JPH07252173A - Production of isopropanol and ether from acetone - Google Patents

Abstract

PURPOSE: To produce the subject compounds simultaneously in one step by reacting acetone over a bifunctional catalyst comprising a hydrogenation catalyst composed of a specific metal and an etherification catalyst composed of zeolite and a specific metal oxide, wherein the hydrogenation catalyst is carried on the etherification catalyst.

CONSTITUTION: A saw material rich in acetone as an acetone flow is made to react over a bifunctional catalyst consisting of 5-45 wt.% of a hydrogenation catalyst comprising one or more metal elements selected from among Ni, Cu, Pt, Pd, Sn, and Cr and 95-55 wt.% of an etherification catalyst comprising zeolite and at least one oxide of a metal element selected from among the groups III and IV elements in the periodic table, which is supported on a carrier, in a weight ratio of the former (zeolite) to the latter (metal oxide) of 5:95 to 95:5 to obtain the objective ether from the acetone flow. It is preferable that the acetone flow further contains both of methanol and t-butanol by 5% or more.

COPYRIGHT: (C)1995,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a new integrated one-step process for producing high octane blend components for use in reblended gasoline from an acetone stream. This process involves reacting a crude acetone stream over a bifunctional catalyst to obtain an effluent rich in diisopropyl ether (DIPE), methyl-tert-butyl ether (MTBE) and isopropyl-tert-butyl ether (IPTBE). . Isopropyl alcohol is an intermediate product of the process, which may be isolated if desired.

Bifunctional (hydrogenation / etherification) catalysts are
It includes a zeolite selected from the group consisting of β-zeolite, medium-pore pentasil-type zeolite, and Y-zeolite; and a hydrogenation catalyst supported on a carrier made of a Group III or IV oxide of the periodic table.

[0003]

It is known to those skilled in the art that ethers, including symmetrical and unsymmetrical ethers, can be prepared to form the desired products by reacting one alcohol with another. . The reaction mixture containing the catalyst and / or condensing agent can be separated and further processed to give the desired product. Such further processing usually involves one or more distillation operations.

Hydrogenation catalysts are known and are generally selected from Group VIII of the Periodic Table. Suitable metals include, but are not limited to, platinum, palladium, tin, nickel and copper (alone or in combination).

US Pat. No. 3,955,93 to Sommer et al.
No. 9 (1976) discloses the production of an anhydrous mixture of isopropyl alcohol, diisopropyl alcohol, diisopropyl ether and by-products by catalytic hydration of propylene in the gas phase at temperatures of 140-170 ° C. The anhydrous mixture formed by this method can be used as such as an additive to gasoline fuels.

US Pat. No. 5,144,0 to Harandi et al.
No. 86 is an integrated multi-stage process for producing diisopropyl ether and substantially pure propylene, the second stage of which comprises isopropyl alcohol containing about 0-20% water, 30: 1 to 50:
A method of contacting with an etherification catalyst which is a large pore acidic zeolite consisting of β-zeolite having a Si: Al ratio of 1 is disclosed.

Another class of molecular sieve zeolites that has been studied for industrial use is the pentasil-type zeolite. The pentasil family of zeolites includes a continuous system in which ZSM-5 and ZSM-11 are end members. "Zeolite A by TE Whyte et al.
dvances in the Chemical and Fuel Industries: ATech
nical Perspective "(Catal. Rev.-Sci. Eng., 24,
(4), 567-598 (1982)).

An excellent review of zeolite applications, including pentasil-type zeolites, can be found in "Zeolite Catalysts Fa
"Ce Strong Industrial Future" (Europe
an Chemical News, 10 July, 1989, p. 23). For example, medium pore size H-ZSM-5 is often added to Y-zeolite catalytic cracking catalysts to increase the aromatic hydrocarbon content of the gasoline cut and thus the engine octane number. ZSM-5, which has two kinds of pores with a diameter of about 5 to 6Å intersect and give a space region with a diameter of about 9Å at the intersection.
Of in limited space, resulting from the deformation of the wide range of raw materials, alkanes, the product containing olefins and alcohols, there is a separation boundary around the C ₁₀ -C _11.

