CN109651104A - The preparation method of tert amyl methyl ether(TAME) - Google Patents
The preparation method of tert amyl methyl ether(TAME) Download PDFInfo
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- CN109651104A CN109651104A CN201710936959.XA CN201710936959A CN109651104A CN 109651104 A CN109651104 A CN 109651104A CN 201710936959 A CN201710936959 A CN 201710936959A CN 109651104 A CN109651104 A CN 109651104A
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- methyl ether
- amyl methyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/177—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by selective oligomerisation or polymerisation of at least one compound of the mixture
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The present invention provides a kind of methods for preparing tert amyl methyl ether(TAME), are related to tert amyl methyl ether(TAME) preparation technical field.The present invention carries out polymerization reaction by catalyst bed with liquid phase according to diolefin and the active difference of monoolefm polymerisations, by coarse isoamylene, makes the diolefin polymerization in coarse isoamylene, and the catalyst is weak-base anion-exchange resin, and mass space velocity is 1~20hr‑1, reaction temperature is 20~60 DEG C, and reaction pressure is 0.3~2.0MPa, to reduce the content for being etherified diolefin in preceding coarse isoamylene raw material, has then obtained the tert amyl methyl ether(TAME) of 98% or more purity by etherificate and rectifying.Through the invention, existing processing step is simplified, defect of the existing technology is effectively overcomed.
Description
Technical field
The present invention relates to tert amyl methyl ether(TAME) preparation technical fields.
Background technique
Tert amyl methyl ether(TAME) (TAME) is the excellent additive for improving octane number, and is also the weight of reformulated gasoline
Component part is wanted, the environmental-protection function of TAME is maximum, and volatile C5 alkene certain in gasoline can be converted to vapour pressure very by it
Ether low and that burning is clean, principal synthetic route are using the C 5 fraction and methanol progress ether in catalytic cracking and drippolene
Change reaction.It is usually reacted by C5 fraction with methanol and generates tert amyl methyl ether(TAME), be then refining to obtain high-purity methyl uncle penta
Base ether.
In etherification reaction, since the diolefin contained in coarse isoamylene easily leads to the inactivation of catalyst for etherification, existing skill
Art such as Chinese patent CN201210363942.7 etc. generallys use plus the method for hydrogen, diene content in raw material is reduced, to mention
The cycle of operation of high catalyst for etherification.But the alkaline matter that contains of coarse isoamylene and Determination of Trace Sulfur easily cause selection plus hydrogen to be urged
The inactivation of agent, therefore add and the techniques such as wash it is usually necessary to use desulfurizing agent and Purified Water before hydrogen raw material is pre-processed, with
Reduce sulfur content and removing alkaline matter in raw material.
In the prior art, selection hydrogenation process not only increases equipment investment, consumes selective hydrogenation catalyst and hydrogen,
And it inevitably increased the loss of coarse isoamylene, while washing repeatedly produces waste water in large quantities, increases at the three wastes
Reason expense.
Summary of the invention
It is an object of the invention to: overcome the deficiencies of the prior art and provide a kind of method for preparing tert amyl methyl ether(TAME).
Present invention solves the technical problem that be the process conditions for how selecting suitable catalyst and control suitable, it will be in coarse isoamylene
Micro diolefin direct polymerization meets etherification procedure to original to reduce the content for being etherified diolefin in preceding coarse isoamylene raw material
The limitation requirement of material.
The following are the specific technical solutions of the present invention:
A method of tert amyl methyl ether(TAME) is prepared, the following steps are included:
1) coarse isoamylene carries out polymerization reaction by catalyst bed with liquid phase, make isoprene in coarse isoamylene,
The diolefin polymerizations such as pentadiene;The catalyst is weak-base anion-exchange resin, and mass space velocity is 1~20hr-1, reaction temperature
Degree is 20~60 DEG C, and reaction pressure is 0.3~2.0MPa;
2) reaction product iso-amylene and methanol are obtained in macropore styryl anion-exchange resin catalyst by step 1)
Upper carry out etherification reaction generates tert amyl methyl ether(TAME) (TAME);The mass exchange capacity of sulfonic group cation exchange resin is 3.0
~6.0mmol/g, mass space velocity are preferably 3~15hr-1, reaction temperature is preferably 30~70 DEG C, and reaction pressure is preferably 0.3~
1.2MPa;
3) using tert amyl methyl ether(TAME) and other impurities boiling point difference, by rectifying by tert amyl methyl ether(TAME) (TAME)
It is separated with other substances;Tower bottom of rectifying tower temperature is 100~160 DEG C, and tower top temperature is 40~90 DEG C, and reflux ratio is 3~7, tower
Kettle obtains the tert amyl methyl ether(TAME) (TAME) that purity is 98% or more.
