USOO6500992B1

(12) United States Patent (10) Patent No.: US 6,500,992 B1

Ali (45) Date of Patent: Dec. 31, 2002

(54) SYNTHESIS OF METHYL TERTIARY BUTYL Chu, P. and Kuhl, H., Preparation of methyl tertiary butyl
ETHER FROM METHANOLAND ether (MTBE) over Zeolite catalysts. Industrial and Engi
ISOBUTENE USING ALUMNUM neering Chemistry Research, 1987, vol. 26, 365-369.
FLUORIDE-MODIFIED ZEOLITE Izquierdo, J.F., Cunill, F., Vila, M., Tejero, J. and Iborra, M.
CATALYSTS Equilibrium constants fro methyl tertiary butyl ether liquid
phase Synthesis. Journal of Chemical and Engineering Data,
(75) Inventor: Mohammad Ashraf Ali, Dhahran (SA) 1992, vol. 37, p. 339.
Brockwell, H.L., Sarathy, S.R. and Troffa, R. Synthesize
(73) Assignee: King Fahd University of Petroleum & Ethers. Hydrocarbon Processing, Sep.1991, p. 133, vol. 70,
Minerals, Dhahran (SA) No. 9.
Tejero, J. Molecular mechanism of MTBE synthesis on a
(*) Notice: Subject to any disclaimer, the term of this Sulfonic acid ion-exchange resin. Journal of Molecular
patent is extended or adjusted under 35 Catalysis, 1987, vol. 42, p. 257.
U.S.C. 154(b) by 0 days. Subraminium, C. and Bhatia, S. Liquid phase Synthesis of
MTBE4&talyzed by ion-exchange resin. Canadian Journal
(21) Appl. No.: 09/708,545 of Chemical Engineering, 1987, vol. 65, p. 613.
(22) Filed: Nov. 9, 2000 * cited by examiner
(51) Int. Cl. ................................................ C07C 41/06 Primary Examiner Rosalynd Keys
(52) U.S. Cl. .......................................... 568/697; 502/64 (74) Attorney, Agent, or Firm-Dennison, Schultz &
(58) Field of Search ............................. 568/697; 502/64 Dougherty
(56) References Cited (57) ABSTRACT
U.S. PATENT DOCUMENTS This invention concerns an improved and novel catalyst for
preparing methyl tertiary butyl ether (MTBE). This inven
4,182,913 A 1/1980 Takezono et al. tion is advantageous in that the reaction of methanol and
4,530,756 A * 7/1985 Chang et al. ........... 208/111.15 isobutene takes place Such that the catalysts exhibit levels of
4,564,719 A * 1/1986 Chang et al. ............... 585/408 isobutene conversion as high as 98%, and the MTBE selec
4,605,787 A 8/1986 Chu et al. ................... 568/697
5,157,162. A 10/1992 Knifton tivity reaches as high as 98%. The improved catalysts
5,220,078 A 6/1993 Knifton et al. comprises of a crystalline aluminosilicate Zeolites, particu
5,300,697 A 4/1994 Knifton et al. larly MFI-type Zeolites which has been treated with alumi
5,783,321. A * 7/1998 Verduijn et al. ............ 423/702 num fluoride in the ratio 1 gram to 10 grams of Zeolite with
FOREIGN PATENT DOCUMENTS 0.5 gram to 5 grams of aluminum fluoride. A specific
application of this improved and novel catalyst is reacting
JP 360231793 A * 11/1985 ............ C10G/3/OO methanol and isobutene in a molar amount of about 0.1 mole
OTHER PUBLICATIONS
to 10 moles of methanol per mole of isobutene, in the
presence of said catalyst in a batch reactor, at about 70° C.
Davenport, Robert, E., Gasoline Octane Improvers. Chemi to about 100° C., and a pressure of about 1 bar to 33 bar, to
cal Economics Handbook, CEH Marketing Report, 1986, p. obtain MTBE product.
543, Standard Research Institute, SRI International, Minlo
Park, California. 13 Claims, No Drawings
 US 6,500,992 B1
1 2
SYNTHESIS OF METHYL TERTARY BUTYL apparatus are corroded by the Strong acids released. In this
ETHER FROM METHANOLAND reaction, diisobutene and tertiary butyl alcohol (TBA) are
ISOBUTENE USING ALUMINUM the by-products of dimerization of isobutene and reaction of
FLUORIDE-MODIFIED ZEOLITE water with isobute ne respectively. The amount of
CATALYSTS disobutene formed increases with rise in temperature Chu
and Kohl, Industrial and Engineering Chemistry Research,
BACKGROUND OF THE INVENTION 1987, Vol 26, p. 365). TBA formation is insignificant as long
as the feedstocks are thoroughly dried. According to
It is well known that ethers may be prepared by reacting LeChatlier's principle, the reaction equilibrium for MTBE
an alcohol with an olefin to form the desired product. The formation is more favorable at lower temperatures, but
reaction mixture containing catalysts and/or condensing reaction rate is decreased considerably. Thus current opera
components may be separated and further treated to permit tion temperatures appear to be limited by three factors: (i).
attainment of the desired product specification. resin catalyst instability at temperature above 100° C.; (ii).
MTBE is being used as a blending component in high 15
poor selectivity due to dimerization above 100° C.; and (iii).
octane gasoline, as the gasoline additives based on lead and equilibrium conversion limitation. It is also pointed out that
manganese have been phased out. Currently, all commercial the progreSS of the reaction over cationic ion-exchange resin
processes for the manufacture of MTBE are based upon the is usually complicated by various adsorption and diffusion
