CN107537568A - A kind of method of modifying of cationic ion-exchange resin and the method for preparing tert amyl methyl ether(TAME) - Google Patents
A kind of method of modifying of cationic ion-exchange resin and the method for preparing tert amyl methyl ether(TAME) Download PDFInfo
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Abstract
The present invention discloses a kind of method of modifying of cationic ion-exchange resin and the preparation method of tert amyl methyl ether(TAME), sulfonic group cation exchange resin is soaked with toluene, methyl iso-butyl ketone (MIBK) successively, soaked stage by stage with distilled water again, the ratio surface of resin, aperture structure are improved, improve sulfonic group cation exchange resin catalyst stability and selectivity；As catalyst, using C5 alkene and methanol as raw material, tert amyl methyl ether(TAME) is prepared under 75 DEG C ~ 250 DEG C, 0.5MPa ~ 3.0Mpa, it is possible to achieve continuous production, have the advantages that high conversion rate, stability are good, be a green new technology.
Description
Technical field
It is the present invention relates to a kind of method of modifying of cationic ion-exchange resin, and using the cationic ion-exchange resin of modification
The method of catalyst preparation tert amyl methyl ether(TAME).
Background technology
With the development of human society, countries in the world are to environmental protection pay attention to day by day, in order to reduce the pollution of vehicle exhaust,
Unleaded, oxygen-containing, high-knock rating gasoline demand is surged, particularly nineteen ninety, the U.S. promulgates Clean Air Act Amendment (CAA)
Since, various countries' oil plant greatly develops reformulated gasoline to adapt to the requirement of environmental protection.
(oxidizing process octane number RON is 105 to tert amyl methyl ether(TAME) (TAME), 100) engine octane number MON is is after methyl
Another production is unleaded, oxygen-containing and high-octane rating reformulated gasoline after tertbutyl ether (MTBE) (RON 117, MON 102)
Preferable oxygenatedchemicals.Though TAME octane number slightly below MTBE, it is better than in vapour pressure, water in the index such as solubility
MTBE, and production TAME can also reduce C_5 olefins high with atmospheric photochemistry activity in gasoline.Therefore, as market is to ether
Class oxygenatedchemicals demand is continuously increased, and the research and development of TAME production technologies are at home and abroad increasingly by the weight of people
Depending on.
TAME be by 2- methyl butenes and methanol production, have MTBE all advantages, even more like in gasoline.
In all ether, TAME acts on maximum in terms of environmental protection, and it can reduce pollution emission, and will be some most volatile in gasoline
The high C5 alkene of reactivity change into the graceful vapour pressure of thunder（RVP）The clean ether of low-down burning.Because addition TAME can
The RVP of gasoline is reduced, this just makes oil plant have greater flexibility in terms of the control regulation for meeting RVP from now on, calls in gasoline
In amount can with it is some more without influence specification gasoline.
Mainly contain monoolefine and diene hydrocarbons in C5, by separator, may separate out the high C of added value5Diene
Hydrocarbon, the C5 after raffinate contains 2-methyl-1-butene alkene in monoolefine and 2- methyl-2-butenes can be as TAME raw material.So
Both a large amount of components needed for gasoline mediation can have been solved, can also improve C5 utilization rate and surcharge comprehensively.
TAME production processes and technique and MTBE are substantially similar, generally using 2- methyl butenes and methanol as raw material, in strong acid
Liquid phase synthesis in the presence of property resin cation, General reactions temperature 60 C ~ 70 DEG C, pressure 0.2MPa, air speed 1.0h-1~2.0h-1,
Alcohol/alkene mol ratio 1.0 ~ 1.5.
Cationic ion-exchange resin is industrially widely used catalyst for etherification at present, and principal item is macropore sulfonic acid type
Cationic ion-exchange resin.It is external to use Amberlyst-15 (A-15), Amberlyst-35 (A-35), Lewatit mostly
K2631, Bayer K2631 types etc..D-72, S-54, D005, QRE type resin that is domestic then mainly voluntarily being researched and developed using China is urged
Agent etc., these resins are all the poly styrene polymers of divinylbenzene crosslink.
