve washing rate, the industrial mode that also can adopt static mixer and water wash column to combine removes containing the methyl alcohol in iso-butylene material.The method specifically can be adopted in two ways and be realized: the first is first oil and water to be sent into static mixer by a certain percentage, mix for the first time contact, jointly enter again water wash column bottom rising, through washing column plate or packing layer, mix for the second time contact, to water wash column top amplifier section, logistics speed step-down, profit layering, oil phase, by overhead extraction, has absorbed the water of methyl alcohol by tower reactor extraction; The second way is that wash water is divided into two portions, and first part enters static mixer together with oil, and all the other wash waters, still from the charging of water wash column napex, further carry out drip washing to oil phase, to obtain better washing effect.
But the above-mentioned washing removal efficiency containing methyl alcohol in the material of iso-butylene still needs further to be improved.
Summary of the invention
Contriver's discovery in the water wash column containing in the iso-butylene material of methyl alcohol, can improve washing efficiency by ul-trasonic irradiation, reduces washing ratio, has the effect of the operation easier, reduction energy consumption and the material consumption that reduce device; The present invention simultaneously does not introduce other impurity, has advantages of pollution-free, simple to operate, not high to equipment requirements.Further, the inventor also finds, containing in iso-butylene material continuously in the process of methanol removal, not by ul-trasonic irradiation in water wash column, but acted on the static mixer mixing for water oil two-phase before water wash column, equally also can solve above-mentioned reduction washing and compare problem; And the method need not be transformed water wash column itself, its difficulty further declines, and still less, in addition, the two is compared in facility investment, and while reaching same washing effect, the latter can also use more low power ultrasonic wave, saves running cost.
Therefore, the invention provides a kind of removal methods containing methyl alcohol in the material of iso-butylene, comprise first water is mixed in static mixer with the material containing iso-butylene, mixture is sent in water wash column again and is made methyl alcohol separated with oil phase material, wherein water with containing the material of iso-butylene the mixing process in static mixer under hyperacoustic existence, carry out, and described hyperacoustic power is 0.01～100KW, frequency is 10～1000KHZ.Particularly, preferably the described material containing iso-butylene is that MTBE cracking obtains.
In the present invention, can be that the described content containing iso-butylene in the material of iso-butylene is 10～80wt%, the content of methyl alcohol is 2～50wt%; Also be the present invention while being applicable to contain magnanimity methyl alcohol in material by methanol stripper.In the present invention, can be also that the described content containing iso-butylene in the material of iso-butylene is 95～99.999wt%, the content of methyl alcohol is 0.001～0.2%, i.e. 10～2000ppm; Also be the present invention while being applicable to contain Trace Methanol in material by methanol stripper.Certainly, more preferably, the material of MTBE cracking iso-butylene first removes magnanimity methyl alcohol under ul-trasonic irradiation in the present invention, and the product obtaining removes Trace Methanol under ul-trasonic irradiation in the present invention again, makes the methanol content in iso-butylene product reach 5ppm or following.
In the present invention, further preferably described hyperacoustic frequency is 20～80KHZ.
Ultrasonic wave of the present invention can continuous action in static mixer, but can be also that ultrasonic wave is interrupted and is acted on static mixer.In ultrasonic wave, be interrupted and do the used time, be less than or equal to the residence time of material in static mixer the interval time of preferred described ul-trasonic irradiation, more preferably 1/10～1/2 of the residence time of material in static mixer.In addition, can be 1～120 minute hyperacoustic each action time, is preferably 5～30 minutes.
In the present invention, the total water using in described water washing process is 0.1～25:1 with the weight ratio that contains the material of iso-butylene, and washing temperature is 0～100 ℃, and washing pressure is 0～15MPa; Preferably total water is 0.2～5:1 with the weight ratio that contains the material of iso-butylene, and washing temperature is 10～50 ℃, and washing pressure is 0～3MPa.In the present invention, the charging air speed LHSV that contains the material of iso-butylene in continuous water wash column is 0.5～20h
-1, be preferably 2～10h
-1.
Embodiment
Below be only preferred embodiment of the present invention, can not limit scope of the present invention with this; Be every variation of doing according to the present patent application scope 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
A static mixer and a water wash column that the present embodiment water washing device used is series connection; The stainless steel pressure tank of establishing plate washer in traverse of static mixer, volume is 2L, and water wash column is Stainless Steel Helices tower, and bottom and top are amplifier sections, and top amplifier section has visual window, is convenient to observe water-oil interface, and its internal diameter is 33mm, and filler is
porcelain ring, packed height is 2m.By ul-trasonic irradiation, in static mixer, control ultrasonic frequency is 35KHZ, and power is 50KW, and static mixer and water wash column pressure are 0.6MPa, and temperature is 25 ℃.
