CN101597203B - Method for improving content of 2-methyl-2-butylene in coarse isoamylene - Google Patents
Method for improving content of 2-methyl-2-butylene in coarse isoamylene Download PDFInfo
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- CN101597203B CN101597203B CN200810038636A CN200810038636A CN101597203B CN 101597203 B CN101597203 B CN 101597203B CN 200810038636 A CN200810038636 A CN 200810038636A CN 200810038636 A CN200810038636 A CN 200810038636A CN 101597203 B CN101597203 B CN 101597203B
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Abstract
The invention relates to a method for improving the content of 2-methyl-2-butylene in coarse isoamylene, which comprises the following steps: a mixture of tert butyl alcohol and tertiary amyl alcohol is added to the coarse isoamylene; and then the mixture is subjected to an isomerization reaction through a fixed bed catalyst bed layer consisting of sulfonic acid group cation exchange resin so as to ensure that 2-methyl-1-butylene in the coarse isoamylene is converted into the 2-methyl-2-butylene, wherein the addition of the mixture of the tert butyl alcohol and the tertiary amyl alcohol takes the coarse isoamylene as a reference and is 0.1-1.8 percent by weight; the mass ratio of the tert butyl alcohol to the tertiary amyl alcohol is (0.5-1.8)/1; the mass exchange capacity of the sulfonicacid group cation exchange resin is 3-5.5 mmol/g, and the mass space velocity is 1-35 hr<-1>; the reaction temperature is 18-45 DEG C; and the reaction pressure is 0.3-1.0 MPa. The method effectively restrains respective or mutual dipolymer reactions of the 2-methyl-2-butylene and the 2-methyl-1-butylene in the process of the isomerization reaction.
Description
Technical field
The present invention relates to a kind of method that improves 2-methyl-2-butene content in the coarse isoamylene; Be particularly related to coarse isoamylene is carried out isomerization reaction through the fixed bed catalyst bed that is made up of the sulfonic group Zeo-karb, improve the method for 2-methyl-2-butene content in the coarse isoamylene.
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 C 5 fraction or naphtha cracking system ethylene by-product of catalytically cracked gasoline.Because 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 at present is the TAME cracking process, i.e. C 5 fraction and methyl alcohol reaction generates 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.Introduced like Chinese patent ZL01105415.8 and ZL01105416.6; It carries out isomerization reaction with coarse isoamylene through 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 can dipolymer be removed through 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 that improves 2-methyl-2-butene content in the coarse isoamylene, it is converted into the 2-methyl-2-butene through isomerization reaction with the 2-methyl-1-butene alkene in the coarse isoamylene.Technical problem to be solved by this invention is to suppress in the isomerization reaction 2-methyl-2-butene effectively and dimerization reaction takes place 2-methyl-1-butene alkene separately or each other.
Below be the concrete technical scheme of the present invention:
A kind of method that improves 2-methyl-2-butene content in the coarse isoamylene; This method is included in the mixture that adds the trimethyl carbinol and tertiary amyl alcohol in the coarse isoamylene; Then it is carried out isomerization reaction through the fixed bed catalyst bed that is made up of the sulfonic group Zeo-karb, make the 2-methyl-1-butene alkene in the coarse isoamylene be converted into the 2-methyl-2-butene.The add-on of the trimethyl carbinol and tertiary amyl alcohol mixture is benchmark with the coarse isoamylene, is 0.1～1.8wt%, and the mass ratio of the trimethyl carbinol and tertiary amyl alcohol is the trimethyl carbinol/tertiary amyl alcohol=(0.5～1.8)/1.The mass exchange capacity of sulfonic group Zeo-karb is 3～5.5mmol/g, and mass space velocity is 1～35hr
-1, temperature of reaction is 18～45 ℃, reaction pressure is 0.3～1.0MPa.