United States Patent (USP) US4808270A discloses a kind of preparation method of tert amyl methyl ether(TAME), and with methanol, C5 alkene is original
Material, uses polystyrene resin, sulfonated phenol formaldehyde resin etc. as catalyst, in 40 DEG C ~ 120 DEG C of reaction temperature, reaction pressure 0.12 ~
The conversion ratio of 2.0MPa, 2- methyl butene is 65%, the selectivity 93.6% of tert amyl methyl ether(TAME).
United States Patent (USP) US5453550A discloses a kind of preparation method of tert amyl methyl ether(TAME), with methanol and isobutene and 2-
Methyl butene hydrocarbon mixture is raw material, and ion exchange resin is catalyst, in alkene air speed 0.6h-1, 62 DEG C of reaction temperature, reaction pressure
Power 2.2MPa, under conditions of methanol/2- methyl butenes mol ratio 1.0 ~ 2.0, the yield 54% ~ 60% of tert amyl methyl ether(TAME).
United States Patent (USP) US4988366A discloses a kind of preparation method of tert amyl methyl ether(TAME), with methanol, isobutene, 2- first
Base butylene is raw material, acid zeolite, acidic resins（Such as Amberlyst 15）, ZSM-5, β zeolite etc. be catalyst, in reaction temperature
Tert amyl methyl ether(TAME) has been synthesized under conditions of 50 DEG C ~ 70 DEG C of degree.
European patent EP 0026041A1 discloses a kind of preparation method of tert amyl methyl ether(TAME), with methanol 2- methyl butenes
For raw material, zeolite catalyst.In 232 DEG C ~ 288 DEG C, reaction pressure 0.1MPa of temperature, olefin partial pressures<0.05MPa, alkene air speed
0.2h-1~5h-1Tert amyl methyl ether(TAME) is synthesized.
Chinese patent CN103787843A discloses a kind of preparation method of tert amyl methyl ether(TAME), including following content：With
2- methyl butenes and methanol are raw material, and using heteropoly acid/Ti-base composite oxide as catalyst, the volume space velocity of 2- methyl butenes is
0.5h-1~5.0h-1, the mol ratio of methanol and 2- methyl butenes is 1.0：1.0~5.0：1.0, reaction temperature is 80 DEG C ~ 200 DEG C,
Reaction pressure is 0.5MPa ~ 5.0MPa.
Chinese patent CN102557887A discloses a kind of C5The method that raffinate etherificate prepares tert amyl methyl ether(TAME)；Catalysis
Agent is made up of major catalyst, auxiliary agent and acid carrier, major catalyst Ru, Rh, Co, Mo, Ni metal or it is corresponding solvable
Property salt one or more, based on catalyst weight 100% its content be 0.1 ~ 10%；Auxiliary agent is the 3 in the periodic table of elements
Or 4 one or more in major element, its content is 0.05 ~ 1% based on catalyst weight 100%；Carrier is macroporous network
Type polystyrene acid cation exchange resin；Carrier is handled by alcoholic solution, and major catalyst maceration extract is acid solution, H+It is dense
Spend for 0.1 ~ 2.0mol/L.
Chinese patent CN102408316A disclose it is a kind of using 1- methyl -3- butylimidazolium borofluoride ion liquid as
Catalyst, after methanol, the light dydrocarbon raffinate containing iso-amylene and catalyst are well mixed, evenly by equipped with the anti-of filler
The conversion zone of rectifying column is answered, for conversion zone temperature control at 70 ~ 100 DEG C, efflux is cooled to room temperature；Isoamyl obtained by this method
Up to more than 70%, the catalyst of use is easily isolated the conversion per pass of alkene, reusable, is to prepare tert amyl methyl ether(TAME)
A new way.