US Patent Application No. 07/01
No. 7,218, methyl-tert by reacting butanol with methanol in the presence of a catalyst containing superacidic alumina or faujasite type zeolite.
-A method for producing butyl ether is disclosed.

All of the references cited are acetone,
In particular, it does not appear to suggest a one-step conversion of low-value crude acetone in the by-product stream to useful oxygenated organic compounds. The proportion of acetone in the by-product stream containing acetone is usually about 20-80%.

[0011]

Acetone, especially acetone from the by-product stream, is fractionated to diisopropyl ether (DIPE), methyl tert-butyl ether (MTB).
E) and isopropyl-tert-butyl ether (IP
If it could be converted in one step to a useful oxygen-containing organic compound product from which TBE) could be isolated, it would greatly increase the economics of the process for preparing MTBE and other oxygen-containing organic compounds.

[0012]

According to the present invention, a one-step process for producing ether from an acetone stream, preferably a crude acetone stream, especially a crude byproduct acetone stream, wherein the acetone-rich feedstock is nickel, copper or platinum. 5 to 45% by weight of a hydrogenation catalyst consisting essentially of one or more metals selected from the group consisting of palladium, tin and chromium; and zeolite and at least one selected from groups III and IV of the periodic table And the relative weight ratio of the zeolite component and the metal oxide component is 5: 95-9.
There is provided a process comprising reacting over a bifunctional catalyst consisting of 95-55% by weight of etherification catalyst ranging from 5: 5.

Preferably, the zeolite is selected from the group consisting of β-zeolites, pentasil type zeolites and Y-zeolites.

High octane number mixed components for use in reblended gasoline, such as diisopropyl ether (DIPE), methyl tert-butyl ether (MTBE) and isopropyl tert-butyl ether (IPTBE), are prepared by the method outlined above. If so, the acetone stream, in particular the by-product acetone stream, further contains significant amounts of both methanol (MeOH) and tert-butanol (tBA), preferably in excess of 5%. When DIPE, MTBE and IPTBE are produced at the same time, the acetone raw material, particularly the crude acetone raw material, contains methanol and tert-butanol at 10 to 40% respectively.
It is preferable to contain each of them.

This one-step synthesis can be expressed as in Equation 1.

[0016]

[Chemical 1]

In the process for producing propylene oxide, a number of by-products are usually produced along with the desired product. Such by-products include formic acid, acetic acid, tert-butanol and acetone. Acetone can make up about 20-80% of a particular crude byproduct stream. These crude acetone streams may be further mixed with methanol.

It is known in the related art to produce IPA and DIPE by hydrating propylene, followed by etherification of isopropyl alcohol (IPA). The present invention describes the use of crude acetone containing tert-butanol (tBA) and methanol (MeOH) in the presence of a bifunctional catalyst and hydrogen to give I
It allows the production of PA and DIPE as well as other ethers such as MTBE and IPTBE in a single step. The bifunctional catalyst is 5 to 45% by weight of a hydrogenation catalyst consisting essentially of one or more metals selected from the group consisting of nickel, copper, platinum, palladium, tin and chromium.
Of 55% to 95% by weight (calculated based on the total weight of the catalyst) of a carrier consisting essentially of zeolite and a Group III or IV oxide of the Periodic Table.

In the catalyst, the total weight ratio of the portion comprising the hydrogenation catalyst is preferably 5 to 40% by weight. A preferred metal combination for use in the hydrogenation catalyst portion of the catalyst is a combination of nickel and copper, in which case N
The total metal content of i / Cu is in the range of 8-40% by weight, more preferably 25-35% by weight. The catalyst is 20 to
30% by weight, preferably 15-30% by weight, especially about 28
It contains a nominal amount of nickel by weight, and 2 to 15% by weight, preferably about 4% by weight of copper.