liquid phase reaction of isobutene and methanol catalyzed factors, by Swelling phenomenon, and by the variable dis
by cationic ion-exchange resin (see: Izquierdo, J. F., Cunill, tribution of the components between the Solution and cat
F., Vila M., Tejero J. and Tborra M. Equilibrium constants ionic eXchanger phase.
for methyl tertiary butyl ether liquid-phase Synthesis. Jour The Zeolites have a porous Structure and are represented
nal of Chemical and Engineering Data, 1992, vol. 37, p. by the following general formula;
339.; Brockwell, H. L., Sarathy P. R. and Trotta R. Synthe 25
size ethers. Hydrocarbon Processing, 1991, vol. 70, No. 9, p.
133.; Chemical Economics Handbook, Gasoline Octane Where M is an alkali metal or alkaline earth metal cation
Improvers. CEH Marketing Report, 1986, p. 543, Stanford or organic base cation, n is the Valence of the cation and X
Research Institute, SRI International, Menlo Park, Calif.). and y are variables.
The isobutene is obtained by the fluid catalytic cracking In U.S. Pat. No. 5,157,162 to Knifton there is disclosed a
process, from the isomerization of n-butene and dehydro process for one-step synthesis of MTBE using tertiary
genation of isobutane. The methanol is produced from butanol and methanol over a catalyst comprising fluoroSul
Syngas (a mixture of carbon monoxide and hydrogen) fonic acid modified montmorillonite clay at temperature of
obtained from the Steam reforming of natural gas. The 35 about 20° C. to about 250 C.
cationic ion-exchange resins used in MTBE Synthesis nor In U.S. Pat. No. 5,220,078, a process is disclosed for
mally have the Sulfonic acid functionality (see: Tejero, J. producing MTBE using tertiary butanol and methanol over
Journal of Molecular Catalysis, 1987, vol. 42, p. 257; a catalyst comprising of fluorophosphoric acid modified
Subraminium and Bhatia, Canadian Journal of Chemical 40 Y-type Zeolite at temperature of about 20° C. to about 250
Engineering, 1987, vol. 65, p. 613). C.
U.S. Pat. No. 5,300,697 discloses a process for producing
MTBE using tertiary butanol and methanol over a catalyst
These cationic ion-exchange resins are generally based on comprising of hydrogen fluoride modified Y-type Zeolite at
polystyrene-divinylbenzene backbone and have a very lim 45 temperature of about 20° C. to about 250° C. All of these
ited Stability range with regard to operating temperatures, processes are limited by the fact that the conversion is low
with temperatures above 100° C., normally leading to irre and the selectivity of the reaction for MTBE is quite small.
versible destruction of the resin and loSS of catalytic activity. It would be a substantial improvement in the art if MTBE
The catalyst life in commercial operation is about two years. 50
could be Selectively Synthesized from isobutene and metha
The MTBE synthesis reaction is exothermic, yielding -37.7 nol using a catalyst which allows for rapid conversion of
kJ mol of energy. isobutene. In our invention, aluminum fluoride-modified
The detrimental effects of instability of the resin catalyst Zeolite can be used as an improved and novel catalyst for the
used in the preparation of MTBE have been discussed in a selective synthesis of MTBE from isobutene and methanol
patent by Takezono and Fujiwara U.S. Pat. No. 4,182,913). 55 with high conversion. The accompanying examples demon
According to the findings of this study, at higher strate good yields of MTBE when using the modified
temperatures, a large quantity of acids is effused from the Zeolites of the instant invention for Such a reaction.
Strongly acidic cation-exchange resin and the deterioration
SUMMARY OF THE INVENTION
of the catalyst resin is accelerated. Even when the tempera 60
ture is low, a Small quantity of the Strong acidic Substance is In accordance with certain of its aspects, the novel method
effused into the reaction mixture. When Such a reaction of this invention for preparing MTBE from methanol and
mixture containing the acid Substance is fed into the Suc isobutene comprises reacting methanol and isobutene in the
ceeding Step of unreacted gas Separation, So as to Separate presence of a catalyst comprising an aluminum fluoride
the unreacted gas by distillation, the decomposition or 65 modified Zeolite containing at least one metal from Group
reverse reaction of the main product is caused to occur, IIIA of the periodic table. Examples demonstrate particu
which reduces the yield. In addition, various portions of the larly the effectiveness of an aluminum fluoride-modified
 US 6,500,992 B1
3 4
MFI-type Zeolite. MFI is the structure type code (allocated linked through shared oxygen atoms. Because of the net
by the Structure Commission of the International Zeolite negative charge on each of the aluminum-centered
ASSociation) to a number of Zeolites having similar topology tetrahedra, each unit cell contains an equivalent number of
Such as ZSM-5 and silicalite. charge balancing cations. These are exclusively Sodium ions
DESCRIPTION OF THE INVENTION