Chinese patent CN103787842A discloses a kind of preparation method of tert amyl methyl ether(TAME), including following content：With 2-
Methyl butene and methanol are raw material, use heteropoly acid/aluminum-base composite metal oxide as catalyst, and the volume of 2- methyl butenes is empty
Speed is 1.0h-1~5.0h-1, the mol ratio of methanol and 2- methyl butenes is 1.0：1.0~3.0：1.0, reaction temperature is 60 DEG C ~ 120
DEG C, reaction pressure is 0.05MPa ~ 3.0MPa.
《Petrochemical industry》The first phase of volume 32 in 2003, the mixing light dydrocarbon raw material of use are cut by FCC gasoline and DCC gasoline
And obtain, and light dydrocarbon after selecting hydrogenation and removing alkadienes and methanol are raw material, are voluntarily ground with Qilu Petroleum Chemistry Co. Inst.
The QRE type macropore sulfonic acid ion exchange resin catalyst of system is catalyst.Using the combination of pre-reactor and catalytic distillation tower
Etherification technology, synthesis TAME process condition experiments are carried out, achieved suitable etherification technology parameter, tertiary amylene conversion ratio is reachable
More than 95%, TAME purity are not less than 97%.
《Fine-chemical intermediate》The 4th phase of volume 34 in 2004, with raffinate carbon 5 (2- methyl butenes content be more than 20%) and
Methanol is raw material, and benzene sulfonic acid type resin is catalyst, reaction temperature be 62 DEG C ~ 67 DEG C, mole of methanol and 2- methyl butenes
Ratio is 1.4 ~ 1.6, liquid hourly space velocity (LHSV) 1.3h-1~1.5h-1Reaction condition under, the conversion ratios of 2- methyl butenes is more than 70%.
《Jilin Institute of Chemical Technology journal》The 24th phase of volume 18 in 2001, with light FCC gasoline through distillation cut boiling range≤
The 2- methyl butenes and methanol of 60 DEG C of cut methyl butenes containing 2- more than 20% are raw material, and large aperture strong acid is produced with Nankai university student
Property cationic ion-exchange resin is catalyst, using catalytic reaction distillation technology in 70 DEG C ~ 76 DEG C of reaction temperature, pressure 0.08MPa ~
1.0MPa, air speed 2h-1Under conditions of, the conversion ratios of 2- methyl butenes reaches as high as 39.15%, TAME purity up to 83.44%,
Rectifying purity can bring up to more than 95% again.
《Journal of Liaoning Institute of Technology》The 6th phase of volume 20 in 2000, with refinery gas's fractionating device from liquefied petroleum gas
The C 5 fraction isolated, wherein containing 2-methyl-1-butene alkene (1.5%, mole fraction, similarly hereinafter) and 2- methyl-2-butenes (23%),
The two is collectively referred to as 2- methyl butenes, is etherified with industrial methanol under the catalysis of D005 types acid cation exchange resin, is prepared into methyl
Tert-amyl ether, it is 0.6~0.7 in methanol and 2- methyl butenes mol ratio, reaction temperature is 70 DEG C ~ 80 DEG C, and Feed space velocities are
3.0h-1~4.0h-1, under the conditions of operating pressure is 0.8MPa, the total conversion of 2- methyl butenes is 50% ~ 60%.
《Liaoning chemical industry》The 5th phase of volume 26 in 1997, C5 raw materials are catalytic cracking stable gasoline<50 DEG C of cuts, wherein 2-
Methyl butene -1 and the content of 2- methyl butenes -2 are respectively 8.7% and 14.0%.Methanol is industrial methanol, content >=99%, moisture ≯
0.7%, catalyst is acid cation exchange resin, using cartridge type expanded bed reactor.The reactor takes heat using circulation
Mode, i.e., reactor head material is extracted out, through outside cool down after return again to reactor bottom, reach the mesh for taking heat away
's.The operation of logistics up flow type can prevent catalyst granules from luming, while can reduce bed resistance, easy to operate and flexible, reachable
To higher conversion ratio.
