JPH02102727A - Chemical conversion method - Google Patents

Abstract

PURPOSE: To make catalytic selectivity for a desired product higher by bringing a supply source material into contact with a crystalline porous three-dimensional solid catalyst which is present as a liquid slurry having a reactivity lower than that of the supply source material so as to catalytically convert the source material. CONSTITUTION: A crystalline porous three-dimensional solid having an ability to promote conversion is compounded in a liquid which is different from the supply source material or the product and which has a reactivity lower than that of the supply source material so as to prepare a catalyst slurry. The supply source material is brought into contact with the catalyst slurry prepared as above described under effective conditions to convert the supply source material into the product so as to obtain the product by catalytic conversion. The supply source material is more soluble in the liquid than the product, and the product is preferably substantially insoluble with the liquid. It is preferable that the liquid to prepare the catalyst slurry contains an effective component such as a base to improve the catalytic activity.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for chemical conversion using a catalyst. More particularly, the invention relates to such chemical conversion processes using certain defined catalysts and reaction systems that yield significant results.

Chemical conversions using solid catalysts are often carried out using either a fixed bed or a fluidized bed of catalyst particles. That is, the substance to be converted is brought into contact with a solid catalyst present in the particles of a fixed bed or the particles of a fluidized bed. However, each of these two modes of operation has significant disadvantages. For example, the use of fixed catalyst beds often leads to temperature regulation problems that adversely affect catalyst performance. Regenerating and/or reactivating a fixed catalyst bed can lead to significant process downtime because the chemical conversion must be stopped for processing while the catalyst remains in the reaction vessel, for example. In the case of fixed catalyst beds, it is also difficult to obtain a uniform catalyst activity distribution, especially in situations requiring frequent regeneration.

Fluidized catalyst beds typically provide better temperature control than fixed catalyst beds. However, fluidized, catalyst bed reaction systems are also much more complex than fixed catalyst bed reaction systems.
For example, a fluidized catalyst bed reaction system typically includes at least two separate vessels, each containing a fluidized catalyst bed, one to perform the chemical conversion and one to regenerate and/or reactivate the catalyst. . The catalyst particles are transported between two separate containers, eg, transported substantially continuously. Separation equipment, such as a cyclone separator and slide valve assembly, is required to separate the catalyst particles from the feedstock/reaction products and regeneration/reactivation medium and to control the flow of catalyst between the two vessels. It often happens. Also, although the catalyst particles are relatively small in order to flow, they must be blended with additional components such as binders and often fillers to strengthen the particles, for example against abrasion, so that the particles flow. Constant and sometimes even turbulent movements within catalyst bed reaction systems and separation devices can be better tolerated. These additional components are also often present in fixed bed catalysts as well and often promote undesirable chemical reactions or otherwise adversely affect the catalytic performance of the catalyst. These additional components are also particularly troublesome when used with crystalline microporous three-dimensional solid catalysts or CMSCI, catalysts that promote chemical reactions of molecules with selected dimensions, shapes, or transition states. It can be.

One alternative chemical reaction system involves using a catalyst slurry, developed by McGraw-Hill Book Company, New York (
(1980), Charles N., Satterfield (Charles N.

The following is written on page 317 of ``Heterogeneous Scatterist Inbractis'' by J.D. 5 Atterfield: ``Reactions in liquids are often carried out by suspending solid catalysts in finely divided form in the liquid. Often referred to as a "slurry reactor." If the gas is intended to react with the liquid, the gas may be introduced through a distributor at the bottom of the vessel or the gas may be dispersed into the liquid with a mechanical stirrer; this also applies to solids. It also works to keep the substances suspended. ” Thus, in the prior art, “slurry reactors” are used to carry out reactions between liquids or gases and liquids in the presence of catalysts. using the device. A considerable amount of research effort has been directed toward the use of slurry reactors, such as methanol production from synthesis gas, and applications in Fischer-Tropsch reactions. See, e.g., M. B. Sherwin et al., "Make Methanol Bi-Sleeve Nice Reaction," Vitro Garbon Processing, pp. 122-124, November 1976: U.S. Pat. No. 3.888. .896 and 4,03
No. 1,123; M, L, Rie
Kena), et al., “A Comparison of Fischer-Trobsch Reactors,” Chemical Engineering Progress, pp. 86-90, April 1982;
of a slurry type Fischer-Tropsch reactor for processing synthesis
Gas of Raw Hyde “Rodien-Carbon Monooxide Reactors”, Canadian Journal of Chemical Engineering, Vol. 60, pp. 159-162, 1
982.

Slurry reaction systems offer considerable advantages; for example, temperature control is relatively easily maintained in such systems. However, because of the relatively long contact between the catalyst, liquid reactants, and products, selectivity to the desired product can be poor. It would be advantageous to provide a new chemical conversion process that uses solid catalysts.

Methanol can be readily produced from coal and other raw materials using well-known commercial processes, e.g. by burning any carbonaceous material, including coal, or any organic material, e.g. hydrocarbons, carbohydrates, etc. Synthesis gas can be converted into methanol by well-known heterogeneous catalytic reactions.

Marcel Decker Incorporated in New York)
Publishing (1983) Tararence Day, Chan (C
``Hydrocarbons from Methanol'' by George D. Chang) represents a survey and summary of the technology that its title describes. Chan is 21-26
Page discusses the conversion of methanol to olefins in the presence of molecular sieves. Examples cited by Chang as molecular sieves suitable for converting methanol to olefins are chabazite, erionite, and synthetic zeolite ZK-5.

one or more crystalline microporous three-dimensional materials or CMS
Catalysts containing M include naturally occurring molecular sieves and synthetic molecular sieves (together referred to as "molecular sieves").
) and layered clays.

Among the CMSMs that can be used to promote the conversion to methanolic olefins are non-zeolitic molecular sieves or NZMS, such as aluminophosphate or ALPO, particularly U.S. Pat. No. 4,440,871.
Silicoaluminophosphate or S disclosed in No.
There is an APO.