In some cases, it may be useful to include chromium in addition to nickel and copper, as exemplified in Example 4 below. If chromium is included, its proportion is preferably about 1 to 5% by weight, preferably about 2% by weight.

The etherification catalyst portion of the catalyst is composed of 5 to 95% by weight of β-zeolite, medium pore size pentasil-type zeolite or Y-zeolite and Group III or IV of the periodic table.
It is preferably composed of 95 to 5% by weight of a group oxide. For the etherification catalyst part of the catalyst, the zeolite is 5-6
More preferably, it constitutes 5% by weight and the metal oxide constitutes 95 to 35% by weight. In Example 1 described later, Ni-
Illustrating the use of a Cu hydrogenation catalyst supported on a carrier composed of 10% by weight of β-zeolite and 90% by weight of alumina. The use of a carrier supported on 50 wt% is exemplified.

The most useful zeolites for the etherification catalyst portion of this bifunctional catalyst appear to be large pore zeolites, such as β-zeolites, or medium pore pentasil-type zeolites, ie those having pore sizes greater than about 5.5Å. Seen in.

Β-zeolite is a crystalline aluminosilicate having a pore size of more than 5Å. The composition of the zeolite, in its as-synthesized form, can be expressed as follows, as described in US Pat. No. 3,308,069.

[XNa (1.0 ± 0.1-x) TEA]
AlO ₂ · ySiO ₂ · wH ₂ O

Wherein x is less than 1, preferably less than 0.7; TEA represents the tetraethylammonium ion; y is greater than 5 and less than 100; w is the degree of hydration and is present. Depending on the metal cation, it was up to about 60 (it was found that the degree of hydration could be higher than initially defined if w was defined as up to 4).
The TEA component is calculated by the difference between the analytical value of sodium and the single theoretical ratio of cation to structural aluminum.

In the completely base-exchanged form, the β-zeolite has the following composition:

[(X / n) M (1 ± 0.1-x) H] A
lO ₂ · ySiO ₂ · wH ₂ O

In the formula, x, y and w have the above numerical values, and n is the valence of the metal M. This form of zeolite can also be partially converted to the hydrogen form by calcining, for example, at 200-900 ° C or higher. The complete hydrogen form can be obtained by ammonium exchange followed by calcination in air or an inert atmosphere such as nitrogen.

The preferred form of β-zeolite is the highly acidic high silica form, in the as-synthesized form at least 10: 1, preferably 10: 1 to 50: 1 silica: alumina molar ratio, and It has a surface area of at least 100 m ² / g.

Suitable β-zeolites for the practice of the present invention include Valfor C806β, Valfor CP815β and Valfor C86.
There is one Valfor is a registered trademark of PQ Corporation.

Val for C806 β zeolite is a β-zeolite powder in the form of a template cation. It is a highly silica-shaped selective zeolite containing an organic template used in the crystallization step, which was isolated after filtering and washing the synthetic product. C806β is 23-26 SiO ₂ / A
having a molar ratio of l ₂ O ₃ and a crystal size of 0.1 to 0.7 μm.
m, the surface area after firing is about 700 to 750 m ² / g, the cyclohexane adsorption capacity after firing is 19 to 24 g / 100 g, N
a ₂ O content is about 0.01 to 1.0% by weight in an anhydrous state,
The organic content is about 11-13% by weight on a dry basis.

Valfor C815 β-zeolite is a calcined β-zeolite powder in the hydrogen, sodium form. this is,
Similar to C806β, except that it is calcined to decompose the organic template. C815β is a highly silica-shaped selective aluminosilicate with a large pore size. C815β also has a SiO ₂ / Al ₂ O ₃ molar ratio of about 23-26. The crystal size, surface area, cyclohexane adsorption capacity and Na ₂ O are all in the same range as noted for C806β.

Also very effective for bifunctional catalysts is the isomorphous group of medium pore size pentasil-type zeolites.