The add-on of the above-mentioned trimethyl carbinol and tertiary amyl alcohol mixture is a benchmark with the coarse isoamylene, is preferably 0.2～1.0wt%; The mass exchange capacity of sulfonic group Zeo-karb is preferably 4～5.5mmol/g; Mass space velocity is preferably 5～20hr
-1Temperature of reaction is preferably 25～35 ℃; Reaction pressure is preferably 0.4～0.8MPa.
The present invention is not strict to the ingredient requirement of isomerization reaction; It can be highly purified isopentene; Promptly do not contain other impurity; Also can be to contain other carbon pentaene hydrocarbon or alkane, or contain the coarse isoamylene of compound such as TAME, usually can with the split product of TAME after water elution removes methyl alcohol directly as raw material.And 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 raw material, so turndown ratio 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 before the isomerizing raw material is through beds, to have added an amount of trimethyl carbinol and tertiary amyl alcohol mixture earlier, and the contriver finds that through experiment 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, behind the trimethyl carbinol and tertiary amyl alcohol mixture adding 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 isomerizing 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 trimethyl carbinol, tertiary amyl alcohol boiling point are higher, are easy to separate with isopentene, can not produce any detrimentally affect to the isopentene quality product, the purity of the isopentene after refining can reach more than 99%.
Compared with prior art; Advantage of the present invention is through the inhibition to dimerization 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 reaction bed temperature unusual fluctuations phenomenon that causes because of the dimerization reaction heat release basically, reaction has been under the stable status all the time carries out.
Come details of the present invention is done further to describe through embodiment below; Because distinguishing characteristics of the present invention mainly is in reaction system, to add the trimethyl carbinol and tertiary amyl alcohol mixture; Other part is then basic identical with prior art, so embodiment will pay attention to adding in the reaction system enumerating of the trimethyl carbinol and tertiary amyl alcohol mixture experimental data.In an embodiment, transformation efficiency, selectivity be respectively by computes, 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 TAME.
Embodiment
[embodiment 1～10]
One, isomerization reaction raw material
The raw material that embodiment 1～10 uses is coarse isoamylene, obtains TAME by the C5 fraction of naphtha steam cracking system ethylene by-product and methyl alcohol reaction, obtains after removing methyl alcohol through Pintsch process, water elution again.The component of coarse isoamylene is seen table 1.
Table 1.
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 drum 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 drum 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 the trimethyl carbinol and tertiary amyl alcohol mixture 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 is seen table 2.
[comparative example]
Do not add the trimethyl carbinol and tertiary amyl alcohol mixture except that in the reaction raw materials coarse isoamylene of isomerization reaction, all the other are with embodiment 1～10, and concrete reaction conditions is seen table 2.
The reaction product that embodiment and comparative example obtain adopts red, orange, green, blue, yellow (ROGBY) to carry out composition analysis, and calculates transformation efficiency and selectivity of product, and the result sees table 3.
Table 2.
| ? | Mass space velocity (hr -1) | Temperature of reaction (℃) | Reaction pressure (MPa) | The trimethyl carbinol/tertiary amyl alcohol (mass ratio) | The trimethyl carbinol+tertiary amyl alcohol add-on (wt%) |