U.S. Patent 4,499 issued February 12, 1985
．． No. 327 discloses a process for the catalytic conversion of methanol to light olefins using SAPO under effective process conditions. Each of these US patents is incorporated herein by reference in its entirety.

Le beans 51 deaths A method has been discovered for the catalytic conversion of feedstock to product.

In one broad aspect, the method comprises providing a feedstock with a crystalline microporous three-dimensional solid catalyst, CM
The catalyst is contacted with the SC at conditions effective to convert the feedstock to the product, and the catalyst is present in a slurry with a liquid that is different from the feedstock or product and is less reactive than the feedstock. include.

The catalytic conversion method offers considerable advantages, e.g., CM
Less reactive liquids can be used in slurries with SC to improve overall process performance, such as effective temperature control, catalyst selectivity to desired products.

The method according to the invention provides improved temperature control for several reasons; the transfer of heat between a solid surface, such as a catalyst, and a liquid, such as a suspension, The transfer of heat between such solids and gases is much better than in the case of processes. It also increases the rate of heat transfer between the suspension and the reaction zone walls, which allows for better control of the temperature of the reaction zone contents. If overheating occurs, the suspension will boil, thus limiting the extent of thermal runaway. In addition, the possibility of hot spots that could damage the catalyst in fixed catalyst bed systems is less likely to occur with this slurry method.

The slurry environment of the present process allows for effective control of the activity of the catalyst and greatly reduces physical and mechanical attrition and tearing for solid catalysts.

A zero-slurry reaction system in which the composition of catalyst particles can be adjusted to improve catalyst performance without incurring significant physical loss of the catalyst may also be used for other modifications or applications that lead to improved process performance, e.g. Also useful as described herein, the present chemical conversion system can be relatively easily scaled up to commercial size units based on data from relatively small pilot plants.

In summary, the method utilizes MC3C, preferably M
It is an effective approach for chemical conversion that makes extensive use of C5C.

As mentioned above, CMSCs are catalysts that promote chemical reactions of molecules of selected size, shape, or transition state. That is, CMSCs are catalysts that promote chemical reactions of feedstock molecules subject to predetermined molecular size, molecular shape, or transition state constraints. Different CMSCs have different size/shape/transition state constraints depending on the physical structure and chemical composition of the catalyst, such as the effective diameter of the pores. Thus, the particular CMSC chosen for use depends on the particular feedstock employed,
Depends on the specific chemistry (reaction) and products desired. CM
Preferably, the SC has a substantially uniform pore structure, e.g., substantially uniformly sized and shaped pores.
MSCs include, for example, layered clays, zeolitic molecular sieves, and non-zeolitic molecular sieves or NZMS.

Currently useful NZMS include molecular sieves encompassed by the experimental chemical composition represented by the following formula on an anhydrous basis: (1) mR: (QwAlxPySiz)Oa where rQJ is a framework oxide unit with charge rnJ rQO*
"" (rnJ can be -3, -2, -1, 0 or +1); "R" represents at least one element present in the intracrystalline pore system;
represents the organic templating agent of the species: “m” is (Q-A
I-PySiz) "R" present per mole of Ox
"W" represents the molar amount of and has a value of 0 to about 0.3;
, rxJ, "y" and "z" are present as framework oxide units, respectively QO*, A 10g-1PO2, S
i Ox (represents the D mole fraction, "Q" is an average of about 1.51 to about 2.06 in the tetrahedral oxide structure (7)
Characterized as an element with rT-OJ spacing. "Q"
has a cation electronegativity of about 125 to about 310 Kcal/g atom and rQJ is about 59 at 298'K.
Stable Q in crystalline three-dimensional oxide structure with rQ-OJ bond dissociation energy larger than cal/g atom
-0-P, Q-0-AI or Q-0-Q bonds (EP published on October 30, 1985)
rE on pages 8a, 8b and 8a of C Publication No. 0159624
See discussion of the characterization of LJ and rMJ, which are equivalent to Q as used herein); rwJ
, rxJ, "y" and rzJ represent the mole fractions of "Q", aluminum, phosphorus and silicon, respectively, present as framework oxides, which mole fractions are within the limiting composition values or points as follows: W is equal to 0 to 99 mol%; y is equal to 1 to 99 mol%; X is equal to 1 to 99 mol%: Z is equal to 0 to 99 mol%.

rQJ of formula (I) rQAPsOJ molecular sieve
may be defined as representing at least one element capable of forming a framework tetrahedral oxide and may be 1f1 of the following elements: arsenic, beryllium, boron, chromium, cobalt, gallium. , germanium, iron, lithium, magnesium, manganese, titanium, vanadium and zinc are intended to represent Q and such combinations, to the extent present in the structure of QAPSO, are It exists in the range of 1 to 99%. It should be noted that the formula (■) is intended for the case where Q and St do not exist. In such cases, the working structure is aluminophosphate or A I P O
This is the structure of 4. If Z has a positive value, the working structure is that of silicoaluminophosphate or SAPO. From this, the term QAPSO does not necessarily indicate the presence of elements Q and S (actually Si).
When Q is multiple elements, in which case the elements present, to the extent contemplated by this invention, the operative structure is ELAPSO or ELAPO or MeA as discussed herein.
This is the structure of PO or MeAPSO. However, Q
If it is intended to invent molecular sieves of QAPSO variants in which QAPSO is another element, we intend to include them as molecular sieves suitable for carrying out the present invention.

Examples of QAPSO compositions and structures can be found in the patents and patent applications described in Table A below, and in the patents and patent applications listed in Table A below. Murakami, Knee, Shijima, Jie, Double, Ward (J, W, War
Proceedings of the 7th International Zeolite Conference, “New Developments and Zeolite Science Technologies”, edited by d)
Flanigen (1986), pp. 103-112 (1986).
"Aluminophosphate molecular sieves and xaviariodic table" announced by Nigen) etc.
The various compositions and structures described in the paper entitled: Table A U.S. Patent MAPO is MO*-", AIO
*-14,567,029 and PO, a crystalline metal aluminophosphate having a three-dimensional microporous framework structure of tetrahedral units and having an experimental chemical composition represented by the formula MJlyPjOs: In certain two formulas, rRJ represents at least one organic templating agent present in the intracrystalline pore system; "m" has a typical value of 0 to 0.3; and (M, AI.

represents the mole of rRJ present per mole of P-)Os; "M" represents magnesium, manganese, zinc or cobalt; "X", [y" and rzl represent each "M" present as a tetrahedral oxide; ], 0 mole fraction, representing the mole fractions of aluminum and phosphorus, are those that fall within the rectangular composition region defined by points A, B, C, and D of FIG. 1 of the patent diagram.