[Molecular Sieve Cataly by J. Ward
sts "(Applied Industrial Catalysis,
Vol. 3, Ch. 9, p. 271 (1984)) outlines the structure of the petansyl type. These zeolites as well as silicalite have SiO ₂ / Al ₂ O ratios above 10. Silicalite is an inorganic molecular sieve described in US Pat. No. 4,061,724, which is incorporated herein by reference in its entirety. Silicalite typically has a Si / Al ratio of over 200. Silicalite, ZSM-5, ZSM-11 and related substances are
It has a structure of a 10-membered ring channel system as opposed to an 8-membered zeolite such as zeolites and erionites and a 12-membered system such as X- and Y-zeolites.

Pentacyl-type zeolite is more hydrophobic than A-, X- and Y-zeolites. ZSM-5
Have orthorhombic unit cells, while ZSM-11 is tetragonal.

The pentasil structure is highly exothermic and acid stable. These are synthesized in the presence of ammonium ions which are an integral part of the structure. When heated to 600 ° C., the organic cations are decomposed leaving a very porous structure.

The channel size of the pentasil-type substance is, for example, intermediate between that of small-pore erionite and that of large-pore Y-zeolite.

Other ZSM type zeolites are not considered to be pentasil type. ZSM-21, ZSM-35 and ZSM-38 are considered as ferrierite type zeolites. ZSM-20 is considered a faujasite type and ZSM-34 is considered an offretite / erionite group.

Examples of medium-pore pentasil-type zeolite having a 10-membered oxygen-containing ring system include ZSM-5 and ZSM-
11, ZSM-22, ZSM-23, ZSM-48 and Rhomontite. These framework structures contain 5-membered oxygen-containing rings, which contain more silicic acid than known zeolites. Often these zeolites are
A predominant amount of silicon and a very small concentration of other atoms,
For example, it can be synthesized with aluminum. Therefore, these zeolites can be considered as "silicates" with framework substitutions by small amounts of other elements such as aluminum. Of the zeolites in this group, ZS
Only M-5 and ZSM-11 have bidirectional intersecting channels, others have non-intersecting, unidirectional channels.

The medium pore size pentasil type, unlike other zeolites, has pores of uniform size and does not have a large supercage with smaller windows. This feature is believed to explain their tendency for unusually low coke formation in acid-catalyzed reactions. Pentacyl-type zeolite lacks narrow passages in the window / cage structure, so molecules larger than the size of the channel will probably not form, except at intersections.

The preferred form of the pentasil-type zeolite is that of the highly acidic high silica form having a silica: alumina molar ratio of at least 30: 1, preferably 30: 1 to 350: 1 in the as-synthesized form. Is. 5
0: 1 to 150: 1 narrower range of silica: alumina molar ratio of preferably, pentasil-type zeolites as exemplified in the examples, from about 31: 1 to about 350: 1 SiO ₂ / A
It has a 1 ₂ O ₃ ratio.

The zeolite etherification catalyst is a binder,
For example, it is formed in the presence of oxides of Group III or Group IV metals. Zeolites can be combined with binders by a variety of forming techniques. Group III or IV oxides used with the β-zeolite include aluminum, silicon, titanium, zirconium, hafnium,
There are germanium, tin and lead oxides and combinations thereof. Alumina is preferred. The above binders may make up 10-90% of the catalyst formed.

If necessary, the above metal oxide may be further modified with halogen, a halogen-containing organic compound or a halogen-containing acid. The halogen can be fluorine, chlorine, bromine or iodine, but is preferably fluorine. In the case of fluoride treatment, the fluoride content of the treated β-zeolite can range from 0.1 to 10% by weight, but is preferably about 1% by weight. If necessary, the above-mentioned fluoride-treated zeolite,
It may be calcined at 200 ° C. or above before further use or modification.

Another type of zeolite that is useful in the etherification catalyst portion of the integrated catalyst generally comprises a dealuminated Y-zeolite catalyst.