《Petrochemical industry》The 2nd phase of volume 27 in 1998, using raffinate C5 be raw material through process with methanol etherification TAME, adopt
In the presence of domestic catalyst D54 type large hole cation exchanger resins, in 60 DEG C of reaction temperature, LHSV 2.4h-1, methanol/2- first
Under conditions of the amount of base butylene material is than 1.00, reaction pressure 0.2MPa, the 2- methyl butenes in raffinate C5 can react with methanol
Generate ether, the conversion ratios of 2- methyl butenes up to 63.26%, TAME selectivity up to 99.61%.
《Chemical research and application》The 1st phase of volume 11 in 1999, it is raw material in reaction distillation using 2- methyl butenes and methanol
Using benzene sulfonic acid cationic ion-exchange resin as catalyst in post, the conversion ratio in 40 DEG C~80 DEG C etherificates has been investigated with reaction condition
Change.In 69 DEG C, n (2- methyl butenes)/n (methanol)=1/1.2, the conversion ratio of 2- methyl butene etherification reactions reaches as high as
80%, reaction pressure influences little on the conversion ratio of 2- methyl butene etherification reactions.
In summary, it is active high the advantages of strong acid cation exchange resin catalyst, is easily separated with product, to equipment
Corrosivity is smaller, and selectivity is higher etc..Weak point is then mainly reflected in：1. resin catalyst less stable, raise temperature
When (being more than 373.15K), sulfonic acid group is easy to fall off, causes catalyst inactivation, etching apparatus and polluted product；2. with temperature
Rise, resin catalyst are selectively deteriorated, and oligomerisation side reaction increase, accessory substance increases；3. industrially converted to improve alkene
Rate, suppress side reaction, higher alfin ratio is often used, so as to result in the need for higher energy consumption to realize the recycling of alcohol.
Therefore, it is necessary to which the resin that a kind of high temperature stability performance is more preferable, activity is higher is urged in the preparation of tert amyl methyl ether(TAME)
Agent, the conversion ratio of raw material is improved, reduce accessory substance, improve selectivity.
The content of the invention
During to solve in the prior art using cationic ion-exchange resin as catalyst preparation tert amyl methyl ether(TAME), reaction temperature be present
When degree is higher, sulfonic acid group is easy to fall off, and side reaction increase, and the ratio surface of existing catalyst and pore structure have to this synthetic reaction
Certain negative effect, the present invention intend providing a kind of method of modifying of cationic ion-exchange resin, not only improve the surface of catalyst
Pore structure, and sulfonic acid group can be consolidated, make its difficult for drop-off, when being applied to tert amyl methyl ether(TAME) preparation as catalyst, have
Good catalytic activity, conversion ratio and selectivity are improved.
The technical purpose of the present invention is achieved through the following technical solutions：
First, one of technical purpose of the invention is to provide a kind of method of modifying of cationic ion-exchange resin, comprises the following steps：
The first step, sulfonic group cation exchange resin toluene is soaked into 8h ~ 24h at a temperature of 50 DEG C ~ 130 DEG C；
Second step, the sulfonic group cation exchange resin of the first step is soaked at a temperature of 50 DEG C ~ 120 DEG C with methyl iso-butyl ketone (MIBK)
4h~24h；
3rd step, with the sulfonic group cation exchange resin of oxygen content≤10mg/L distilled water immersion second step, and lead to simultaneously
Enter inert gas or nitrogen, the immersion divides three phases to carry out：First stage treatment conditions are pressure 0.5MPa~1.0Mpa,
8h~12h is soaked at 65 DEG C ~ 80 DEG C of temperature, and is passed through inert gas；Second stage treatment conditions be pressure 0.9MPa~
1.0Mpa, 12h~24h is soaked at 85 DEG C~100 DEG C of temperature；Phase III treatment conditions are pressure 1.0MPa~1.5Mpa, temperature
12h~24h is soaked at 120 DEG C~130 DEG C of degree；
4th step, wash, dry, obtain modified sulfonic group cation exchange resin.
Further, in the method for modifying of above-mentioned cationic ion-exchange resin, toluene or methyl in the first step and second step
The volume ratio of isobutyl ketone and sulfonic group cation exchange resin is 5 ~ 10：1；Preferably 5 ~ 8：1, most preferably 5 ~ 6:1.
