CN101597200A - Method by preparing isoamylene from methyl tert-amyl ether - Google Patents
Method by preparing isoamylene from methyl tert-amyl ether Download PDFInfo
- Publication number
- CN101597200A CN101597200A CNA2008100386317A CN200810038631A CN101597200A CN 101597200 A CN101597200 A CN 101597200A CN A2008100386317 A CNA2008100386317 A CN A2008100386317A CN 200810038631 A CN200810038631 A CN 200810038631A CN 101597200 A CN101597200 A CN 101597200A
- Authority
- CN
- China
- Prior art keywords
- reaction
- methyl
- isoamylene
- ether
- amyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of method by preparing isoamylene from methyl tert-amyl ether comprises: 1) tert amyl methyl ether(TAME) is carried out ether with gas phase by beds and is separated reaction, and temperature of reaction is 130～300 ℃; 2) ether is separated reaction product and is removed methyl alcohol, gets the coarse isoamylene material; 3) add tertiary amyl alcohol in the coarse isoamylene material, carry out isomerization reaction with liquid phase by beds then, make the 2-methyl-1-butene alkene in the coarse isoamylene be converted into the 2-methyl-2-butene.The add-on of tertiary amyl alcohol is benchmark with the coarse isoamylene, is 0.1～2.0wt%, and mass space velocity is 1～35hr
-1, temperature of reaction is 18～45 ℃, and reaction pressure is 0.3～1.0MPa, and catalyzer is the sulfonic group Zeo-karb, and its mass exchange capacity is 3～5.5mmol/g.The present invention has suppressed in the isomerization reaction 2-methyl-2-butene and 2-methyl-1-butene alkene separately or the generation of dimerization reaction each other effectively.
Description
Technical field
The present invention relates to a kind of method by preparing isoamylene from methyl tert-amyl ether, be particularly related to ether and separate the coarse isoamylene that obtains and further carry out isomerization reaction, to improve the wherein method for preparing isopentene of 2-methyl-2-butene content by the fixed bed catalyst bed that constitutes by the sulfonic group Zeo-karb.
Background technology
Isopentene is a kind of important chemical material, is used to produce resin and pesticide intermediate etc.Isopentene is the mixture of 2-methyl-2-butene and 2-methyl-1-butene alkene normally, and the 2-methyl-2-butene is an active ingredient owing to only react to great majority, so the high more using value of the 2-methyl-2-butene content of isopentene is also high more.
Isopentene mainly is present in the C 5 fraction of the C 5 fraction of catalytically cracked gasoline or naphtha cracking system ethylene by-product, owing to contain the very approaching compound of many boiling points in these carbon five materials, isopentene therefrom separates and is not easy.The separation method that adopts at most is the tert amyl methyl ether(TAME) cracking process at present, i.e. C 5 fraction and methyl alcohol reaction generates tert amyl methyl ether(TAME), the refining then high-purity methyl tert-amyl ether that obtains, and Pintsch process obtains coarse isoamylene again.2-methyl-2-butene/2-methyl-1-butene alkene is generally (1～5)/1 in the coarse isoamylene that obtains thus, and the 2-methyl-2-butene content is relatively low.Therefore need usually coarse isoamylene is carried out isomerization reaction again, make 2-methyl-1-butene alkene wherein be converted into the 2-methyl-2-butene, to improve the content of 2-methyl-2-butene.Introduce as Chinese patent ZL01105415.8 and ZL 01105416.6, it carries out isomerization reaction with coarse isoamylene by sulfonic group Zeo-karb fixed bed catalyst bed, thereby the content of 2-methyl-2-butene in the raising coarse isoamylene, this method can be increased to (7～14)/1 by (1～5) with the mass ratio of 2-methyl-2-butene in the coarse isoamylene and 2-methyl-1-butene alkene, and the more previous technology of whole technological process is also more simple.
But when isomerization reaction was carried out, 2-methyl-2-butene and 2-methyl-1-butene alkene all were easy to take place dimerization reaction separately or each other, aforesaid method in the ordinary course of things in the product dimer content can reach about 4wt%.Though dipolymer can be removed by treating process, this will cause the reduction of efficiency of pcr product and the increase of energy consumption.On the other hand, the reaction heat of dimerization reaction also can make reaction bed temperature produce unusual fluctuations, makes isomerization reaction be difficult to control reposefully.