The catalysts for use in the reaction of formula 1 in the dealuminated form are the isostructural groups of certain crystalline aluminosilicate zeolites, in particular faujasite-type zeolites including synthetic X- and Y-zeolites. Is.
Among them, Y-zeolite is preferable.

The faujasite-type zeolite unit cells are cubic with a _o ≈2.5 nm and each contain 192 silicon- or aluminum-centered oxygen tetrahedra bonded through shared oxygen atoms. . Due to the net negative charge of each aluminum-centered tetrahedron, each unit cell contains an equal number of charge-balancing cations.
These are exclusively sodium ions in the zeolite in synthetic form. Typical cell contents of Y-zeolite in hydrated form are as follows:

Na ₅₆ [(AlO ₂ ) ₅₆ (SiO ₂ )
₁₃₆ ] _x・ 250H ₂ O

Y-zeolites are distinguished on the basis of their relative concentration of silicon and aluminum atoms and their influence on the detailed structure and related chemical and physical properties. The number of aluminum atoms in the unit cell of Y-zeolite is 76 to 48, resulting in S of 1.5 to 3.0
results in an i / Al ratio. Both the cation concentration and charge density of the aluminosilicate structure are lower for Y-zeolites than for X-zeolites where the unit cell has 96-77 aluminum atoms.

Preferably, the Y-zeolite is ammonium exchanged and then calcined, or treated with ethylenediaminetetraacetic acid (EDTA) or another chelating agent, or with a fluorine or fluorine containing compound such as The dealumination treatment is performed by treatment with silicon tetrafluoride or ammonium fluorosilicate, or by hydrothermal treatment and / or acid treatment. The dealuminated Y-zeolite should have a silica / alumina molar ratio of greater than 3, preferably greater than 5, and most preferably 5-100. The examples demonstrate the utility of catalysts with silica / alumina ratios of 5-50, especially 15-30.

Suitable commercial dealuminated Y-
Examples of zeolites are UOP LZY-82 and L
ZY-72, PQ CP-304-37 and CP-
316-26, and UOP Y-85, Y-8
4, LZ-10 and LZ-210.

The unit cell size and the SiO ₂ / Al ₂ O ₃ molar ratio of a typical dealuminated Y-zeolite are listed in Table 1.

[0052]

[Table 1]

MTBE, IPTBE and DIP in the title
Particularly effective for the simultaneous production of E is β-zeolite containing a metal oxide support.

The catalyst is powder, pellets, granules, spheres,
It can be in the form of shapes and extrudates. The examples described herein demonstrate the benefits of using extrudates.

The reaction can be carried out in either a stirred slurry reactor or a fixed bed continuous flow reactor. The catalyst concentration should be sufficient to provide the desired catalytic effect.

The hydrogenation / etherification to DIPE, MTBE or IPTBE can generally be carried out at 20 to 250 ° C, the preferred range being 50 to 200 ° C. Good results are seen throughout this temperature range. However, it can be noted that the best conversion values are found for the simultaneous production of MTBE and DIPE when the temperature is 99-143 ° C (210-290 degrees Fahrenheit). The total operating pressure can be 0 to 5,000 psig (0.1 to 35 MPa) or higher. The preferred pressure range is 1
0 to 1,000 psig (0.8 to 7 MPa).

Generally, IPA and DIPE are continuous at a total liquid hourly space velocity (LHSV) of up to 10 or more and at relatively mild conditions at concentrations up to about 98% by weight or more in the crude product liquor. Are generated automatically. LH
SV is determined as follows.

[0058]

[Equation 1]

In the following examples, the conversion rate of acetone was estimated using the following equation.

[0060]

[Equation 2]

[0061]

INDUSTRIAL APPLICABILITY According to the present invention, isopropyl alcohol and ethers such as diisopropyl ether can be simultaneously produced from an acetone stream, preferably a crude acetone stream, in one step. The method of the present invention is advantageous because it can utilize, as crude acetone, a by-product such as acetone that is by-produced in the propylene oxide production process. Further, any ether can be produced by subjecting methanol and / or tert-butanol to coexist in the crude acetone stream and subjecting them to the reaction.