in Zeolites in their synthesized form. MFI-type ZSM-5
Zeolite in its hydrated and sodium form has the following
Preparation of the product using this invention may be general formula in which the number of aluminum atoms
carried out typically by reacting methanol and isobutene in should be less than 27.
the presence of an etherification catalyst. The etherification NaAl,Sios.O.192.16H2O
is carried out in one-step and the catalyst preferably com
prises MFI-type Zeolite modified hydrothermally with alu Particularly effective in the subject synthesis of MTBE
minum fluoride. This important reaction does not restrict the are the synthetic MFI-type Zeolites. Preferably said zeolites
Scope of the invention. should be in a strongly acidic form whereby some or all of
the cations (Group I or II, alkali or alkaline earth metals Such
The reaction of isobutene and methanol can be repre 15 as Sodium, potassium, calcium or magnesium)) are
Sented by the following equation: eXchanged by protons either through ammonium exchange
followed by thermal stabilization (deammoniation or
CH CH removal of ammonia) at elevated temperatures (for example
V 400° C. to 500 C.) or through mineral acid treatment, etc.
C=CH + CH-OH - > al-i-o-ch, The mineral acids may include hydrochloric acid, Sulfuric
CH CH acid or nitric acid.
Isobutene Methanol MTBE The aluminum fluoride-modified zeolite is prepared by
treating the said MFI-type Zeolite with aluminum fluoride in
Generally the methanol and isobutene coreactants may be the presence of distilled water. Preferably the aluminum
mixed in any proportion in order to generate the desired 25 fluoride is mixed with the distilled water in a sealed con
MTBE, but preferably the molar ratio of methanol to tainer and heated at elevated temperature before adding the
isobutene in the reaction mixture should be about 0.1 to 10. Zeolite to the said mixture of aluminum fluoride and distilled
Water.
In order to achieve maximum selectivity to MTBE and
optimum conversion per hour, an excess of methanol in the In a further embodiment of the invention, the Zeolite
reaction mixture is desirable. The most preferred methanol catalyst comprises 1 to 2 weight percent of the total reaction
to-isobutene molar ratio is from 1:1 to 5:1. contents. In a further embodiment of the invention, the
The synthesis of MTBE according to the reaction given methanol comprises about 99 weight percent of methanol. In
above can also be conducted where the isobutene and a further embodiment of the invention, the isobutene com
methanol reactants are mixed with other Caliphatic and prises about 98 weight percent of isobutene. In a further
olefinic hydrocarbons Such as isobutane, n-butane and 35 embodiment of the invention, methanol comprises about 41
n-butene. weight percent of the reaction mixture. In a further embodi
The same etherification proceSS may also be applied for ment of the invention, the isobutene comprises about 59
the preparation of other alkyl tertiary ethers. For example, weight percent of the reaction mixture.
the Said etherification proceSS may be applied to the reaction The Said catalyst may be in the form of powders, pellets,
of a C-C primary alcohol Such as methanol, ethanol, 40 granules, Spheres, shapes and extrudates. The examples
n-propanol and n-butanol with a C-C tertiary olefin, Such described herein demonstrate the advantages of using pow
der form.
as for example, tertiary amyl olefin. Reaction of methanol The reaction may be carried out in either a Stirred slurry
with tertiary amyl olefin would then yield methyl tertiary reactor or in a fixedbed continuous flow reactor. The catalyst
amyl methyl ether (TAME). Similarly, reactions of ethanol 45 concentration should be sufficient to provide the desired
with isobutene would then yield ethyl tertiary butyl ether catalytic effect.
(ETBE). Etherification can generally be conducted at temperatures
Good results were realized using certain crystalline alu from 40° C. to 150° C.; the preferred range is 40 to 100° C.
minosilicate Zeolites as catalysts for the reaction of The total operating pressure may be from 1 bar to 66 bar, or
isobutene and methanol to produce MTBE. The preferred 50 higher. The preferred pressure range is about 1 bar to 33 bar.
Zeolites are the MFI-type Zeolites as well as Zeolite beta and The examples which follow illustrate the synthesis of
mordenite, modified hydrothermally with aluminum fluo MTBE from methanol and isobutene using aluminum fluo
ride.
ride MFI-type Zeolite particularly in the form of powder. The
Zeolites possesses a number of catalytically-favorable examples are a means of illustration and it is understood that
properties Such as well-defined crystalline Structure, uniform 55 the invention is not meant to be limited thereby.
pores, high Surface area, good thermal Stability, wide range Conversion of the isobutene (Isobutene, mole %) is esti
of acidity and shape Selectivity. mated in the following examples using the equations:

(Moles of Isobutene in the Feed) - (Moles of Isobutene in the Product) x 100

Moles of Isobutene in the Feed

65
The unit cell of a MFI-type ZSM-5 zeolite contains 96 Selectivity of MTBE (MTBE, mole %) is estimated from
Silicon or aluminum-centered oxygen tetrahedra which are the following equation:
 US 6,500,992 B1
S
Moles of MTBE in the Product
x 100
(Moles of Isobutene in the Feed) - (Moles of Isobutene in the Product)

It may be noted that grams as finely divided powder, was added in 200 ml of
i. Comparing etherification data in Table I and Example 5, distilled water. The mixture was heated at about 100 C. to
using the aluminum-fluoride-modified Zeolite ZCIC about 200 C. in a closed Teflon screw-capped 500 ml bottle
10, prepared by the method of Example 1, with the data for about 12 hours to about 18 hours. The mixture was
of ZCIC-10 alone (Comparative Example A, Table V) cooled and was added with 10 grams of precalcined MEI
it is seen that the isobutene conversion levels with type Zeolite (synthesized Zeolite having a Si/Al molar ratio
aluminum-fluoride-modified Zeolite of Example 5 of 10, in powder form). The calcination of the Zeolite was
occur at all operating temperatures, but particularly at carried out at 400° C. to 500 C. programmed temperature
80 C. to 100° C. are at least three times higher than for 15 in air having 100 ml/hour flow rate. The mixture was again
ZCIC-10 alone. heated at about 100° C. to about 200° C. for about 12 to
ii. Comparing etherification data in Table II and Example about 18 hours and brought to ambient temperature. The
6, using the aluminum-fluoride-modified Zeolite ZCIC resultant mixture was then filtered, washed Several times
10, prepared by the method of Example 2, with data of with distilled water and dried in an air-circulated oven at
ZCIC-10 alone (Comparative Example A, Table V) it is 100 C. for 12 hours to about 18 hours. The recovered white
seen that the isobutene conversion levels with
aluminum-fluoride-modified Zeolite of Example 6 powder was found to have the following elemental compo
occur at all operating temperatures, but particularly at Sition.
80 to 100° C. are at least four times higher than for Fluorine, 1.39 wt %
ZCIC-10 alone as well as higher than that of Example 25 Aluminum, 6.23 wt %
5
Silicon, 36.65 wt %
iii. Comparing etherification data in Table III and Si/Al molar ratio, 5.65
Example 7, using the aluminum-fluoride-modified Zeo
lite ZCIC-10, prepared by the method of Example 3, Si/F molar ratio, 17.84
with data of ZCIC-10 alone (Comparative Example A, Al/F molar ratio, 3.16
Table V) it is seen that the isobutene conversion levels
with aluminum-fluoride-modified zeolite of Example 7 EXAMPLE 2
occur at all operating temperatures, but particularly at
80 to 100 C. are significantly and measurably at least This example illustrates the preparation of an aluminum
five times higher than for ZCIC-10 alone as well as fluoride-modified MFI-type Zeolite. Aluminum fluoride, 4.4
higher than those of Example 5 (Table I) and 6 (Table 35 grams as finely divided powder, was added in 200 ml of
II). distilled water. The mixture was heated at about 100 C. to
iv. Comparing etherification data in Table IV and Example about 200 C. in a closed Teflon screw-capped 500 ml bottle
8, using the aluminum-fluoride-modified Zeolite for about 12 hours to about 18 hours. The mixture was
MZ-25, prepared by the method of Example 4, with cooled and was added with 10 grams of precalcined MFI
data of MZ-25 alone (Comparative Example B, Table 40 type Zeolite (synthesized Zeolite having a Si/Al molar ratio
VI) it is seen that the isobutene conversion levels with of 10, in powder form). The calcination of the Zeolite was
aluminum-fluoride-modified Zeolite of Example 8 carried out at 400° C. to 500 C. programmed temperature
occur at all operating temperatures, but particularly at in air having 100 ml/hour flow rate. The mixture was again