Needing the separated material of removing methyl alcohol is the material after MTBE cracking, and it consists of: iso-butylene 56.19wt%, and methyl alcohol 32.81wt%, MTBE is 10.19wt%, dme 0.37wt%, water 0.24wt%, other is 0.20wt%, hereinafter to be referred as material A.
The inlet amount of water is 1.08KG/h, the inlet amount of material A is 0.72KG/h, water and material A are with the ratio of weight ratio 1.5:1, by being pumped into, opened in hyperacoustic static mixer respectively, by volume pump, with the inlet amount of 1.8KG/h, send into water wash column bottom again, this wash water is all introduced into the water intake mode that static mixer enters water wash column again and classifies mode a as.The material of premix rising in water wash column, at water wash column top amplifier section, material flow obviously reduces, and profit layering has removed the oil phase of methyl alcohol by overhead extraction, has absorbed the water of methyl alcohol by tower reactor extraction.With gas chromatographic analysis oil phase, form, the results are shown in table 1.
Embodiment 2
By the method identical with embodiment 1, remove the methyl alcohol in iso-butylene material, different is that ultrasonic wave is interruption effect, and be 15 minutes each action time, and each intermittent time is 10 minutes; The results are shown in table 1.
Embodiment 3
By the method identical with embodiment 1, remove the methyl alcohol in iso-butylene material, different is that wash water adopts mode b to enter this methanol stripper system, mode b refers to that 1/3 of wash water total amount directly drenches from water wash column top into, and 2/3 first the mixing with oil phase bottom water wash column again and enter through static mixer of wash water total amount without static mixer.The wash water of 0.36KG/h, 1/3 wash water directly enters water wash column by water wash column top; And the wash water of 0.72KG/h, 2/3 wash water is first to enter static mixer, then send into water wash column bottom from static mixer; Material A containing iso-butylene is also first to enter static mixer, then sends into water wash column bottom from static mixer, and its input speed is also 0.72KG/h; The combined feed total feed speed that is water wash column bottom is 1.44KG/h, and in this system, water compares 1.5:1 with the gross weight of material A; In addition hyperacoustic power is 40KW; The results are shown in table 1.
Embodiment 4
By the method identical with embodiment 3, remove the methyl alcohol in iso-butylene material, same wash water adopts mode b to enter system, and different is that total water-oil ratio is 1:1.The wash water of 0.3KG/h, 1/3 wash water directly enters water wash column by water wash column top; And the wash water of 0.6KG/h, 2/3 wash water is first to enter static mixer, then send into water wash column bottom from static mixer; Material A containing iso-butylene is also first to enter static mixer, then sends into water wash column bottom from static mixer, and its input speed is 0.9KG/h; The combined feed total feed speed that is water wash column bottom is 1.50KG/h.In addition, hyperacoustic frequency is 50KHZ, and hyperacoustic power is 45KW.
Comparative example 1
By the method identical with embodiment 1, remove the methyl alcohol in iso-butylene, different is not open ultrasonic wave, the results are shown in table 1.
Comparative example 2
By the method identical with embodiment 3, remove the methyl alcohol in iso-butylene, different is not open ultrasonic wave, the results are shown in table 1.
Embodiment 5
By the method identical with embodiment 3, remove the methyl alcohol in iso-butylene material, it is used that different is is material B containing iso-butylene material, and it consists of iso-butylene 99.59wt%, methyl alcohol 0.08wt%, and MTBE is 0.04wt%, dme 0.17wt%, water 0.12wt%; Total water-oil ratio is 0.3:1.The wash water of 0.072KG/h, 1/3 wash water directly enters water wash column by water wash column top; And the wash water of 0.144KG/h, 2/3 wash water is first to enter static mixer, then send into water wash column bottom from static mixer; Material A containing iso-butylene is also first to enter static mixer, then sends into water wash column bottom from static mixer, and its input speed is 0.72KG/h; The combined feed total feed speed that is water wash column bottom is 0.864KG/h.In addition, hyperacoustic frequency is 50KHZ, and hyperacoustic power is 40KW.