Abovementioned steps 1) catalyst, preferably macropore sulfonic group cation exchange resin.
Abovementioned steps 2) described in amount air speed be preferably 4~8hr-1, reaction temperature is preferably 50~70 DEG C, and reaction pressure is excellent
It is selected as 0.5~1.0MPa.
Abovementioned steps 3) bottom temperature is preferably 120~140 DEG C, and tower top temperature is preferably 50~75 DEG C, reflux ratio
Preferably 4~6.
The present invention has obtained the tert amyl methyl ether(TAME) of high-purity by micro diolefin polymerization, etherificate, rectifying, and key is
Before coarse isoamylene is reacted with methanol etherification, the process conditions for selecting suitable catalyst and control suitable will be in coarse isoamylene
Micro diolefin direct polymerization, reduce coarse isoamylene raw material in diolefin content.
Inventor is found through experiments that, according to diolefin and the active difference of monoolefm polymerisations, the weak of bulky grain can be selected
Alkalescence anion-exchange resin controls suitable process conditions, by the micro diolefin direct polymerization in coarse isoamylene, to meet
Limitation requirement of the etherification procedure to raw material.
The present invention is due to using the technology described above, compared with prior art, other without introducing into reaction system
Substance does not increase additional burden to the purifying of product or purification, and only by the control to polymerization reaction, make etherification reaction
The content of preceding diolefin can be down to 0.3% hereinafter, simplify existing processing step, effectively overcome of the existing technology
Defect.
Detailed description of the invention
Fig. 1 is the method and process flow chart provided in an embodiment of the present invention for preparing tert amyl methyl ether(TAME).
Description of symbols:
Polymer reactor 100, methyltertiarvbutyl ether reactor 200, first rectifying column 300.
Specific embodiment
The method provided by the invention for preparing tert amyl methyl ether(TAME) is made below in conjunction with the drawings and specific embodiments further
It is described in detail.It should be noted that the combination of technical characteristic described in following embodiments or technical characteristic should not be recognized
For be it is isolated, they can be combined with each other to reaching superior technique effect.
Technology, method and apparatus known to person of ordinary skill in the relevant may be not discussed in detail, but suitable
In the case of, the technology, method and apparatus should be considered as authorizing part of specification.Institute that is shown here and discussing
Have in example, any occurrence should be construed as merely illustratively, not as limitation.Therefore, exemplary embodiment
Other examples can have different values.
Embodiment
The process flow of embodiment is shown in Figure 1, has obtained height by following technical process using coarse isoamylene as raw material
The methyl tert-amyl ether product of purity:
Step 1), coarse isoamylene in iso-amylene head tank is with liquid phase by being provided with the polymer reactor of catalyst bed
100, polymerization reaction is carried out in polymer reactor 100, keeps the diolefins such as isoprene, the pentadiene in coarse isoamylene poly-
It closes, the catalyst is macropore styryl anion exchange resin.
Mass space velocity in polymer reactor is 1~20hr-1, corresponding reaction temperature is 20~60 DEG C, corresponding reaction
Pressure is 0.3~2.0MPa.
By the aforementioned control to diolefin polymerization reaction condition, the content of diolefin before etherification reaction can be made to be down to
0.3% or less.
Step 2) obtains reaction product material W1 by step 1), and the iso-amylene and methanol in material W1 are being provided with macropore
Etherification reaction occurs in the methyltertiarvbutyl ether reactor 200 of sulfonic group cation exchange resin catalyst, generates product material W2, material W2
Main component be tert amyl methyl ether(TAME) (TAME).