Summary of the invention
The invention provides a kind of method by preparing isoamylene from methyl tert-amyl ether, ether is separated the coarse isoamylene that obtains and is further carried out isomerization reaction by the fixed bed catalyst bed that is made of the sulfonic group Zeo-karb, to improve wherein 2-methyl-2-butene content.The technical problem that the present invention solves is to have suppressed in the isomerization reaction 2-methyl-2-butene and 2-methyl-1-butene alkene effectively separately or the generation of dimerization reaction each other.
Below be the concrete technical scheme of the present invention:
A kind of method by preparing isoamylene from methyl tert-amyl ether may further comprise the steps:
1) tert amyl methyl ether(TAME) is carried out ether with gas phase by beds and is separated reaction, and temperature of reaction is 130～300 ℃;
2) ether is separated reaction product and is removed methyl alcohol, gets the coarse isoamylene material;
3) add tertiary amyl alcohol in the coarse isoamylene material, carry out isomerization reaction with liquid phase by beds then, make the 2-methyl-1-butene alkene in the coarse isoamylene be converted into the 2-methyl-2-butene, the tertiary amyl alcohol add-on is benchmark with the coarse isoamylene, be 0.1～2.0wt%, mass space velocity is 1～35hr
-1, temperature of reaction is 18～45 ℃, and reaction pressure is 0.3～1.0MPa, and catalyzer is the sulfonic group Zeo-karb, and its mass exchange capacity is 3～5.5mmol/g.
Above-mentioned steps 3) product that obtains of described isomerization reaction can further carry out rectifying again, rectifying Tata still temperature is 115～125 ℃, tower top temperature is 59～68 ℃, rectifying pressure is 0.1～0.5MPa, reflux ratio is 1～3, the smart isopentene of side line output, cat head, tower still are discharged light constituent and heavy constituent impurity respectively.
Above-mentioned steps 1) described ether is separated catalyst for reaction and is generally solid acid, as by H
2SO
4, HF or HCl modification α-Al
2O
3, or the silicon-dioxide of the oxide compound of load tungsten; Temperature of reaction is preferably 180～230 ℃.
Above-mentioned steps 2) described ether is separated reaction product and can be adopted water elution to remove methyl alcohol.
Above-mentioned steps 3) described tertiary amyl alcohol add-on is a benchmark with the coarse isoamylene, is preferably 0.2～1.5wt%; The mass exchange capacity of sulfonic group Zeo-karb is preferably 4～5mmol/g; Mass space velocity is preferably 5～20hr
-1Temperature of reaction is preferably 25～35 ℃; Reaction pressure is preferably 0.4～0.8MPa.
Technical scheme of the present invention mainly comprises three steps, wherein the heating pyrolyze of tert amyl methyl ether(TAME), water elution remove methyl alcohol and prior art basic identical fully.Split product removes the coarse isoamylene that obtains behind the methyl alcohol through water elution and directly carries out isomerization reaction, the mass ratio of 2-methyl-2-butene and 2-methyl-1-butene alkene all can make isomerization reaction carry out smoothly in the scope of (1～5)/1 in the coarse isoamylene, and the turndown ratio of reaction is bigger.After isomerization reaction, the mass ratio of 2-methyl-2-butene and 2-methyl-1-butene alkene can be increased to (7～14)/1 in the product that obtains.
Key of the present invention is that coarse isoamylene has added an amount of tertiary amyl alcohol earlier before carrying out isomerization reaction by beds, and the contriver found through experiments, and this is very effective to the generation that suppresses dimerization reaction in the isomerization reaction.Infer that in theory dimerization reaction requires catalytic center to have higher strength of acid than isomerization reaction, after tertiary amyl alcohol adds reaction mass, will be adsorbed in resin surface, make the strength of acid appropriateness of resin reduce.Strength of acid after the reduction is enough to satisfy the carrying out of isomerization reaction, yet but can reduce the speed of reaction of dimerization reaction greatly, thereby effectively suppresses the generation of dimerization reaction.
Product after the isomerization can adopt general rectificating method further to make with extra care, the high purity isopentene of side line output high content of 2-methyl-2-butene.Because the tertiary amyl alcohol boiling point is higher, is easy to separate with isopentene, can not produce any detrimentally affect to the isopentene quality product, the purity of the isopentene after making with extra care can reach more than 99%.
Compared with prior art, advantage of the present invention is by the inhibition to dimerization reaction in isomerization reaction, significantly reduced the content of dipolymer in the isomerization reaction product, the content of dipolymer can be reduced to below 1% in the product, makes the transformation efficiency of isomerization reaction and selectivity all be significantly improved.Simultaneously eliminated the isomerization catalyst bed layer temperature anomaly wave phenomenon that causes because of the dimerization reaction heat release basically, isomerization reaction has been under the stable status all the time carries out.