Comparative example 3
By the method identical with embodiment 5, remove the methyl alcohol in iso-butylene, different is not open ultrasonic wave, and wash water adopts mode a to enter this methanol stripper system, the results are shown in table 1.
Comparative example 4
By the method identical with comparative example 3, remove the methyl alcohol in iso-butylene, different is that water and material A weight ratio are 0.6:1, and the inlet amount of water is 0.432KG/h, and the inlet amount of material A is 0.72KG/h, the results are shown in table 1.
Comparative example 5
By the method identical with embodiment 1, remove the methyl alcohol in iso-butylene.Different is that ultrasonic wave is not to act on static mixer, but acts on the water wash column being connected to after static mixer, and ultrasonic frequency is 50KHZ, and power is 100KW; The results are shown in table 1.
Table 1
As can be seen from Table 1, ul-trasonic irradiation, in static mixer, is compared with not adding ultrasonic wave, can be improved the efficiency of washing methyl alcohol; If the water elution that generates iso-butylene in MTBE scission reaction is except in magnanimity methyl alcohol, add ultrasonic wave to compare with not adding ultrasonic wave, the methanol content in iso-butylene is in a ratio of its half left and right.More favourable for the Trace Methanol removing in the iso-butylene that MTBE cracking generates, under the condition of identical washing ratio, add ultrasonic wave to compare with not adding ultrasonic wave, the methanol content in iso-butylene be only its 1/3; From another angle, consider, if reach same low methanol content in the rear iso-butylene of washing, the water consumption while not adding ultrasonic wave at least must be enhanced about more than once.In addition, by ul-trasonic irradiation in water wash column with ul-trasonic irradiation is compared in static mixer, the two can reduce washing ratio equally; The latter need not transform water wash column itself, and its difficulty further declines, and facility investment still less; And the latter can also use more low power ultrasonic wave while reaching same washing effect, save running cost.
Claims (10)
1. the removal methods containing methyl alcohol in the material of iso-butylene, comprise first water is mixed in static mixer with the material containing iso-butylene, mixture is sent in water wash column again and is made methyl alcohol separated with oil phase material, wherein water with containing the material of iso-butylene the mixing process in static mixer under hyperacoustic existence, carry out, and described hyperacoustic power is 0.01～100KW, frequency is 10～1000KHZ.
2. method according to claim 1, is characterized in that, the described material containing iso-butylene is that MTBE cracking obtains.
3. method according to claim 1, is characterized in that, the described content containing iso-butylene in the material of iso-butylene is 10～80wt%, and the content of methyl alcohol is 2～50wt%.
4. method according to claim 1, is characterized in that, the described content containing iso-butylene in the material of iso-butylene is 95～99.999wt%, and the content of methyl alcohol is 0.001～0.2%.
5. according to the method described in any one in claim 1～4, it is characterized in that, hyperacoustic frequency is 20～80KHZ.
6. according to the method described in any one in claim 1～4, it is characterized in that, described ultrasonic wave is that continuous action is in static mixer.
7. according to the method described in any one in claim 1～4, it is characterized in that, described ultrasonic wave is to be interrupted to act on static mixer.
8. method according to claim 7, is characterized in that, is less than or equal to the residence time of material in static mixer the interval time of described ul-trasonic irradiation, is preferably 1/10～1/2 of the residence time of material in static mixer.
9. according to the method described in any one in claim 1～8, the total water using in water washing process is 0.1～25:1 with the weight ratio that contains the material of iso-butylene, and washing temperature is 0～100 ℃, and washing pressure is 0～15MPa; Preferably total water is 0.2～5:1 with the weight ratio that contains the material of iso-butylene, and washing temperature is 10～50 ℃, and washing pressure is 0～3MPa.
10. according to the method described in any one in claim 1～8, the charging air speed LHSV that contains the material of iso-butylene in continuous water wash column is 0.5～20h
-1, be preferably 2～10h
-1.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310192422.9A CN104177217B (en) | 2013-05-22 | 2013-05-22 | The removal methods of methanol in a kind of material containing isobutene. |
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| CN201310192422.9A CN104177217B (en) | 2013-05-22 | 2013-05-22 | The removal methods of methanol in a kind of material containing isobutene. |
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| CN104177217B CN104177217B (en) | 2016-12-07 |
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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 |
-
2013
- 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 |
|---|
| 周继东等: "异丁烯制备工艺脱甲醇分离流程的优化", 《石油化工设计》 * |
| 林仲茂: "超声清洗及功率超声在化工方面的一些应用", 《化学清洗》 * |
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