Further, in the method for modifying of above-mentioned cationic ion-exchange resin, the soaking temperature in the first step is preferably 80
DEG C ~ 120 DEG C, soak time is preferably 10h ~ 16h.
Further, in the method for modifying of above-mentioned cationic ion-exchange resin, the soaking temperature in second step is preferably 60
DEG C ~ 80 DEG C, soak time is preferably 6h ~ 12h.
Further, in the method for modifying of above-mentioned cationic ion-exchange resin, the immersion process of first stage in the 3rd step
In to be passed through inert gas or the flow velocity of nitrogen be 20m3/ h~50m3/ h, be passed through in the immersion process of second stage inert gas or
The flow velocity of nitrogen is 10m3/ h~25m3/ h, it is 5m to be passed through inert gas or the flow velocity of nitrogen in the immersion process of phase III3/h
~10m3/h。
Further, in the method for modifying of above-mentioned cationic ion-exchange resin, the oxygen content of distilled water is with 25 in the 3rd step
DEG C, count under conditions of 100kPa, as preferable technical scheme, the oxygen content preferably≤5mg/L, most preferably≤3mg/L.
Further, in the method for modifying of above-mentioned cationic ion-exchange resin, the sulfonic group cation exchange resin can
Usual resins well-known to those skilled in the art are selected, can be made by oneself according to prior art or using commercial goods, commercial goods
The DNW type sulfonic group cation exchange resins of Dandong Mingzhu Special Type Resin Co., Ltd.'s production as used in the present invention.
Another technical purpose of the present invention is to provide a kind of preparation method of tert amyl methyl ether(TAME), and the preparation method is with C5
Alkene and methanol are raw material, using above-mentioned method of modifying be modified cationic ion-exchange resin as catalyst, in 75 DEG C ~ 250 DEG C,
Reaction prepares tert amyl methyl ether(TAME) under 0.5MPa ~ 3.0Mpa.
Further, in above-mentioned preparation method, the reaction temperature is preferably 80 DEG C ~ 160 DEG C, most preferably 100 DEG C ~
140 DEG C, pressure is preferably 1.0MPa ~ 2.0Mpa, most preferably 1.5MPa ~ 2.0MPa.
Further, in above-mentioned preparation method, the C5 alkene is 2-methyl-1-butene alkene and/or 2- methyl -2- fourths
Alkene.It will be apparent to a skilled person that 100% 2-methyl-1-butene alkene and/or 2- first can be used when selecting raw material
Base -2- butylene, mixing monoene hydrocarbon feed also may be selected, it is described to mix 2-methyl-1-butene alkene and/or 2- first in monoene hydrocarbon feed
The content of base -2- butylene is more than 15%, and preferred content is more than 20%, and more preferably content is more than 25%.
Further, in above-mentioned preparation method, the mol ratio of methanol and C5 alkene is 1:1~8:1, preferably 1:1~5:
1, most preferably 1.5:1~3:1；The volume space velocity of C5 alkene is 0.5h during charging-1~3.0h-1, preferably 1.0h-1~2.0h-1, most
Preferably 1.0h-1~1.5h-1。
The present invention is modified to cationic ion-exchange resin, is soaked with toluene, methyl iso-butyl ketone (MIBK) successively, and is entered with water
Row segmentation partial pressure immersion treatment, not only increases ratio surface, pore volume and the aperture of cation exchange resin catalyst, also improves
Sulfonic stability in catalyst, reduce the turnover rate of sulfonic acid group；It is used for C5 alkene and methanol as catalyst
Synthetically prepared tert amyl methyl ether(TAME), it is possible to achieve continuous production, have the advantages that high conversion rate, stability are good, be one green
Color environmental-protecting process.
Embodiment
Following non-limiting examples can make one of ordinary skill in the art be more fully understood the present invention, but not with
Any mode limits the present invention.
The sulfonic group cation exchange resin used in embodiments of the invention is Dandong Mingzhu Special Type Resin Co., Ltd.
DNW types, DZH types, the types of D005- II and the D005 type sulfonic group cation exchange resins of production, respectively numbering be L1, L2, L3 and
L4, specific nature are shown in Table 1.