This patent states that in column 6, aluminum Phosphate as a phosphorus source (26 ~28 lines) and as an aluminum source US patent 4,440,871 Possible (lines 38-40) Seed the desired molecule using seed crystals. assisting in the crystallization of (lines 59 to 63) are described.

Example 85 uses MAPO-36 as a seed crystal. To produce MnAPO-36 using It represents that. MnAPO The chemical composition of -36 is magnesium It doesn't show any presence.

SAPO molecular sieve is a common glass of microporous crystalline silicoaluminophosphate. The pores have a nominal diameter greater than about 3 mm. The "essential experimental composition" is mR:(SIJlyPx)Oi: where rRJ represents at least one organic templating agent present in the intracrystalline pore system = "m" is a representative of O ~ 0,3 and (Si.

"X", ryJ and rzJ represent the mole fractions of silicon, aluminum and phosphorus, respectively, present as tetrahedral oxides; within the pentagonal composition area defined by points A%B, C, D and E of the ternary figure of Figure 1, preferably defined by points a, b, c%d and e of Figure 2 of the patent diagram. Located within a pentagonal compositional region. The S APO molecular sieve must meet at least Table I, ■, ■, ■, ■, Xl, X [II% XV, XVII, XlX, X
XI, XXIII or XXV (7) have an intrinsic X-ray powder diffraction diagram containing the d-spacing described in No. Furthermore, the as-synthesized crystalline silicoaluminophosphates of said patent are disclosed in commonly assigned U.S. Patent Application filed April 13, 1984, for all organic compounds present in intracrystalline pore systems as a result of such synthesis. 600,312 The plate can be fired at a temperature high enough to remove at least some of the material. Silicoaluminophosphates are collectively referred to in the patent as rsAPOJ, or class, or rsAPo-nJ, where rnJ is an integer denoting the particular SAPO whose preparation is reported in the patent. .

U.S. Patents, Column 8, 12-16 In the row, grow SAPO seeds using seed crystals. It describes what will be accomplished. That technique The method is described in Examples 22.51 and 53. ing.

ELAPSO molecular sieve has E L Ox and A 10sP O* in the framework structure.
, S i Ot unit content and U mR on anhydrous basis:
(having an experimental chemical composition represented by the formula ELwAlxPySljOz: where "EL" is the charge rn or + 1) represents at least one element present as a framework oxide unit "EL01"J: "R" represents at least one organic templating agent present in the intracrystalline pore system; represents: "m" is (ELwAl, P.

5it) indicates the molar amount of (RJ) present per mole of Os and has a value from 0 to about 0.3: "W", rxJ, "y", rzJ are each present as a framework oxide unit; ELOz, A l 02-1PO*, S
rELJ, which represents the mole fraction of iO
cal/g - cationic electrocathogenicity of the atom, (c) 29
Stable M-0-P, M-0-AI, or M-0 in a crystalline three-dimensional oxide structure with an "M-0" bond dissociation energy greater than about 59 kcal/g-atom at 8°K. It is characterized as an element that has the ability to form -M bonds.

rwJ, rxJ, ryJ and rzJ exist as skeletal oxides. ELJ, aluminum, phosphorus and 0 mole representing the mole fraction of silicon The fraction is the limit composition value or Get within the range of points: D O,010,010,98 E　　O,600,010,39 Here rpJ is rELJ (EL.

A1 yo PySi, ) Ox is an integer corresponding to the number of elements represented in the composition.

February 1985 Patented on the 9th US Patent 4.500° No. 651 where "p" is as defined above It is.

The EP publication states on page 16 that crystallinity and and amorphous aluminophosphate Used as a carbon and aluminum source It discloses that and on page 17, Seed the reaction mixture 0 examples 11A and 12A described.

93A-103A, 5B, 6B.

55B, 58B, 59B, 50D- 56D, 59D-62D and 12F -15F indicates use of seed crystals ing.

TAPO molecular sieve consists of a three-dimensional microporous crystalline framework structure of [T i O□], [AIO□], [poil tetrahedral units, which has a unit empirical formula on an anhydrous basis of the following formula: mR :(TIJlyPz)Oi (1) [wherein,
R is present in the intracrystalline pore system and rELJ can be defined as representing at least one element forming a framework tetrahedral oxide and preferably arsenic, beryllium, boron, chromium, cobalt, gallium, selected from the group consisting of germanium, iron, lithium, magnesium, manganese, titanium, and zinc; "W", rxJ, ryJ and rzJ are the mole fractions of rELJ, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides; dO,550,100,35 where the mole fraction falls within the limiting composition values or points as follows: d O,550,100,35 "m" represents (T+J1yP ,)031
represents the moles of rRJ present per mole, and from 0 to 5.
0, the maximum value in each case depends on the molecular dimensions of the templating agent and the effective pore volume of the pore system of the particular titanium molecular sieve; "X", "y", rzJ are the tetrahedral oxides; represents the mole fractions of titanium, aluminum, and phosphorus, respectively, present as, for "x", ryJ, rzJ: A 01001 0.45 8 G, 88 0.01 CD, 98 0.01 D O,290,70 E O,00010,70 0,549 0,11 0,01 0,01 0,299 The parameters rxJ, ryJ, rzJ preferably have the following values for rxJ, ryJ, rzJ Enters: a θ, 002 0.499 0.49
9bO12Q Q, 40 Q, 4
0 c O, 200, 500, 30 d O, 100, 60 G, 30 e O, 0020, 600, 398 TAPO molecular sieves typically also have an intracrystalline adsorption capacity of water at 4.6 Torr and about 24°C. Characterized by 3.0% by weight. Water adsorption was observed to be completely reversible, retaining the same essential framework morphology in both hydrated and dehydrated states.

