CN107540524A - A kind of preparation method of tert amyl methyl ether(TAME) - Google Patents
A kind of preparation method of tert amyl methyl ether(TAME) Download PDFInfo
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- CN107540524A CN107540524A CN201610457377.9A CN201610457377A CN107540524A CN 107540524 A CN107540524 A CN 107540524A CN 201610457377 A CN201610457377 A CN 201610457377A CN 107540524 A CN107540524 A CN 107540524A
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Abstract
The present invention provides a kind of preparation method of tert amyl methyl ether(TAME), high temperature high pressure process is carried out by being placed in suitable for the strong-acid cation-exchange resin catalyst of catalysis C5 alkene and methanol etherification low-carbon alcohol solution, the ratio surface of resin, aperture structure are improved, improve sulfonic group cation exchange resin catalyst stability and selectivity;Using C5 alkene and methanol as raw material, tert amyl methyl ether(TAME) is prepared under 80 DEG C 200 DEG C, 0.1MPa 4.0Mpa, 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
The method that modified cationic ion-exchange resin is catalyst preparation tert amyl methyl ether(TAME) is utilized the present invention relates to a kind of.
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:
A kind of preparation method of tert amyl methyl ether(TAME), comprises the following steps:
1. removing the oxygen in low-carbon alcohols and deionized water in advance, strong-acid cation-exchange resin catalyst is placed in the water of low-carbon alcohols
In solution, it is put into closed container and is heated to handling 8 ~ 24h under 100 DEG C ~ 250 DEG C self-generated pressures;
The low-carbon alcohols are at least one of C1 ~ C4 alcohol;
2. the strong-acid cation-exchange resin catalyst for taking step to be 1. modified, it is placed in continuous fixed bed stainless steel reactor, will
C5 alkene and methanol, which are passed through in reactor, to carry out etherificate and prepares tert amyl methyl ether(TAME).
Further, the low-carbon alcohols be selected from methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, the tert-butyl alcohol, sec-butyl alcohol and
At least one of isobutanol, more preferably methanol and ethanol.
Further, the volumetric concentration of alcohol is 0.5% ~ 20%, preferably 1% ~ 10% in the aqueous solution of the low-carbon alcohols, low-carbon
The aqueous solution of alcohol and the mixed volume ratio of strong-acid cation-exchange resin are(5~15):1, be preferably(5-10):1.
During handling strong-acid cation-exchange resin, used solution has to pass through deoxygenation processing,
It additionally should ensure that and metal ion do not contained in treatment fluid, especially iron.
Further, the strong-acid cation-exchange resin, which refers to, can be catalyzed C5 alkene and methanol generation tert amyl methyl ether(TAME)
Resin catalyst, may be applicable to technical scheme, such as the type strong-acid cations of DNW- II prepared in the present invention
Exchange resin catalyst, it can also be obtained by buying.
Further, the temperature of step 1. middle heating is preferably 100 DEG C ~ 150 DEG C, and the time of heating is preferably
12~24h。
Further, step 1. the middle closed container used for the anti-of all kinds of inert material substrates suitable for hydro-thermal reaction
Device is answered, such as the container of enamel, glass, ceramics or tetrafluoroethene substrate.
Further, step 2. described in C5 alkene and during methanol etherification, the mol ratio of methanol and C5 alkene is 1 ~ 5.5:
The liquid quality air speed of 1, C5 alkene is 0.5h-1~5.0h-1, reaction temperature be 80 DEG C ~ 200 DEG C, reaction pressure be 0.1MPa ~
4.0MPa。
Further, in above-mentioned preparation method, the reaction temperature is preferably 100 DEG C ~ 160 DEG C, most preferably 120 DEG C
~ 140 DEG C, pressure is preferably 1.5MPa ~ 2.5Mpa, 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 1:1.0~5.5:1.0, be preferably
2:1~5:1, most preferably 2.5:1~3:1;The volume space velocity of C5 alkene is 0.5h during charging-1~5.0h-1, preferably 1.0h-1~
3.0h-1, most preferably 1.0h-1~1.5h-1。
Beneficial effects of the present invention:
The present invention is modified to cationic ion-exchange resin, is handled using low-carbon alcohols aqueous solution soaking, is not only increased sun
Ratio surface, pore volume and the aperture of ion-exchange resin catalyst, also improve sulfonic stability in catalyst, reduce sulphur
The turnover rate of acid groups;It is used for C5 alkene as catalyst and prepares tert amyl methyl ether(TAME) with methanol-fueled CLC, it is possible to achieve even
Continuous metaplasia production, has the advantages that high conversion rate, stability are good, is a green new technology.