Table 1
Embodiment 1 ~ 4 is the embodiment citing that p-sulfonic acid base cationic ion-exchange resin is modified.
Embodiment 1
The DNW type sulfonic group cation exchange resin toluene that commercially available Dandong Mingzhu Special Type Resin Co., Ltd. is produced is 40
Bubble 28h DEG C is invaded, bubble 40h is invaded after filtering at a temperature of 50 DEG C with methyl iso-butyl ketone (MIBK) again, through washing, dried for standby, first after filtering
Benzene or methyl iso-butyl ketone (MIBK) are 10 with the volume ratio of sulfonic group cation exchange resin：1.Take above-mentioned catalyst 500ml, be placed in for
In 3mg/L deoxygenated water, with 20m per hour3Flow velocity enters nitrogen, and bubble 16h is invaded at pressure 0.6MPa, 65 DEG C of temperature；Then will
Nitrogen flow rate is adjusted to 15m3/ h, pressure is upgraded to 1.0MPa, temperature, which is upgraded at 90 DEG C, invades bubble 18h；Nitrogen flow rate is adjusted to 5m again3/
H, pressure is upgraded to 1.5MPa, temperature, which is upgraded at 140 DEG C, invades bubble 24h, and processing carries out washing and dries the sulphur for being made modified after terminating
Acidic group cationic ion-exchange resin GL1.
Embodiment 2
DNW type sulfonic group cation exchange resins are simply changed into DZH type sulfonic group cations by other conditions with embodiment 1
Exchanger resin GL2.
Embodiment 3
DNW type sulfonic group cation exchange resins are simply changed into the type sulfonic groups of D005- II sun by other conditions with embodiment 1
Ion exchange resin GL3.
Embodiment 4
DNW type sulfonic group cation exchange resins are simply changed into D005 type sulfonic group cations by other conditions with embodiment 1
Exchanger resin GL4.
The pore structure of L1-L4, GL1-GL4 after before modified are determined with 2400 adsorption instruments, as a result such as the institute of table 2
Show.
In the glass tube that internal diameter is Φ 10mm, load 3mL catalyst samples and 6mL water, after tube sealing, be placed in autoclave
In, heatproof experiment is carried out at 200 DEG C.After certain time, according to HG2-885-76 standard test resin catalyst exchange capacities,
Sulfonic acid group turnover rate is calculated, as a result as shown in table 3.
Table 2
Table 3
Embodiment 5
L1-L4, GL1-GL4 resin catalyst after before modified is applied to prepare in tert amyl methyl ether(TAME) reaction, with 2- methyl
Butylene and methanol are raw material, and etherification reaction is carried out in Φ 18mm × 1200mm stainless steel fixed bed reactors, anti-
Answer and each catalyst 30mL, reactor head and bottom are respectively charged into device, be respectively charged into a diameter of Φ 0.5mm~1.2mm stone
Sand, after reactor installs, with nitrogen displacement three times, and air seal test is qualified, by 2- methyl butenes, methanol measuring pump
Preheater is sent into, reaction condition and reaction result are shown in Table 4.
Table 4
Claims (10)
1. a kind of method of modifying of cationic ion-exchange resin, comprises the following steps：
The first step, sulfonic group cation exchange resin toluene is soaked into 8h ~ 24h at a temperature of 50 DEG C ~ 130 DEG C；
Second step, the sulfonic group cation exchange resin of the first step is soaked at a temperature of 50 DEG C ~ 120 DEG C with methyl iso-butyl ketone (MIBK)
4h~24h；
3rd step, with the sulfonic group cation exchange resin of oxygen content≤10mg/L distilled water immersion second step, and lead to simultaneously
Enter inert gas or nitrogen, the immersion divides three phases to carry out：First stage treatment conditions are pressure 0.5MPa~1.0Mpa,
8h~12h is soaked at 65 DEG C ~ 80 DEG C of temperature, and is passed through inert gas；Second stage treatment conditions be pressure 0.9MPa~
1.0Mpa, 12h~24h is soaked at 85 DEG C~100 DEG C of temperature；Phase III treatment conditions are pressure 1.0MPa~1.5Mpa, temperature
12h~24h is soaked at 120 DEG C~130 DEG C of degree；
4th step, wash, dry, obtain modified sulfonic group cation exchange resin.