The US patent describes crystalline or amorphous aluminophosphate in column 8, lines 65-68 and column 9, lines 15-18, and US Patent Application No. 600, 179, filed on April 13, 1984, 1985. According to EPC Publication No. 0161488 published on November 21st, we are considering using it as an aluminum source. Column 6, lines 1-5 states that seed addition facilitates the crystallization procedure. Comparative Example 44 describes a composition of amorphous T i O* and 95% by weight AlPO418, but does not indicate how the composition was prepared.

TiAPSO molecular sieve is TiO! with an experimental chemical composition represented by the following formula on an anhydrous basis: ,AIO,-1P0z” and 5i02 with a three-dimensional microporous framework structure of tetrahedral oxide units: mR: (71wAl+1PySi,1)Os where rR
J represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of rRJ present per mole of (TfwAI*PySil)02, ranging from O to about has a value of 0.3: "1" rxJ. The zero mole fractions rwJ, rxJ, "y", and rzJ having values of . A 0.60 B 0.311 C84 old DO, θl E Q, 6Q 1APS 0.38 0.02 0.60 0.02 0.60 0.39 0, old 0.98 0.01 0. 390 In the subclass of molecular sieves, the values in the above formula, rwJ, rxJ, "y", and rzJ, are the quadrilateral composition defined by points a, b% C5 and d of the ternary diagram in Figure 2 of the application. and these points a, b, c, and d represent the following values for r w J, rxJ, "y", and rzJ: a O,550,430,02 b O,430, 550,02c O,10Q,55 Q,35d
O, 550, 100, 35, the publication describes on page 13 the use of crystalline or amorphous aluminophosphate as a source of phosphorus and aluminum, and on page 14 that seeding the reaction mixture There is a US Pat.

Ferroaluminophosphate (F APO) is disclosed in U.S. Pat. No. 4.554.143, herein incorporated by reference, and is
10*, has a three-dimensional microporous crystalline framework structure of F802 and PO2 tetrahedral units, and has the following essential experimental chemical composition on an anhydrous basis: mR: (FelIAlyPjOa where rRJ is the intracrystalline pore “m” represents at least one organic template agent present in the system; “m” is (FeyoAl, P,)O
represents the mole of rRJ present per mole of l and O
~0,3, with the maximum value in each case depending on the molecular dimensions of the templating agent and the effective void volume of the pore system of the particular ferroaluminophosphate involved = "X", "y", and rzJ represents the mole fraction of iron, aluminum, and phosphorus, respectively, present as tetrahedral oxides, and represents the following values for rxJ, r/J, and "Z": A 0.01 0.60 0.3
9B O,010,390,60 CO,350,050,60 D O,350,600,05 When synthesized, the minimum value of rmJ in the above formula is 0.02. In a preferred subclass of ferroaluminophosphates, the rxJ, "y", and rzJO values in the above formula represent the following values of rxJ, ryJ, and rzJ: Lμueyu a O,010,520,47 b O,010,390,60 c O,250,150,60 do, 250.40 0.35FeO□The iron in the structural unit mainly depends on the iron source in the synthetic gel. and can be in either the ferric or ferrous ionic valence state.

That is, the F e O* tetrahedra in the structure can have a net charge of either -1 or -2.

The patent is in column 5, lines 43-45 and In lines 54-56, crystalline or amorphous Aluminophosphate It can be used as a source of aluminum and and Column 6, lines 1-5, show the reaction mixture reaction mixture. If the addition of hydrogen accelerates the crystallization procedure, April 1984 Apply on the 13th US Patent application no. 600, 173 issue, November 1985 Announced on the 21st was done EPC announcement No. 0161491 It is listed.

FeAPSO molecular sieves include FeO□-2 (and/or Fees), A I Oa, Pot and Si
It has a three-dimensional microporous crystalline framework structure of tetrahedral oxide units of Oa, and has the following unit empirical formula on an anhydrous basis: mR: (Few^1mPyS1glOz (
1) In the formula, "R" represents at least one organic template agent present in the intracrystalline pore system; "m" represents "R" present per mole of (Fe, A1.P, 5ix)Oa. '' and has a value from 0 to about 0.3; the maximum value of rmJ in each case depends on the molecular dimensions of the templating agent and the effective pore volume of the pore system of the particular molecular sieve involved. “W”, rxJ, ryJ, and rzJ represent the mole fractions of iron, aluminum, phosphorus, and silicon, respectively, present as tetrahedral oxides, which mole fractions are within the limit composition values or point ranges as follows: The values of rwJ, rxJ, "y" and rzJ can be as follows: The EP publication on page 12 describes the crystallization procedure using seeding of the reaction mixture. It states that it will be promoted. Published on page 18, Molecular U.S. Patent Application No. 600,170, EPC Publication No. 0158975, published on September 23, 1985 - Crystalline or amorphous aluminophosphate phosphorus and aluminum in making sieves It states that it is used as a source.

US Pat.
Contains a framework structure of tetrahedral units of s: mR: (ZnwAlxPySiz)0*wherein rRJ
represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of rRJ present per mole of (ZnwAlxPySlm)02 and has a value of 0 to about 0.3; has: "W", rxJ, ryJ and rzJ represent the mole fractions of zinc, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides and each has a value of at least 0.01, 0 mole fraction rwJ , rxJ, ryJ and rzJ are generally defined to fall within the following limiting composition values or points: In a preferred subclass of ZnAPSO molecular sieves, the values rwJ, rxJ, ryJ and rzJ in the above formula are U.S. patent application Ser. It is shown on page 14 that crystalline or amorphous aluminophosphates can be used as the phosphorus or aluminum source and that seeding the reaction mixture with the crystals accelerates the crystallization procedure.

Examples 12-15 use the seeding procedure. It describes that there is.