The mass exchange capacity of macropore styryl anion exchange resin can be 3.0~6.0mmol/g, preferably 4
~5.5mmol/g;Mass space velocity can be 3~15hr-1, preferably 5~10hr-1;Reaction temperature can be 30~70 DEG C, excellent
It is selected as 40~50 DEG C;Reaction pressure can be 0.3~1.2MPa, preferably 0.5~1.0MPa.
Step 3), for the material W2 that step 2) obtains, using the difference of tert amyl methyl ether(TAME) and the boiling point of other impurities,
By material W2 by first rectifying column 300, tert amyl methyl ether(TAME) (TAME) and other substances are separated by rectifying.Tower reactor obtains
Material W3, material W3 are the tert amyl methyl ether(TAME) (TAME) of 98% or more purity.
The bottom temperature of first rectifying column 300 can be 100~160 DEG C, preferably 120~140 DEG C;Tower top temperature can be with
It is 40~90 DEG C, preferably 50~75 DEG C;Reflux ratio can be 3~7, preferably 4~6.
The methyl of high-purity has been obtained by micro diolefin polymerization, etherificate and rectification step by above-mentioned process flow
Tert-amyl ether product.
Claims (6)
1. a kind of preparation method of tert amyl methyl ether(TAME), it is characterised in that the following steps are included:
1) coarse isoamylene carries out polymerization reaction by catalyst bed with liquid phase, makes the diolefin polymerization in coarse isoamylene;It is described
Catalyst is weak-base anion-exchange resin, and mass space velocity is 1~20hr-1, reaction temperature is 20~60 DEG C, and reaction pressure is
0.3~2.0MPa;
2) reaction product iso-amylene and methanol is obtained on macropore sulfonic group cation exchange resin catalyst by step 1) to carry out
Etherification reaction generates tert amyl methyl ether(TAME);
3) using tert amyl methyl ether(TAME) and other impurities boiling point difference, by rectifying by tert amyl methyl ether(TAME) and other impurities
Separation, tower reactor obtain the tert amyl methyl ether(TAME) that purity is 98% or more.
2. according to the method described in claim 1, it is characterized by: the catalyst is macropore styryl anion exchange tree
Rouge.
3. according to the method described in claim 1, it is characterized by: abovementioned steps 2) in, sulfonic group cation exchange resin
Mass exchange capacity is 3.0~6.0mmol/g, and mass space velocity is 3~15hr-1, reaction temperature is 30~70 DEG C, and reaction pressure is
0.3~1.2MPa.
4. according to the method described in claim 3, it is characterized by: the mass space velocity is 5~10hr-1;Reaction temperature is
40~50 DEG C;Reaction pressure is 0.5~1.0MPa.
5. according to the method described in claim 1, it is characterized by: abovementioned steps 3) in, the bottom temperature of rectifying column is 100~
160 DEG C, tower top temperature is 40~90 DEG C, and reflux ratio is 3~7.
6. according to the method described in claim 5, tower top temperature is it is characterized by: the bottom temperature is 120~140 DEG C
50~75 DEG C, reflux ratio is 4~6.
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2398930A (en) * | 1943-01-23 | 1946-04-23 | Filtrol Corp | Process for separating monomeric diolefins from mixtures of relatively low boiling diolefin and mono-olefin monomers |
CN103664458A (en) * | 2012-09-25 | 2014-03-26 | 中国石油化工股份有限公司 | Selective hydrogenation method of crude isopentene |
-
2017
- 2017-10-10 CN CN201710936959.XA patent/CN109651104A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2398930A (en) * | 1943-01-23 | 1946-04-23 | Filtrol Corp | Process for separating monomeric diolefins from mixtures of relatively low boiling diolefin and mono-olefin monomers |
CN103664458A (en) * | 2012-09-25 | 2014-03-26 | 中国石油化工股份有限公司 | Selective hydrogenation method of crude isopentene |
Non-Patent Citations (2)
Title |
---|
徐泽辉: "《中国博士学位论文全文数据库 工程科技Ⅰ辑》", 15 September 2010 * |
杨忠保等: "异戊烯的生产", 《石油化工》 * |
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Application publication date: 20190419 |