2. method of modifying according to claim 1, it is characterised in that toluene or methyl-isobutyl in the first step and second step
The volume ratio of ketone and sulfonic group cation exchange resin is 5 ~ 10：1；Preferably 5 ~ 8：1, most preferably 5 ~ 6:1.
3. method of modifying according to claim 1, it is characterised in that the soaking temperature in the first step is preferably 80 DEG C ~ 120
DEG C, soak time is preferably 10h ~ 16h.
4. method of modifying according to claim 1, it is characterised in that the soaking temperature in second step is preferably 60 DEG C ~ 80
DEG C, soak time is preferably 6h ~ 12h.
5. method of modifying according to claim 1, it is characterised in that be passed through in the 3rd step in the immersion process of first stage
The flow velocity of inert gas or nitrogen is 20m3/ h~50m3/ h, inert gas or nitrogen are passed through in the immersion process of second stage
Flow velocity is 10m3/ h~25m3/ h, it is 5m to be passed through inert gas or the flow velocity of nitrogen in the immersion process of phase III3/ h~
10m3/h。
6. the preparation method of tert amyl methyl ether(TAME), it is characterised in that using C5 alkene and methanol as raw material, with claim 1 ~ 5 times
The cationic ion-exchange resin that method described in meaning one is modified is catalyst, is reacted under 75 DEG C ~ 250 DEG C, 0.5MPa ~ 3.0Mpa
Prepare tert amyl methyl ether(TAME).
7. preparation method according to claim 6, it is characterised in that the reaction temperature is 80 DEG C ~ 160 DEG C, more preferably
For 100 DEG C ~ 140 DEG C.
8. preparation method according to claim 6, it is characterised in that the C5 alkene is 2-methyl-1-butene alkene and/or 2-
Methyl-2-butene.
9. preparation method according to claim 6, it is characterised in that the mol ratio of methanol and C5 alkene is 1:1~8:1, it is excellent
Elect 1 as:1~5:1, most preferably 1.5:1~3:1.
10. preparation method according to claim 6, it is characterised in that the volume space velocity of C5 alkene is 0.5h during charging-1~
3.0h-1, preferably 1.0h-1~2.0h-1, most preferably 1.0h-1~1.5h-1。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111377788A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Method for oligomerization of isobutene |
| CN113461495A (en) * | 2020-03-30 | 2021-10-01 | 中国石油化工股份有限公司 | Method for improving selectivity of ethylene glycol mono-tert-butyl ether and ethylene glycol mono-tert-butyl ether |
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| CN1356300A (en) * | 2000-12-06 | 2002-07-03 | 中国科学院大连化学物理研究所 | Process for preparing diisobutylene |
| CN1506444A (en) * | 2002-12-13 | 2004-06-23 | 中国石油天然气股份有限公司 | Catalytically cracking process of modifying gasoline |
| CN102408316A (en) * | 2010-09-21 | 2012-04-11 | 中国石油天然气股份有限公司 | Method for preparing tertiary amyl methyl ether |
| CN103304382A (en) * | 2012-03-13 | 2013-09-18 | 上海博润石化科技发展有限公司 | Combined process for comprehensively utilizing partial hydrogenation C5 fraction |
| CN103787843A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Method for preparing tert-amyl methyl ether |
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| CN111377788A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Method for oligomerization of isobutene |
| CN111377788B (en) * | 2018-12-28 | 2023-01-10 | 中国石油化工股份有限公司 | Method for oligomerization of isobutene |
| CN113461495A (en) * | 2020-03-30 | 2021-10-01 | 中国石油化工股份有限公司 | Method for improving selectivity of ethylene glycol mono-tert-butyl ether and ethylene glycol mono-tert-butyl ether |
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