MgAPSO molecular sieve is MgO*-”, A10a-1PO1 and S
iO, has a three-dimensional microporous framework structure of tetrahedral oxide units, and has an experimental chemical composition represented by the following formula on an anhydride basis: mR: (MgJIIIP, 5ix)Oa, where rRJ
represents at least one organic templating agent according to EPC Publication No. 0158348 present in the intracrystalline pore system; "m" represents the molar amount of rRJ present per mole of (Mg-AI-PySia)Os; and has a value from 0 to about 0.3: "W", "x", "y" and rzJ represent the mole fractions of magnesium, aluminum, phosphorous and silicon, respectively, present as tetrahedral oxides, and each provides that the mole fractions rwJ, rxJ·ryJ and rzJ, preferably having a value of at least 0.01, generally fall within the following limiting composition values or points: In a preferred subclass of 39MgAPSO molecular sieves, the values rwJ, rxJ, ryJ, and rzJ in formula 1% are as follows: falls within the range of values or points; d O, 550, 100, 35 This publication is published on page 14 and Example 5. 6.55.58 and 59 are shown to be seeded to produce the product.

The MnAPSO molecular sieve of U.S. Application No. 600,175, filed on April 13, 1984, has an experimental chemical composition of MnOz-'', AIOz, PO2 and S on an anhydride basis.
It has a framework structure of tetrahedral units of i O2: mR: (MnJlmPySig) OxEPC Publication No. 0161490, where rRJ represents at least one organic templating agent present in the intracrystalline pore system; "m" is (MnwA1 *PySix) represents the molar amount of rRJ present per mole of Oa and has a value of 0 to about 0.3 = "W", rxJ, "y"
and rzJ represent the mole fractions of manganese, aluminum, phosphorus, and silicon, respectively, present as tetrahedral oxides. 0 mole fraction rwJ, rxJ, "y" and rzJ are generally within the range of values or points as follows: It is defined when entering: E O,600,010,39rwJ,rxJ
, ryJ The value of rzJ can be as follows: U.S. Patent Application No. 600,174, filed April 13, 1984, published November 21, 1985 d O,550,100,35 The publication describes, on page 13, the use of crystalline or amorphous aluminophosphate as a source of phosphorus or aluminum and features the use of the crystals to facilitate the crystallization procedure.

Examples 54-56 and 59-62 are Crystals for production of MnAPSO products It describes what was used.

The CoAPSO molecular sieve of U.S. Pat. It has an experimental composition represented by the following formula: mR: (COwAlxPySfg
) O'zEPC publication, where rRJ represents at least one organic templating agent present in the intracrystalline pores (l16148'1);"m" is the mole of "R" present per mole (COJIJySljOz); "W", rxJ, ryJ and rz
J represents the mole fraction of cobalt, aluminum, phosphorus, and silicon, respectively, present as tetrahedral oxides, and the mole fractions rwj, rxj, ryj, rzj are each at least 0.01 and are generally as follows: defined as falling within a range of limiting composition values or points; CoAPSO Molecular Sieve US Pat. and on page 14, Examples 11.12.13.93 and 97-103, which describe that seeding the reaction mixture accelerates the crystallization procedure, demonstrate the use of seed crystals.

M e A P O molecular sieve is a crystalline microporous aluminophosphate in which the substituent metal is one or a mixture of two or more divalent metals of the group magnesium, manganese, zinc, and cobalt. Yes, disclosed in U.S. Patent No. 4.567.028 and 599.80? 599.809 599.811 599.8+2 599.813 600.166 600.171, EPC publication no. and PO□ has a three-dimensional microporous crystalline framework structure of tetrahedral units and has the essential experimental chemical composition of the following formula on an anhydrous basis: mR: (MJIyPx) Da where rRJ is present in the intracrystalline pore system. "m" represents at least one organic templating agent that
0 to about 0.3, the maximum value in each case depending on the molecular dimensions of the templating agent and the effective pore volume of the pore system of the particular metal aluminophosphate involved. : "X", ryJ, rzJ represent the mole fractions of the metals "M" (i.e., magnesium, manganese, zinc, cobalt), aluminum and phosphorus, respectively, present as tetrahedral oxides, where the mole fractions are rxJ, ry'', rzJ represents the following values: D O,350,600,05 When synthesized, the minimum value of rmJ in the above formula is 0.02 0 Preferred metal aluminophosphates of the present invention In the subclass, rxJ, ryJ, rzJ in the above formula represent the following values for rxJ, "y", rzJ: d O, 250, 400, 35 The as-synthesized composition is exposed to air for long periods of time. , i.e. calcination at 350° C. for at least 2 hours. be able to.

EP publication is on pages 14 and 15, Crystalline and amorphous aluminophosphates as an active phosphorus and aluminum source and on page 15, Can be seeded into the reaction mixture Describes promoting the crystallization procedure Example 8 seeded with crystals This is disclosed.

The rELAPOJ molecular sieve has at least one element capable of forming a three-dimensional microporous framework containing Al01. PO2, and Mol tetrahedral oxide units [where rMOiJ is at least one tetrahedral oxide unit rMOiJ present with charge rnJ (rnJ can be -3, -2, -1, O or +1) different species (other than AI or P), EPC Application No. 85104388.5 filed on April 11, 1985 (EPC Publication No. 158348, published on 10416/1985) ] is a class of crystalline molecular sieves that form a crystalline framework structure. The elements of this new class of molecular sieve compositions have a crystalline framework structure of AIO*, P02, and MO□ tetrahedral units and have an experimental chemical composition represented by the following formula on an anhydrous basis: mR:( MyoAl,P,>02 where rRJ represents at least one organic templating agent present in the intracrystalline pore system; rmJ is the amount of rRJ present per mole of (M,AI,P,)01; represents a molar amount; rMJ represents at least one element capable of forming a framework tetrahedral oxide; represents the mole fraction. rMJ is at least one different element (M,) such that the molecular probe contains at least one framework tetrahedral unit in addition to AlO2 and Po2.

rMJ is arsenic, beryllium, boron element, chromium, gallium, germanium lithium, selected from the group consisting of At least one element, rMJ represents two elements, then the second The element can be one of the above can and/or cobalt, iron, mag nesium, manganese, titanium and At least one selected from the group consisting of lead It is a seed element.