80 to 100° C. are significantly and measurably higher heated at about 100° C. to about 200° C. for about 12 hours
than for MZ-25 alone. 45 to about 18 hours and brought to ambient temperature. The
Comparing the etherification data in Table I and resultant mixture was then filtered, washed Several times
Example 5, using the aluminum-fluoride-modified Zeo with distilled water and dried in an air-circulated oven at
lite ZCIC-10, prepared by the method of Example 1, 100 C. for 12 hours to about 18 hours. The recovered white
with the data of aluminum-fluoride-modified Zeolite powder was found to have the following elemental compo
MZ-25, prepared by the method of Example 4 and 50 Sition.
given in Table VI, it is seen that the isobutene conver Fluorine, 1.70 wt %
Sion levels with aluminum-fluoride-modified Zeolite of
Example 5 occur at all operating temperatures are Aluminum, 7.23 wt %
Significantly and measurably higher than for Silicon, 33.98 wt %
aluminum-fluoride-modified zeolite MZ-25, prepared 55 Si/Al molar ratio, 4.52
by the method of Example 4 and given in Table VI. Si/F molar ratio, 12.56
vi. Comparing the etherification data in Table V and
Comparative Example A, using the ZCIC-10 Zeolite, Al/F molar ratio, 2.99
with the data of MZ-25 zeolite given in Table VI and EXAMPLE 3
Comparative Example B, it is seen that the isobutene
conversion levels with ZCIC-10 zeolite given in Table 60 This example illustrates the preparation of an aluminum
V occur at all operating temperatures are significantly fluoride-modified MFI-type Zeolite. Aluminum fluoride, 6.6
and measurably higher than for MZ-25 Zeolite given in grams as finely divided powder, was added in 200 ml of
Table VI. distilled water. The mixture was heated at about 100 C. to
EXAMPLE 1.
about 200 C. in a closed Teflon screw-capped 500 ml bottle
65 for about 12 hours to about 18 hours. The mixture was
This example illustrates the preparation of an aluminum cooled and was added with 10 grams of precalcined MFI
fluoride-modified MFI-type Zeolite. Aluminum fluoride, 2.2 type Zeolite (synthesized Zeolite having a Si/Al molar ratio
 US 6,500,992 B1
7 8
of 10, in powder form). The calcination of the Zeolite was vessel. The controller maintained the temperature of the
carried out at 400° C. to 500 C. programmed temperature autoclave in the range 0 C. to 400 C. with the use of a
in air having 100 ml/hour flow rate. The mixture was again thermocouple.
heated at about 100° C. to about 200° C. for about 12 hours
to about 18 hours and brought to ambient temperature. The The isobutene measuring and feed tube was made of thick
resultant mixture was then filtered, washed Several times QVF glass tube of 1.0 inch internal diameter and 18.0 inch
with distilled water and dried in an air circulated oven at in length. It was fitted at the top with a flange holding two
100° C. for 12 hours to about 18 hours. The recovered white Valves, a vent valve and a valve connected to the inverted
powder was found to have the following elemental compo isobutene cylinder for allowing the isobutene in the tube. A
Sition. Second flange with a valve was attached at the bottom end
Fluorine, 1.94 wt % for feeding isobutene to the preheater. This tube was cali
Aluminum, 7.73 wt % brated to provide an accurate measure of the Volume of
Silicon, 33.74 wt % isobutene fed into the preheater. The isobutene measuring
Si/Al molar ratio, 4.21 15 and feed tube was connected to an inverted pressurized
Si/F molar ratio, 11.80 isobutene cylinder by metal tubings through which the liquid
Al/F molar ratio, 2.80 isobutene was drawn from the cylinder.
EXAMPLE 4
The reactor vessel was charged with 20.5 grams of
methanol (0.64 mole) along with 1.0 gram of aluminum
This example illustrates the preparation of an aluminum fluoride-modified zeolite catalyst prepared by the method of
fluoride-modified MFI-type Zeolite. Aluminum fluoride, 2.2 Example 1 and was closed with the reactor head using Split