| Embodiment 1 | 1.0 | 18 | 0.3 | 0.5 | 0.1 |
| Embodiment 2 | 5.0 | 25 | 0.4 | 1.0 | 0.2 |
| Embodiment 3 | 7.0 | 27 | 0.5 | 0.7 | 0.4 |
| Embodiment 4 | 8.5 | 29 | 0.6 | 0.8 | 0.5 |
| Embodiment 5 | 11.0 | 31 | 0.7 | 1.2 | 0.6 |
| Embodiment 6 | 13.0 | 33 | 1.0 | 1.4 | 0.8 |
| Embodiment 7 | 17.0 | 35 | 0.7 | 1.8 | 0.9 |
| Embodiment 8 | 20.0 | 40 | 0.8 | 1.0 | 1.0 |
| Embodiment 9 | 35.0 | 45 | 0.6 | 1.1 | 1.8 |
| Embodiment 10 | 8.0 | 30 | 0.5 | 1.3 | 0.7 |
| Comparative example | 8.0 | 30 | 0.5 | - | - |
Annotate: the trimethyl carbinol and tertiary amyl alcohol mixture add-on are 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 | 91.38 | 12.94 | 0.78 | 71.80 | 95.66 |
| Embodiment 2 | 91.53 | 13.22 | 0.77 | 72.35 | 95.75 |
| Embodiment 3 | 91.75 | 13.43 | 0.64 | 72.72 | 96.49 |
| Embodiment 4 | 91.80 | 13.51 | 0.62 | 72.86 | 96.60 |
| Embodiment 5 | 91.81 | 13.47 | 0.59 | 72.78 | 96.76 |
| Embodiment 6 | 91.87 | 13.50 | 0.55 | 72.82 | 96.98 |
| Embodiment 7 | 91.89 | 13.46 | 0.50 | 72.74 | 97.25 |
| Embodiment 8 | 91.60 | 12.80 | 0.46 | 71.42 | 97.43 |
| Embodiment 9 | 91.73 | 12.88 | 0.37 | 71.56 | 97.94 |
| Embodiment 10 | 91.89 | 13.41 | 0.48 | 72.64 | 97.36 |
| Comparative example | 83.44 | 7.32 | 4.38 | 54.48 | 67.89 |
Claims (6)
1. method that improves 2-methyl-2-butene content in the coarse isoamylene; This method is included in the mixture that adds the trimethyl carbinol and tertiary amyl alcohol in the coarse isoamylene; Then it is carried out isomerization reaction through the fixed bed catalyst bed that is made up of the sulfonic group Zeo-karb, make the 2-methyl-1-butene alkene in the coarse isoamylene be converted into the 2-methyl-2-butene, the add-on of the trimethyl carbinol and tertiary amyl alcohol mixture is benchmark with the coarse isoamylene; Be 0.1～1.8wt%; The mass ratio of the trimethyl carbinol and tertiary amyl alcohol is the trimethyl carbinol/tertiary amyl alcohol=(0.5～1.8)/1, and the mass exchange capacity of sulfonic group Zeo-karb is 3～5.5mmol/g, and mass space velocity is 1～35hr
-1, temperature of reaction is 18～45 ℃, reaction pressure is 0.3～1.0MPa.
2. the method for 2-methyl-2-butene content in the raising coarse isoamylene according to claim 1 is characterized in that the add-on of the described trimethyl carbinol and tertiary amyl alcohol mixture is benchmark with the coarse isoamylene, is 0.2～1.0wt%.
3. the method for 2-methyl-2-butene content in the raising coarse isoamylene according to claim 1, the mass exchange capacity that it is characterized in that described sulfonic group Zeo-karb is 4～5.5mmol/g.
4. the method for 2-methyl-2-butene content in the raising coarse isoamylene according to claim 1 is characterized in that described mass space velocity is 5～20hr
-1
5. the method for 2-methyl-2-butene content in the raising coarse isoamylene according to claim 1 is characterized in that described temperature of reaction is 25～35 ℃.
6. the method for 2-methyl-2-butene content in the raising coarse isoamylene according to claim 1 is characterized in that described reaction pressure is 0.4～0.8MPa.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1989002882A1 (en) * | 1987-10-01 | 1989-04-06 | Exxon Chemical Patents, Inc. | Increasing the level of 2-methyl-2-butene in isoamylene |
| 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 |
| CN1371895A (en) * | 2001-02-23 | 2002-10-02 | 中国石化上海石油化工股份有限公司 | Method for raising 2-methyl-2-butene content in isopentene |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1989002882A1 (en) * | 1987-10-01 | 1989-04-06 | Exxon Chemical Patents, Inc. | Increasing the level of 2-methyl-2-butene in isoamylene |
| 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 |
| CN1371895A (en) * | 2001-02-23 | 2002-10-02 | 中国石化上海石油化工股份有限公司 | Method for raising 2-methyl-2-butene content in isopentene |
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