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.
Embodiment 1 ~ 13 is the specific embodiment being modified to cationic ion-exchange resin.
Embodiment 1
(1)The preparation of the type strong-acid cation-exchange resins of DNW- II:
The preparation method of the type heatproof strong-acid cation-exchange resin catalysts of DNW- II is a lot, according to method system of the prior art
Standby resin catalyst may be applicable to the present invention, and the resin catalyst in the present embodiment is using polymerization, extracting, chlorination, sulfonation
It is specific as follows and active group stabilizes five steps and prepared:Polymerization obtains styrene-divinylbenzene copolymer microballoon, is swelled, will be molten
Copolymer after swollen and benzene are blended in 180 DEG C, stirring extracting processing 16h under 2.0MPa, cooling, discharge benzene, then copolymer is put
Extracting is handled under similarity condition in absolute ethyl alcohol, washing, chlorination, sulfonation, active group is carried out successively to copolymer after purification
After group stabilizes, the type heatproof strong-acid cation-exchange resin catalysts of DNW- II are obtained.
(2)The pretreatment of the type strong-acid cation-exchange resins of DNW- II:
Isopropanol, sec-butyl alcohol and deionized water are subjected to deoxygenation processing in advance, are with preparing isopropanol and sec-butyl alcohol volume fraction
5% low-carbon mixed alkoxide solution, the type strong-acid cation-exchange resins of DNW- II are placed in above-mentioned low-carbon mixed alkoxide solution, are put into
Enamelled vessel.Low-carbon mixed alkoxide solution is 5 with the type strong-acid cation-exchange resin volume ratios of DNW- II:1, in 100 DEG C of spontaneous pressures
8h is handled under power.
Embodiment 2
Remove(2)In replaced with ethanol and n-butanol outside isopropanol and sec-butyl alcohol, other conditions are same as Example 1.
Embodiment 3
Remove(2)In replaced with ethanol and isopropanol outside isopropanol and sec-butyl alcohol, other conditions are same as Example 1.
Embodiment 4
Remove(2)In replaced with sec-butyl alcohol outside isopropanol and sec-butyl alcohol, other conditions are same as Example 1.
Embodiment 5
Remove(2)In replaced with isopropanol outside isopropanol and sec-butyl alcohol, other conditions are same as Example 1.
Embodiment 6
Remove(2)In replaced with methanol and isopropanol outside isopropanol and sec-butyl alcohol, other conditions are same as Example 1.
Embodiment 7
Remove(2)In replaced with methanol and sec-butyl alcohol outside isopropanol and sec-butyl alcohol, other conditions are same as Example 1.
Embodiment 8
Remove(2)In with 5% methanol replace low-carbon mixed alkoxide solution outside, other conditions are same as Example 1.
Embodiment 9
Remove(2)The middle concentration by isopropanol and sec-butyl alcohol changes into 0.5% and 9.5% respectively, and other conditions are same as Example 1.
Embodiment 10
Remove(2)The middle concentration by isopropanol and sec-butyl alcohol changes into 9.5% and 0.5% respectively, and other conditions are same as Example 1.
Embodiment 11
Remove(2)The middle concentration by isopropanol and sec-butyl alcohol changes into 0.5% and 0.5% respectively, and other conditions are same as Example 1.
Embodiment 12
Remove(2)It is middle that low-carbon mixed alkoxide solution and the type strong-acid cation-exchange resin volume ratios of DNW- II are changed to 10:1, pretreatment
Condition is changed to handle 24h under 150 DEG C and self-generated pressure, and other conditions are same as Example 1.