grams as finely divided powder, was added in 200 ml of ring closures. A known volume of isobutene, 50 ml (0.53
distilled water. The mixture was heated at about 100 C. to mole), was taken into a isobutene measuring and feed tube.
about 200 C. in a closed Teflon screw-capped 500 ml bottle 25 This constitutes a methanol-to-isobutene molar ratio of 1.2.
for about 12 hours to about 18 hours. The mixture was Isobutene was charged into the reactor through the inlet
cooled and was added with 10 grams of precalcined MFI valve of the reactor head assembly. The reactor was then
type Zeolite (Mobil MZ-25, powder form, having a Si/Al pressurized with nitrogen to 13 bar to 17 bar. The reaction
molar ratio of 25.50). The calcination of the Zeolite was was carried out at 70° C. to 100° C. under constant stirring.
carried out at 400° C. to 500 C. programmed temperature The reaction time was 3 hours after the reactor achieved the
in air having 100 ml/hour flow rate. The mixture was again desired temperature. The temperature of the reactor was
heated at about 100° C. to about 200° C. for about 12 to maintained by circulating the oil in the Stainless Steel coils
about 18 hours and brought to ambient temperature. The present in the reactor. At the end of the run, the reactor was
resultant mixture was then filtered, washed Several times 35 allowed to cool and the contents were centrifuged to Sepa
with distilled water and dried in an air-circulated oven at rate the fine particles of Zeolite catalyst from the reaction
100° C. for 12 hours to about 18 hours. The recovered white product. The reaction products were analyzed using capil
powder was found to have the following elemental compo lary column gas chromatography using a flame ionization
Sition. detector. The reaction products were analyzed by mixing
40
Fluorine, 0.47 wt % with a known amount of diisopropyl ether as an internal
Standard.
Aluminum, 3.74 wt %
Silicon, 42.02 wt % Typical analysis data for Samples taken under these con
Si/Al molar ratio, 10.57 ditions are Summarized in Table I. Performance at a series of
Si/F molar ratio, 59.22 45 other temperatures and methanol to isobutene molar ratioS
Al/F molar ratio, 05.60 was determined using the same procedure. These results are
Summarized in Table I. Of note, isobutene conversion and
EXAMPLE 5 MTBE selectivity are as follows:
This example illustrates the production of MTBE from 50
methanol and isobutene using aluminum-fluoride-modified
MFI-type Zeolite. The catalytic reactions were carried out in Reaction Isobutene Conversion MTBE Selectivity
a batch reactor (manufactured by Parr Instrument Company, Sample Temperature( C.) % %
Moline, Ill., USA) using 1 gram of the said Zeolite catalyst. 1. 8O 57 98
This reactor consisted of reactor vessel, reactor head, heater, 55 2 1OO 74 95
temperature controller, and temperature indicator. The reac
tor was equipped with all required fittings Such as inlet
Valve, a gas release valve, a Safety rupture disk, a pressure EXAMPLE 6
gauge, a stirrer driving System, oil circulating Stainless Steel 60
coil and a thermowell for holding the thermocouple. The This example illustrates the production of MTBE from
reactor vessel was a 500 ml stainless steel cylindrical methanol and isobutene using another aluminum-fluoride
preSSure vessel. Vigorous mixing of the reactants, as well as modified MFI-type Zeolite. Following the procedure of
uniform distribution of the catalyst or Suspended Solids, was Example 5, the batch reactor was charged with 1.0 gram of
achieved by impellers that were located on the Stirring rod 65 Zeolite catalyst of Example 2 and the performance was
near the bottom of the vessel. The heater provided uniform monitored over a series of temperature (70° C. to 100° C.)
heat distribution around the sides and the bottom of the and methanol to isobutene molar ratios (1:1.1 to 2:1). These
 US 6,500,992 B1
10
results are Summarized in Table II. Calculated isobutene COMPARATIVE EXAMPLEA
conversion and MTBE selectivity are as follows:

This example illustrates the performance of an unmodi

Reaction Isobutene Conversion MTBE Selectivity fied MFI-type Zeolite in the production of MTBE from
Sample Temperature( C.) % %
methanol and isobutene over a range of operating condi
1.
2
8O
1OO
76
91
98
96
tions. Using the equipment and procedures of Example 5,
the batch reactor was charged with 1.0 gram of Zeolite
catalyst (ZCIC-10 synthesized zeolite having Si/Al molar
ratio of 10, in powder form) and the performance was
EXAMPLE 7
monitored over a series of temperature (70° C. to 100° C.)
and methanol to isobutene molar ratios (1:1.1 to 2:1). These
15 results are Summarized in Table IV. Calculated isobutene
This example illustrates the production of MTBE from conversion and MTBE selectivity at 80° C. and 100° C. are
as follows:
methanol and isobutene using another aluminum-fluoride
modified MFI-type Zeolite. Following the procedure of
Example 5, the batch reactor was charged with 1.0 gram of
Zeolite catalyst of Example 3 and the performance was Reaction Isobutene Conversion MTBE Selectivity
monitored over a series of temperature (70° C. to 100° C.) Sample Temperature( C.) % %
and methanol to isobutene molar ratios (1:1.1 to 2:1). These 1. 8O 19 8O
results are Summarized in Table III. Calculated isobutene 2 1OO 35 79
conversion and MTBE selectivity are as follows: 25

Reaction Isobutene Conversion MTBE Selectivity

Sample Temperature( C.) % % COMPARATIVE EXAMPLEB
1. 8O 79 98
2 1OO 98 97

This example illustrates the performance of an unmodi

35 fied MFI-type Zeolite in the production of MTBE from
EXAMPLE 8 methanol and isobutene over a range of operating condi
tions. Using the equipment and procedures of Example 5,
This example illustrates the production of MTBE from the batch reactor was charged with 1.0 gram of Zeolite
methanol and isobutene using another aluminum-fluoride 40
catalyst (Mobil MZ-25, powder form, having weight percent
modified MFI-type Zeolite. Following the procedure of composition of silicon 42.71, aluminum 1.61 and Si/Al
Example 5, the batch reactor was charged with 1.0 gram of molar ratio of 25.50) and the performance was monitored
Zeolite catalyst Example 4 and the performance was moni over a series of temperature (70° C. to 100° C.) and
tored over a series of temperature (70° C. to 100° C.) and methanol to isobutene molar ratios (1:1.1 to 2:1). These
methanol to isobutene molar ratios (1:1.1 to 2:1). These 45 results are Summarized in Table V. Calculated isobutene
results are Summarized in Table III. Calculated isobutene conversion and MTBE selectivity at 80° C. and 100° C. are
conversion and MTBE selectivity are as as follows:

50
Reaction Isobutene Conversion MTBE Selectivity Reaction Isobutene Conversion MTBE Selectivity
Sample Temperature( C.) % % Sample Temperature( C.) % %
1. 8O 27 99 1. 8O 16 94
2 1OO 48 97 2 1OO 3O 91