[0062]

EXAMPLES In the following examples, the following is noted. (1) Acetone is almost completely converted to IPA (major product) and a small amount of 2-methylpentane and an unknown alcohol.

(2) In Example 1, about 140 to 149 ° C.
At a reaction temperature of (284 to 289 degrees Fahrenheit), optimum selectivity to DIPE (15.4 to 15.9%) was achieved.
Temperatures above 143 ° C. (290 degrees Fahrenheit) are detrimental to the combined yield of the desired products (IPA and DIPE) and accelerate the dehydration reaction of IPA to propylene, forming a large amount of gaseous product. Tend to bring.

(3) In Example 2, over a temperature range of 99 to 129 ° C. (210 to 264 degrees Fahrenheit), the yield of DIPE increased as the temperature increased.

(4) D at each comparable temperature
A comparison of IPE yields between Example 2 and Example 1 shows that the DIPE yield increases as the β-zeolite content increases. Selectivity to DIPE of up to 20% was achieved in Example 2 at 129 ° C (264 ° F). The combined yield of IPA and DIPE is 119 ° C.
It reaches a maximum of 96.2% at (246 degrees Fahrenheit).

(5) The results show that high yields of IPA and DIPE are obtained from hydrogenating pure acetone over Ni / Cu catalysts supported on β-zeolite / alumina support. Demonstrate. The total metal content of Ni + Cu is in the range of 8-40% by weight, and Ni: C
The atomic ratio of u is in the range of 1: 1 to 1:10. The β-zeolite content in the carrier is in the range of 5-95%.

The following examples merely illustrate preferred embodiments. Many modifications may be made thereto without departing from the essence of the disclosed invention, as will be apparent to those skilled in the art.

Example 1 A support containing 50 g of 10% β-zeolite / 90% alumina was impregnated with 40 ml of an aqueous solution containing 51 g of nickel nitrate hexahydrate and 5.4 g of copper nitrate hemipentahydrate. Ni on the above carrier containing 10% of β-zeolite
A catalyst supporting 32% / Cu was prepared. The impregnated carrier was dried at 121 ° C (250 ° F) for 2 hours and then calcined at 315 ° C (600 ° F) for 4 hours. The calcined support was again impregnated with 37 ml of an aqueous solution containing 51 g of nickel nitrate hexahydrate and 5.4 g of copper nitrate hemipentahydrate. The impregnated carrier was dried at 121 ° C (250 ° F) for 2 hours and then calcined at 482 ° C (900 ° F) for 8 hours.

Catalyst screening experiments were carried out in a microreactor test unit having two reactors in series separated by a quench zone. Both reactors were operated in downflow mode. The upper reactor was filled with 4 ml of catalyst. The second reactor had two catalyst beds, each containing 4 ml of catalyst, separated by a bed of 4 ml of inert material. The total catalyst loading in the unit was 12 ml. An internal thermocouple was placed at the bottom of each catalyst bed. A liquid raw material was supplied to the unit using a high-pressure pump, and hydrogen was measured by a mass flow controller. Hydrogen and the liquid raw material were mixed and supplied to the unit. The molar ratio of hydrogen to acetone is about 0.
It was 5: 1 to 30: 1, preferably about 1: 1 to 3: 1. In order to simplify the analysis of liquid products by GC,
Pure acetone was used as a raw material to demonstrate the chemical treatment included in the present invention.