ELAPO molecular sieve is In the same specification, AI O2, POi and MO, within the framework of tetrahedral oxide units To represent the element rMJ, the head is generally It is called jizume or rELAPOJ. There is. The actual class elements are the initials The final rELJ is defined as M Os tetrahedral unit. to replace it with an element that exists as will be identified by

When rMJ represents two elements, rM” also represents cobalt, iron, and magnetism. Si, manganese, titanium and zinc At least one type selected from the group consisting of 0 examples that can be made into elements of For example, in each case, rMJ is First element group, such as As, Be, etc. Contains at least one of the following, two types or where more elements exist If the second and higher elements are The first element group and/or as studied can be selected from the second group of elements. Ru.

ELAPO molecular sieve is AIO□, po, and M Oz tetrahedron from aluminum, manganese, titanium and zinc. At least one element selected from the group It can be made plain.

The relative amounts of element "M", aluminum and phosphorus are determined by the following empirical chemical formula (anhydrous): mR: (v*A+yPz)2, where rxJ, ryJ and rzJ are the mole fractions of element M% aluminum and phosphorus. ). The individual mole fractions of each rMJ (or M+ Ms, Ms, etc. when M represents two or more elements) are rx, J, "x2", "x3", etc. (where "xl"","x2","x3", etc. represent the individual mole fractions of the elements M r , M z , Ml, etc. for rMJ as defined above.

11R has a crystalline three-dimensional microporous framework structure of the unit and has a chemical composition represented by the following formula on an anhydrous basis: (M,AlyPm)Os, where rRJ is the least represents one type of organic template agent; r m J is (M, Al, P,)0. represents the molar amount of rRJ present per mole of At least one element selected from the group consisting of arsenic, beryllium, boron, chromium, gallium, germanium, and lithium. When "M" includes an additional element, such additional element rMJ is cobalt, iron, magnesila rx+J, "xl", rxsJ, etc., whose values are as defined for rxJ hereinafter; rx+ J + rx* J + rX3J'...
・= “X” and ・X Is X a・x3, etc. are each at least 0.01.

The E I APO molecular sieve has a crystalline three-dimensional microporous framework structure of MO, A 10 z , and po2 tetrahedral units with an experimental chemical composition represented by the following formula on an anhydrous basis: mR: (M!AI , PK) 02 where rRJ represents at least one organic templating agent present in the intracrystalline pore system; "m" is the mole of rRJ present per mole of (MyoAl,P,)0□. "M" represents at least one different element (other than Al or P) capable of forming a framework tetrahedral oxide as defined above; and rxJ, ryJ and rzJ represent the mole fractions of "M", aluminum and phosphorus, respectively, present as tetrahedral oxides; the mole fractions rxJ, ryJ and rzJ generally represent In a preferred subclass of ELAPO of the present invention, the values of rxJ, ryJ and rzJ in the above formula fall within the following values for rxJ, ryJ and rzJ: ”U.S. Pat. No. 4,310,440f (1,390,6G O,QIAL
PO is the basic and simplest of the crystalline aluminophosphates. The ALPOs each have a framework structure whose chemical composition, expressed by the molar ratio of its oxides, is: Al5Os:1. Q±Q, 2hQs (each of the framework structures is microporous and the pores are uniform) and a nominal diameter in the range of about 3 to about 1 OA, The intracrystalline adsorption capacity of at least 3.5% by weight and the adsorption and desorption of water have the same essential framework morphology (tobology) in both the hydrated and dehydrated states as described in U.S. Patent Application No. 600, 168. 600' 18+.

600, 182. 600, 183 issue, October 1985 Announced on the 16th yaw loppa patent Announcement No. 0158350 completely reversible while maintaining

5ENAPSO has a tetrahedral oxide position "MO1" and A10i-2POz, S'i
02 having a framework structure of at least two elements (where "n" is -3, -2, -1,0 or +1) having tetrahedral oxide units, and is represented by the following formula on an anhydrous basis: It is a five-component and six-component molecular sieve with the chemical composition: l11R: (MeA1MP, Si)0°, where rR
J represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of rl'(J present per mole of (MWAl*P, 5il) oa and 0 ~0.3 = "M" is at least two selected from the group consisting of arsenic, beryllium, boron, chromium, cobalt, gallium, germanium, iron, lithium, magnesium, manganese, titanium, vanadium, and zinc. ``n'' is as defined above: ``W'', rxJ, ryJ and rzJ are the mole fractions of element ``M'', aluminum, phosphorous and silicon, respectively, present as tetrahedral oxides; , each having a value of at least 0.01.

Published on pages 14-15 - Boat fishing Add seeds to the reaction mixture as desired states that it produces a product of There is.

Zeolitic molecular sieves can be represented by the following general formula: MeX[(A10t), (SiOz)yl',)IzO
where Me is a metal cation, x/n is the number of exchangeable metal cations of valence n, X is also the number of aluminum ions bonded in the form of aluminate, and y is the number of silicon atoms. where Z is the number of water molecules and the removal of water molecules creates a characteristic pore or constriction system. The z/x ratio is a number from 1 to 5, usually from 1 to 2.

Representative zeolite-based molecular sieves are chabazite, faujasite levinite, linde type A, gismmondin, erionite, sodalite, and linde type X.
and Y, analcyme, gmelinite, hermotoum,
levinite, mordenite, epistilbite, hyurandite, stilbite, edgingtonite, menrite, natrolite, scolithite, tomunite, bluesterite, laumontite, phillipsite,
28Ms (e.g., ZSM-5 (U.S. Pat. No. 4702.8)
No. 86), ZSM-20 (U.S. Pat. No. 1972.98)
5), ZsM-12 (US patent!% 852.4
49), ZSM-s4 (U.S. Pat. No. 4.079.0)
95), etc.), Beta (U.S. Pat. No. 450 & 069)
(see U.S. Patent No. Reissue No. 2a341), etc.

Representative examples of suitable zeolite molecular sieves that can be employed in the practice of the present invention are as follows:
Zeolite A, AgX%AgY, AIRY, Alkylammonium X and Y%BaX, BaY%BeYbC
a-A% Ca-=Ahojasite, Ca-HX.