Embodiment 13
Remove(2)It is middle that low-carbon mixed alkoxide solution and the type strong-acid cation-exchange resin volume ratios of DNW- II are changed to 15:1, pretreatment
Condition is changed to handle 12h under 150 DEG C and self-generated pressure, and other conditions are same as Example 1.
It is modified in itself and embodiment 1 ~ 13 to the type strong-acid cation-exchange resins of DNW- II before modified as a comparison case 1
The pore structure of resin catalyst afterwards is measured with 2400 adsorption instruments, as a result as shown in table 1.
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 2.
Table 1
Table 2
Embodiment 14
Take the above-mentioned stainless steel for loading Φ 18mm × 1200mm with resin catalyst modified in embodiment 1 ~ 13 before modified anti-
Answer in device, reactor head and bottom, be respectively charged into a diameter of Φ 0.5mm-1.2mm quartz sand, after reactor installs,
With nitrogen displacement three times, and air seal test is qualified.It is passed through 2- methyl butenes and carries out etherification reaction, reaction condition and reaction with methanol
It the results are shown in Table 3.
Table 3
Claims (10)
1. a kind of preparation method of tert amyl methyl ether(TAME), comprises the following steps:
1. removing the oxygen in low-carbon alcohols and deionized water in advance, strong-acid cation-exchange resin catalyst is placed in the water of low-carbon alcohols
In solution, it is put into closed container and is heated to handling 8 ~ 24h under 100 DEG C ~ 250 DEG C self-generated pressures;
The low-carbon alcohols are at least one of C1 ~ C4 alcohol;
2. the strong-acid cation-exchange resin catalyst for taking step to be 1. modified, it is placed in continuous fixed bed stainless steel reactor, will
C5 alkene and methanol are passed through progress etherification reaction in reactor and prepare tert amyl methyl ether(TAME).
2. preparation method according to claim 1, it is characterised in that:The low-carbon alcohols are selected from methanol, ethanol, propyl alcohol, different
At least one of propyl alcohol, n-butanol, the tert-butyl alcohol, sec-butyl alcohol and isobutanol.
3. preparation method according to claim 2, it is characterised in that:The low-carbon alcohols are methanol and ethanol.
4. preparation method according to claim 1, it is characterised in that:The volumetric concentration of alcohol in the aqueous solution of the low-carbon alcohols
For 0.5% ~ 20%.
5. preparation method according to claim 4, it is characterised in that:The volumetric concentration of alcohol in the aqueous solution of the low-carbon alcohols
For 1% ~ 10%.
6. preparation method according to claim 1, it is characterised in that:Step 1. the aqueous solution of middle low-carbon alcohols and strong acid sun from
The mixed volume ratio of sub-exchange resin is 5 ~ 15:1.
7. preparation method according to claim 1, it is characterised in that:Step 1. middle heating temperature for 100 DEG C ~
150℃。
8. preparation method according to claim 1, it is characterised in that:The time of step 1. middle heating is 12 ~ 24h.
9. preparation method according to claim 1, it is characterised in that:Step 2. described in C5 alkene and during methanol etherification,
The mol ratio of methanol and C5 alkene is 1 ~ 5.5:The liquid quality air speed of 1, C5 alkene is 0.5h-1~5.0h-1, reaction temperature 80
DEG C ~ 200 DEG C, reaction pressure is 0.1MPa ~ 4.0MPa.
10. preparation method according to claim 9, it is characterised in that:The C5 alkene be 2-methyl-1-butene alkene and/or
2- methyl-2-butenes.
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CN107537567A (en) * | 2016-06-23 | 2018-01-05 | 中国石油化工股份有限公司 | A kind of method of modifying of sulfonic group cation exchange resin and the method for preparing tert amyl methyl ether(TAME) |
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CN86102001A (en) * | 1985-04-06 | 1986-10-01 | 德国泰克萨科股份公司 | The processing method of strongly acidic cation exchange catalysts |
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CN107537567A (en) * | 2016-06-23 | 2018-01-05 | 中国石油化工股份有限公司 | A kind of method of modifying of sulfonic group cation exchange resin and the method for preparing tert amyl methyl ether(TAME) |
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