Come details of the present invention is further described below by embodiment, because the present invention is that mainly other parts are then basic identical with prior art, so embodiment will pay attention to enumerating of isomerization reaction experimental data to the improvement of isomerization reaction part.In an embodiment, the transformation efficiency of isomerization reaction, selectivity are calculated by following formula respectively, in the formula and the 2MB1 in each table be that 2-methyl-1-butene alkene, 2MB2 are that 2-methyl-2-butene, TAME are tert amyl methyl ether(TAME).
Embodiment
[embodiment 1～10]
One, tert amyl methyl ether(TAME) heating pyrolyze
Reaction raw materials is the C5 fraction of naphtha steam cracking system ethylene by-product and the tert amyl methyl ether(TAME) that the methyl alcohol reaction obtains.Behind the tert amyl methyl ether(TAME) heating and gasifying, pass through by HF modified alpha-Al with gas phase
2O
3The beds of filling carries out ether and separates reaction, and temperature of reaction is controlled to be 180～230 ℃.Ether is separated the reaction product water elution and is removed wherein methyl alcohol, obtains coarse isoamylene, and its component sees Table 1.
Table 1.
| 2MB2 (wt％) | 2MB1 (wt％) | 2MB2/2MB1 (mass ratio) | TAME (wt％) | Isopentene dipolymer (wt%) | Other carbon five impurity such as grade |
| 74.18 | 25.04 | 2.96 | 0.57 | 0.04 | Surplus |
Two, isomerization reaction
Isomerization reaction is carried out in being of a size of the stainless steel tubular type fixed-bed reactor of φ 25mm * 1500mm.40 gram particles of packing in the reactor directly are the spherical sulfonic group cation exchange resin catalyst of 0.40～1.25mm, constitute the fixed bed catalyst bed, and the mass exchange capacity of resin is 3～5.5mmol/g.The outside dress of reactor circulating hot water temperature control chuck is installed the thermometric RTD respectively in the upper, middle and lower of beds.The reaction feed amount is controlled by fresh feed pump, and system pressure is regulated by back pressure valve.
Add tertiary amyl alcohol in the reaction raw materials coarse isoamylene in the desired amount, pass through fixed bed, and carry out isomerization reaction by the reaction conditions of setting by the inlet amount of setting.The reaction conditions of each embodiment sees Table 2.
[comparative example]
Do not add tertiary amyl alcohol except that in the reaction raw materials coarse isoamylene of isomerization reaction, all the other are with embodiment 1～10, and concrete reaction conditions sees Table 2.
The isomerization reaction product that embodiment and comparative example obtain adopts red, orange, green, blue, yellow (ROGBY) to carry out composition analysis, and calculates the transformation efficiency and the selectivity of product of isomerization reaction, the results are shown in Table 3.
Table 2.
| Mass space velocity (hr -1) | Temperature of reaction (℃) | Reaction pressure (MPa) | Tertiary amyl alcohol add-on (wt%) | |
| Embodiment 1 | 1.0 | 18 | 0.3 | 0.1 |
| Embodiment 2 | 5.0 | 20 | 0.4 | 0.3 |
| Embodiment 3 | 7.0 | 23 | 0.5 | 0.5 |
| Embodiment 4 | 10.0 | 25 | 0.7 | 0.8 |
| Embodiment 5 | 15.0 | 28 | 0.8 | 1.0 |
| Embodiment 6 | 20.0 | 35 | 1.0 | 1.2 |
| Embodiment 7 | 25.0 | 38 | 0.5 | 1.4 |
| Embodiment 8 | 30.0 | 40 | 0.5 | 1.5 |
| Embodiment 9 | 35.0 | 45 | 0.5 | 2.0 |
| Embodiment 10 | 8.0 | 30 | 0.5 | 0.7 |
| Comparative example | 8.0 | 30 | 0.5 | - |
Annotate: the tertiary amyl alcohol add-on is a benchmark in the reaction raw materials coarse isoamylene.