Ca-X, Ca-Y, CdX% CdY% C
eY, CoA.

CoX, CoY% CrY, CsL, Cs
X% CaY, Cu-X, Cu-Y, Cu-diethylammonium Y1Cu-x thylammonium Y, Fe
-XIIFa-Y.

Group IAX, Group IAY, Group TIAY.

HY, KL% KX, KY, L, La-X% La-Y.

LiA, LiX, LtY%LZ-10, LZ-210゜MgHY, MgNa, MgNll4Y%MgX, MgY
%MnX.

MnY, Na-A%Nm-=Ahojasite, Na
-L%Na-X, Na-Y, NH4L%NH4X1NH
4YsNi-A%N1-X%N1-Y%N H4L s
N H4X %NH,Y, N1-A%N1-X, N
1-Y, omega, PdY, phosphate, pt, rare earth X, rare earth Y.

RbX, RhY, SrX, SrY, steam stabilized or super stable Y, tetramethylammonium Y.

TIX, lJ ether ammonium Y, X%Y1Y-82
, ZK-5, Zn-mordenite% Zn-X 5
An-Y, the above 28Ms, etc.

Other zeolitic CMSCFs useful in the present invention
i boron-treated aluminosilicate, e.g. rice 5i1
! ! ! Including those described in Japanese Patent Application No. 4,614720. Other NZMS are silica molecular sieve,
For example, rice F! 1 patent No. 4.061.724.

The average diameter of the pores of currently useful CMSCs was determined by Donald W.
"Zeolite Molecular Sieve" by Breck)
from about 3 to about 1 as determined by measurements described in
A range of 5 angstroms is preferred. This average diameter is called the average effective diameter. When the feedstock and the desired product are organic components that are relatively small, e.g. containing from 1 to about 10, preferably from 1 to about 4 carbon atoms per molecule, the CMSC is preferably pore-forming, comprising: At least a portion, preferably a major portion, of the pores have an adsorption capacity (as determined by the standard Matsukubein-Baker gravimetric adsorption method using a given adsorbate molecule) of oxygen (with a mean kinetic diameter of approximately α 346 nm) and has a patented average effective diameter that adsorbs inbutane (average kinetic diameter (L 5 nm) of negligible amounts).

- the layer preferably has an average effective N diameter that adsorbs xenon (average kinetic diameter (L 4 nm)) and adsorption of isobutane is negligible; - the layer preferably adsorbs n-hexane (average kinetic diameter 143 nm); It is characterized by a very small amount of adsorption of isobutane.Adsorption of a given adsorbate means adsorption of less than 3% by weight of CMSC, and adsorption of adsorbate means adsorption of less than 3% by weight of CMSC. Some of the CMSCs useful in the present invention contain pores with average effective diameters ranging from about 3 to about 5 angstroms.

Any currently available catalyst may be incorporated into the solid particles, and the catalyst may be present in an amount effective to promote the desired chemical conversion. In one embodiment, the solid particles include a catalytically effective amount of a catalyst and at least one of a binder material and a filler to impart desired properties to the solid particles, such as desired catalyst dilution, mechanical strength, etc. do. Such filler and binder materials, ie, matrix materials, are porous to some extent in nature and may or may not be effective in promoting the desired chemical conversion. Such matrix materials include, for example, synthetic and naturally occurring substances, metal oxides,
Clay silica, alumina, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria,
Includes silica-beryria, silica-titania, silica-alumina-thoria, silica-alumina-zirconia, mixtures thereof, and the like.

If one or more matrix materials are included in the solid particles, the catalyst may contain other solid materials, such as matrix materials, in about 75 - or less layers, preferably about 35
It is preferably contained in solid particles containing not more than i% by weight. Preferably, the amount of matrix material in the solid particles is small compared to the amount of matrix material used in the solid particles of a fixed bed catalyst or the solid particles of a fluidized bed catalyst used to promote the same chemical conversion. . The solid particles in the slurry reaction system of the present invention are not exposed to the relatively frequent and often extensive temperature and other conditions to which fixed bed catalysts are exposed, or to the turbulence and attrition to which fluidized bed catalysts are exposed. It was found that there was no exposure to the exercise that caused it. Thus, the present slurry catalysts require less protection than the N& that such matrices typically provide for fixed bed and fluidized bed catalysts. Since matrix materials often promote undesirable chemical reactions, reducing the amount of the material also helps.
This can lead to improved overall process performance.

Therefore, a reduction in the amount of such materials can lead to a reduction in undesirable products. In one embodiment, substantially pure catalyst, ie, catalyst particles substantially free of matrix material, is used in the present slurry reaction system.

Methods of manufacturing solid particles comprising CMSCs and matrix materials are conventional and well known in the art and therefore need not be discussed in detail herein. Such manufacturing method I
Some of the Ins are described in the patents and patent applications previously incorporated by reference, as well as in US Patent No. 14 to 253 and Reissue Patent No. 27.659. Catalysts formed during and/or as part of the process of producing solid particles are within the scope of this invention.

The solid particles containing the catalyst can be of any size conveniently suited to the present invention. In order to use the catalyst more effectively, the solid particles are preferably small compared to fixed bed solid particles used to promote similar chemical conversions.

- the layer preferably has a maximum transverse dimension, e.g. from about 1 to about 500 microns in diameter;
It has a range of approximately 200 microns.

To obtain the desired particle size for the catalyst and/or solid particles,
Mechanical comminution, such as grinding, crushing, kneading, etc., can be carried out. However, the catalyst-containing homogeneous particles are cleaner and preferably also more spherical than solid particles of similar composition obtained by mechanical grinding. The smoothness and sphericity of such spheres tends to improve the flowability and useful life of the slurry, and can also increase the solids fraction in the slurry, if desired. One particularly useful processing step to achieve such smoothness and sphericity is to employ spray drying as part of the solid particle manufacturing process to form the solid particles or solid particle precursors. An additional advantage of employing such spray drying is that the conditions of such a process can be adjusted so that the product solid particles are of a desired particle size or size range.