TABLE I
MeOHAIB Reactants Temperature Product Composition, mole %
Example Catalyst molar ratio Charged (g) o C. MTBE TEBA IB MeOH
5 Example 1 1.2 50 70 7.2 O3 41.2 51.3
8O 12.6 OS 38.1 48.8
90 2O2 O8 33.6 45.4
1OO 28.9 O.7 29.0 41.4
 US 6,500,992 B1

TABLE II
MeOHAIB Reactants Temperature Product Composition, mole %
Example Catalyst molar ratio Charged (g) o C. MTBE TBA B MeOH
6 Example 2 1.2 50 70 11.1 O.S. 38.9 49.5
8O 2O.O O.8 33.7 45.4
90 33.4 1.4 25.9 39.4
1OO SO.1 12 16.9 31.8

TABLE III
MeOHAIB Reactants Temperature - Product Composition, mole %
Example Catalyst molar ratio Charged (g) o C. MTBE TBA B MeOH
7 Example 3 1.2 50 70 12.7 O.S. 38.1 48.8
8O 23.1 O.9 32.O 44.1
90 39.1 1.5 22.6 36.8
1OO 6O.O 1.4 11.4 27.3

TABLE IV
MeOHAIB Reactants Temperature Product Composition, mole %
Example Catalyst molar ratio Charged (g) o C. MTBE TBA B MeOH
8 Example 4 1.2 50 70 3.8 O.1 43.3 52.8
8O 6.5 O.1 41.8 51.6
90 1O.O O.2 39.8 SO.O
1OO 13.8 O.2 37.8 48.3

TABLE V
MeOHAIB Reactants Temperature Product Composition, mole %
Example Catalyst molar ratio Charged (g) o C. MTBE TBA B MeOH
A. ZCC-10 1.2 50 70 2.4 1.2 43.0 53.5
8O 4.0 2.0 41.3 52.7
90 6.1 3.O 39.1 51.8
1OO 8.3 2.5 38.4 SO.8

TABLE VI
MeOHAIB Reactants Temperature Product Composition, mole %
Example Catalyst molar ratio Charged (g) o C. MTBE TBA B MeOH
B MZ-25 1.2 50 70 2.1 O.3 44.1 53.6
8O 3.5 O.4 43.1 53.0
90 5.3 O.7 41.9 52.1
1OO 7.2 O.6 41.O 51.3

While the instant invention has been described by specific 55 3. A proceSS according to claim 1 wherein the Zeolite
examples and embodiments, there is no intent to limit the catalyst comprises 1 to 2 weight percent of the total reaction
COntentS.
inventive concept except as Set forth in the following claims. 4. A process according to claim 2 wherein the methanol
What is claimed is: comprises about 99 weight percent of methanol.
1. A proceSS for the preparation of an alkyl tertiary-alkyl 60
5. A process according to claim 2 wherein the isobutene
ether, comprising reacting an alcohol and an olefinic hydro comprises about 98 weight percent of isobutene.
carbon at a temperature of about 40 C. to about 150° C. in 6. A process according to claim 2 wherein methanol
the presence of an aluminum fluoride-modified Zeolite cata comprises about 41 weight percent of the reaction mixture.
7. A process according to claim 2 wherein the isobutene
lyst having an pre-calcined Silica/alumina ratio 10, and comprises about 59 weight percent of the reaction mixture.
recovering the alkyl tertiary-alkyl ether. 65 8. A process according to claim 2 wherein the methanol
2. A process according to claim 1 wherein the alcohol is and isobutene are present in a molar ratio of one mole of
methanol and the olefnic hydrocarbon is isobutene. isobutene to 0.1 mole to 10 moles of methanol.
 US 6,500,992 B1
13 14
9. A proceSS according to claim 1 in which the alkyl 12. A process according to claim 1 wherein the catalyst is
tertiary-alkyl ether is methyl tertiary butyl ether. a crystalline aluminosilicate MFI-type Zeolite modified with
10. A process according to claim 1 wherein the alkyl aluminum fluoride Salt.
tertiary-alkyl ether comprises mainly methyl tertiary butyl 13. A process according to claim 1 wherein the reaction is
ether rich mixture containing unreacted isobutene and 5 carried out at a pressure of about 1 bar to 33 bar.
methanol.
11. A process according to claim 1 wherein the Said
aluminum-fluoride-modified Zeolite catalyst is in the hydro
gen form of Zeolite.