Table 3.
| 2MB2 content (wt%) | 2MB2/2MB1 (mass ratio) | Isopentene dimer content (wt%) | 2MB1 transformation efficiency (%) | 2MB2 selectivity (%) | |
| Embodiment 1 | 91.34 | 12.83 | 0.80 | 71.53 | 96.31 |
| Embodiment 2 | 91.48 | 13.02 | 0.75 | 71.91 | 96.61 |
| Embodiment 3 | 91.81 | 13.56 | 0.68 | 72.93 | 97.04 |
| Embodiment 4 | 92.00 | 13.85 | 0.62 | 73.44 | 97.39 |
| Embodiment 5 | 91.87 | 13.51 | 0.59 | 72.81 | 97.53 |
| Embodiment 6 | 91.89 | 13.48 | 0.55 | 72.74 | 97.75 |
| Embodiment 7 | 91.93 | 13.45 | 0.50 | 72.67 | 98.02 |
| Embodiment 8 | 91.74 | 12.93 | 0.42 | 71.63 | 98.44 |
| Embodiment 9 | 91.80 | 12.85 | 0.32 | 71.44 | 98.99 |
| Embodiment 10 | 91.96 | 13.47 | 0.47 | 72.70 | 98.19 |
| Comparative example | 82.90 | 7.32 | 4.38 | 54.74 | 68.64 |
[embodiment 11～14]
The isomerization reaction product that embodiment 3 obtains further carries out rectified purified, the smart isopentene of side line output, and cat head, tower still are discharged light constituent and heavy constituent impurity respectively.Concrete rectifying condition sees Table 4, and smart isopentene product adopts red, orange, green, blue, yellow (ROGBY) to carry out composition analysis, and leading indicator sees Table 5.
Table 4.
| Tower still temperature (℃) | Tower top temperature (℃) | Working pressure (MPa) | Reflux ratio | |
| Embodiment 11 | 125 | 68 | 0.50 | 3.0 |
| Embodiment 12 | 120 | 63 | 0.12 | 2.0 |
| Embodiment 13 | 123 | 65 | 0.30 | 3.0 |
| Embodiment 14 | 115 | 59 | 0.10 | 1.0 |
Table 5.
| 2MB2 content (wt%) | 2MB2/2MB1 (mass ratio) | Isopentene dimer content (wt%) | Purity (%) | |
| Embodiment 11 | 92.83 | 13.15 | 0.00 | 99.89 |
| Embodiment 12 | 93.15 | 14.09 | 0.00 | 99.76 |
| Embodiment 13 | 93.30 | 14.14 | 0.00 | 99.90 |
| Embodiment 14 | 93.00 | 13.58 | 0.00 | 99.85 |
Claims (10)
1, a kind of method by preparing isoamylene from methyl tert-amyl ether may further comprise the steps:
1) tert amyl methyl ether(TAME) is carried out ether with gas phase by beds and is separated reaction, and temperature of reaction is 130～300 ℃;
2) ether is separated reaction product and is removed methyl alcohol, gets the coarse isoamylene material;
3) add tertiary amyl alcohol in the coarse isoamylene material, carry out isomerization reaction with liquid phase by beds then, make the 2-methyl-1-butene alkene in the coarse isoamylene be converted into the 2-methyl-2-butene, the add-on of tertiary amyl alcohol is benchmark with the coarse isoamylene, be 0.1～2.0wt%, mass space velocity is 1～35hr
-1, temperature of reaction is 18～45 ℃, and reaction pressure is 0.3～1.0MPa, and catalyzer is the sulfonic group Zeo-karb, and its mass exchange capacity is 3～5.5mmol/g.
2, the method by preparing isoamylene from methyl tert-amyl ether according to claim 1, it is characterized in that the product that the described isomerization reaction of step 3) obtains further carries out rectifying, rectifying Tata still temperature is 115～125 ℃, tower top temperature is 59～68 ℃, rectifying pressure is 0.1～0.5MPa, reflux ratio is 1～3, the smart isopentene of side line output, and cat head, tower still are discharged light constituent and heavy constituent impurity respectively.
3, the method by preparing isoamylene from methyl tert-amyl ether according to claim 1 is characterized in that it is solid acid that the described ether of step 1) is separated catalyst for reaction, takes from by H
2SO
4, HF or HCl modification α-Al
2O
3, or the silicon-dioxide of the oxide compound of load tungsten.
4,, it is characterized in that the described temperature of reaction of step 1) is 180～230 ℃ according to claim 1 or 3 described methods by preparing isoamylene from methyl tert-amyl ether.
5, the method by preparing isoamylene from methyl tert-amyl ether according to claim 1 is characterized in that step 2) described ether separates reaction product and adopts water elution to remove methyl alcohol.