Under a nitrogen stream, 70 psig (0.5 MPa)
) From room temperature to 315 ° C (60 ° F) for 8 hours.
The catalyst of Example 1 was activated by slowly heating to (0 degrees). Next, the unit pressure is 500 ps with hydrogen
The catalyst bed was maintained at 315 ° C. (600 degrees Fahrenheit) for 12 hours under a stream of hydrogen and ig (3.5 MPa). The catalyst bed was cooled to below 93 ° C (200 ° F). Technical grade acetone (97% pure) at 1 LHSV and 500 psig
It was supplied to the unit at (3.5 MPa). The flow rate of hydrogen was adjusted so that the hydrogen: acetone molar ratio was 5: 1. The reaction temperature is 99 ° C to 163 ° C (210 to 325 ° F).
Degree). -32 ° C (0 ° F) and 300
Liquid product was collected periodically in a cooled receiver at psig (2.1 MPa). The product was analyzed by GC,
The composition of hydrocarbons and oxygen-containing organic compounds was determined and the water content was measured by Karl-Fischer titration.

The results of the analysis of the liquid product are summarized in Table 2.

[0072]

[Table 2]

Example 2 In the catalyst of Example 2, the carrier used was β-zeolite 50.
% And 50% alumina, but prepared by the same procedure described above for Example 1.

The catalyst was activated and technical grade acetone was fed in the same manner as used in Example 1. The results of analysis of the liquid product are summarized in Table 3.

[0075]

[Table 3]

Example 3 The catalyst of Example 3 was prepared by the same procedure described above for Example 1 except that the support was a mixture of 60% β-zeolite and 40% alumina.

The catalyst was activated and tested by the same method used in Example 1. The results of analyzing the liquid product are summarized in Table 4.

The result is that the reaction temperature is 124 ° C. (256 ° F.
), A selectivity of up to 25% by weight to DIPE was achieved, indicating that the combined IPA and DIPE yield was 89.8%.

[0079]

[Table 4]

Example 4 The catalyst of Example 4 is used to illustrate the application of medium pore size pentasil-type zeolite ZSM-5 to the process of the present invention. The catalyst was prepared using a carrier (8162CT91) consisting of 80 wt% ZSM-5 zeolite with a silica / alumina molar ratio of 223 and 20 wt% alumina. 50 g of the dried carrier are impregnated with 35 ml of a solution containing 11.4 g of copper nitrate, 2.2 g of nickel nitrate and 4.4 g of chromium nitrate. The impregnated carrier is 121 ° C (25 ° F)
It was dried at 0 ° C. for 2 hours and calcined at 315 ° C. (600 ° F.) for 2 hours and 427 ° C. (800 ° F.) for 4 hours.
The obtained catalyst contained 7% by weight of CuO, 2% by weight of CrO ₃ , and 1% by weight of NiO.

The catalyst was activated and tested in the same manner used in Example 1. The results of analyzing the liquid product are shown in Table 5.
Put together. The results show that with the ZSM-5 zeolite-containing catalyst, IPA and D at 104 ° C. (219 ° F.)
Yield 92.5% by weight combined with IPE, and DIP
It shows that a yield of E of about 10% by weight was obtained.

[0082]

[Table 5]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C07C 29/145 41/09 43/04 B 7419-4H // C07B 61/00 300 C07C 31/10 9155-4H (72) Inventor Pay-Shin Eugene Dye USA, Texas 77642, Port Arthur, Brittany 3437 (72) Inventor Robert Joel Taylor Jr. USA, Texas 77642, Port Arthur, Sleepy Hollow Lane 4120 (72) Inventor Bobby Ray Martin USA, Texas 77707, Beaumont, East Coldwood Drive 285

Claims (2)

[Claims] 1. A one-step process for producing ether from an acetone stream, wherein the acetone-rich raw material is hydrogen consisting essentially of one or more metals selected from the group consisting of Ni, Cu, Pt, Pd, Sn and Cr. 5 to 45% by weight of catalyst; and zeolite and II of the periodic table
From an etherification catalyst consisting essentially of at least one metal oxide selected from Group I and Group IV and having a relative weight ratio of zeolite component to metal oxide component in the range of 5:95 to 95: 5. Reacting on a bifunctional catalyst containing 95 to 55% by weight of the carrier. 2. The acetone stream is further mixed with methanol and te.
The method of claim 1 containing at least 5 wt% each of rt-butanol.