6, the method by preparing isoamylene from methyl tert-amyl ether according to claim 1 is characterized in that the add-on of the described tertiary amyl alcohol of step 3) is benchmark with the coarse isoamylene, is 0.2～1.5wt%.
7, the method by preparing isoamylene from methyl tert-amyl ether according to claim 1, the mass exchange capacity that it is characterized in that the described sulfonic group Zeo-karb of step 3) is 4～5.5mmol/g.
8, the method by preparing isoamylene from methyl tert-amyl ether according to claim 1 is characterized in that the described mass space velocity of step 3) is 5～20hr
-1
9, the method by preparing isoamylene from methyl tert-amyl ether according to claim 1 is characterized in that the described temperature of reaction of step 3) is 25～35 ℃.
10, the method by preparing isoamylene from methyl tert-amyl ether according to claim 1 is characterized in that the described reaction pressure of step 3) is 0.4～0.8MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100386317A CN101597200A (en) | 2008-06-05 | 2008-06-05 | Method by preparing isoamylene from methyl tert-amyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100386317A CN101597200A (en) | 2008-06-05 | 2008-06-05 | Method by preparing isoamylene from methyl tert-amyl ether |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101597200A true CN101597200A (en) | 2009-12-09 |
Family
ID=41418824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008100386317A Pending CN101597200A (en) | 2008-06-05 | 2008-06-05 | Method by preparing isoamylene from methyl tert-amyl ether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101597200A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1371894A (en) * | 2001-02-23 | 2002-10-02 | 中国石化上海石油化工股份有限公司 | Process for preparing isopentene containing high content of 2-methyl-2-butene from methyl tertiary amyl ether |
-
2008
- 2008-06-05 CN CNA2008100386317A patent/CN101597200A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1371894A (en) * | 2001-02-23 | 2002-10-02 | 中国石化上海石油化工股份有限公司 | Process for preparing isopentene containing high content of 2-methyl-2-butene from methyl tertiary amyl ether |
Non-Patent Citations (1)
| Title |
|---|
| 徐泽辉等: "叔丁醇对异丁烯二聚反应选择性的影响", 《化学反应工程与工艺》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101555197B (en) | Comprehensive use method of mixed C-4 | |
| CN101092323B (en) | Method for preparing olefin in lightweight by catalytic cracking olefin of containing carbon | |
| CN101279879A (en) | Method for producing propone by comprehensive utilization of mixed C4 | |
| CN102701969A (en) | Etherified C4 superimposition esterification cogeneration method of isooctane and sec-butyl acetate | |
| CN103342624B (en) | Preparation method of high purity cyclopentene | |
| CN108774100B (en) | Combined method for preparing methyl tert-butyl ether and isobutene from tert-butyl alcohol and methanol | |
| CN107721791B (en) | Preparation system and preparation method for preparing propylene from methanol | |
| CN102040452A (en) | Method for preparing isoamylene by using tertiary amyl methyl ether | |
| CN101723777B (en) | Method for preparing isoamylene by taking tertiary amyl methyl ether as raw material | |
| CN102070390B (en) | The method of refinery's mixed c 4 propylene | |
| CN101597197A (en) | A kind of method by preparing isoamylene from methyl tert-amyl ether | |
| CN101671221B (en) | Preparation method of polymer solvent iso-butane | |
| CN101723787B (en) | Method for increasing content of 2-methyl-2-butene in isoamylene | |
| CN104250204B (en) | A kind of complex etherified technique | |
| CN102603452A (en) | Method for preparing isoalkenes through isomerizing linear alkenes | |
| CN101723776B (en) | Method for preparing isoamylene | |
| CN106588550B (en) | Method for increasing content of 2-methyl-2-butene | |
| CN202465559U (en) | Combined device for producing methyl tertiary butyl ether (MTBE) by utilizing mixed carbon 4 (C4) | |
| CN101597200A (en) | Method by preparing isoamylene from methyl tert-amyl ether | |
| CN101597202A (en) | Method with preparing isoamylene from methyl tert-amyl ether | |
| CN104529730A (en) | Method for preparing 3-pentanone by using 2-pentene | |
| CN101597198B (en) | Method for improving content of 2-methyl-2-butylene in coarse isoamylene | |
| CN101597203B (en) | Method for improving content of 2-methyl-2-butylene in coarse isoamylene | |
| CN101597201B (en) | Method for isomerizing 2-methyl-1-butylene into 2-methyl-2-butylene | |
| CN102040450A (en) | Method for isomerizing isopentene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20091209 |