The use of spray drying in the production of such catalysts/solid particles is conventional and well known as sb1. Therefore, there is no need to discuss it in detail herein.

Non-zeolitic molecular sieves *ijNZMs are particularly useful in the practice of this invention.

Among the NZMS, SAPO is particularly useful.

SAPO-17 and SAPO-54, which is described in detail in Example 38 of U.S. Pat. 6, preferably up to about 4, such as ethylene, propylene, butylene, and the like. At present, SAPO-14 is most preferred.

The amount of catalyst or solid particles in a slurry, ie, one made of solids and a suspended, substantially non-reactive liquid, can vary over a wide range depending, for example, on the particular processing application involved. Catalyst/catalyst in slurry to provide effective spatial and temporal contact between feedstock and catalyst.
Relatively high loadings of solid particles may be appropriate. On the other hand, excessive loading of tIX/solid particles should be avoided as this can lead to a reduction in the desired product. Also, the slurry may have to be flowable or pumpable to transfer the slurry to another vessel to regenerate the catalyst, if desired. The catalyst/solid particles occupy about [11
~50% by weight, -layer preferably about (L2~2~30% by weight)
%.

One important feature of the present invention is that the currently available slurries have similar reactivity than the feedstocks! g. Use liquid solution. That is, the Full liquid is, rather, under the conditions of the feed/catalyst contacting step, e.g. it only contains the feed, product, diluent (if any)
It seems like it will react chemically. Thus, the chemical conversion or reaction rate of the suspension is reduced, preferably considerably reduced, compared to the rate for the feedstock at the conditions of the feedstock/catalyst contacting step. - layer preferably 'a
The suspension is substantially non-reactive, i.e., substantially chemically unreacted, under the conditions of the present feedstock/catalyst contacting step, particularly with respect to the chemical reactions promoted by currently available catalysts. or substantially chemically inert. Suspensions may decompose or degrade under contact conditions, such as elevated temperatures, over relatively long periods of time, such as by oxidation, thermal decomposition, and the like. Such degradation or deterioration may lead to replacement of the suspension, but should not be considered in determining whether a liquid is substantially non-reactive. The composition of the suspension is preferably chosen such that the size and/or shape of the liquid molecules opposes the passage of the catalyst into and out of the pores. For example, if the molecules of the liquid are too large, they cannot enter the pores of the catalyst.

Suspensions can be selected from a wide variety of compositions, provided they perform as described herein. The liquid should be stable. i.e. high temperatures, e.g.
It should resist substantial decomposition or degradation at catalyst/feedstock contact conditions, which often involve temperatures in excess of 0°C. - In an embodiment, the molecules of the suspension have a kinstle diameter of a size that substantially prevents them from entering the pores of the catalyst. The liquid may be inorganic or organic. Is or larger silicones and similar materials can be used as suspensions. Suitable organic liquids preferably contain carbon and hydrogen-layers, preferably at least one other element, such as halogen, nitrogen, oxygen, phosphorus, sulfur and mixtures thereof, and liquids containing carbon-, hydrogen-, oxygen-containing molecules. is particularly useful. Suspensions from the group consisting of dibenzylbenzene, diphenyl ether and mixtures thereof have been found to be particularly useful, especially when the feedstock molecules contain one carbon atom.

The suspension is preferably VC:p so that the feedstock is more soluble in the liquid than the desired conversion product at the feedstock/catalyst contact conditions. Feed material is Ff! ! Solubility in the residual liquid facilitates feed/catalyst contact, while relative insolubility of the desired product in the liquid facilitates separation of the desired product from the catalyst and decomposition of the product, such as reducing further chemical conversion to help preserve the desired product. It is preferred that the desired product be substantially insoluble in the suspension at the feed/catalyst contacting conditions.

In one embodiment, the suspension includes at least one component effective to improve at least one property of the catalyst. In the context of this paragraph, the term "catalyst" refers not only to the CMSC itself, but also to other components of the solid particles, if present, such as the matrix material. Thus, for example, if the binder material is used as a component in the liquid, the overall performance of the catalyst is improved and at least one property of the catalyst is improved.

Therefore, it is also within the scope of this implementation v4 aspect of the invention to benefit other components of the solid particles in this manner. Selectivity of the catalyst to the desired product is one particularly useful property that can be improved by the components of the suspension. CMSC
In situations where Mm is present in solid particles containing 1e or more matrix, the Mm solution preferably contains at least one component that reduces the undesirable catalytic activity of such matrix phase material. In one particular embodiment, the component in the liquid is a base, the molecules of which, for example, for reasons of size and/or shape and/or transition state, do not substantially enter the pores of the CMSC. It is something that is done. Such bases serve to inactivate and reduce undesirable catalytic activity of the IJ lux material without substantially affecting the desired catalytic activity of the catalyst. The base is preferably selected from the group consisting of pyridine, pyridine derivatives, quinoline, quinoline derivatives and mixtures thereof, especially when using the preferred relatively small effective pore diameter CMSC. The amount of such component included in the suspension can vary over a wide range, provided that the component is effective in improving at least one property of the catalyst. Such components preferably range from about 1001 to about 20 weight f# of the liquid in the slurry.
, S, -layers are preferably present in an amount of about 15 to about 15% by weight.Such components can be added to the suspension periodically or in succession to produce the desired effect at a continuous pace. can.

Substances in a supercritical state essentially behave like liquids.

Accordingly, in some embodiments, substances such as supercritical carbon dioxide, water, etc. may be employed as the present suspension. Therefore, in the present invention, supercritical substances that can function as a suspension liquid and also satisfy the criteria for suspensions described herein are within the scope of the present invention as suspensions. included.

The chemical conversions or reactions obtained by practicing the present invention can vary widely and depend, for example, on the feedstock used, the catalyst, and the feedstock/catalyst contacting conditions used. Virtually any chemical conversion that can be catalyzed by a CMSC can be carried out while practicing the present invention. Examples of reactions that can be cleaved include:
Disproportionation; olefin production from non-olefin feedstocks;
Olefin interconversion; aldols, e.g. aldehydes
Aldehyde, ketone-ketone, aldehyde-ketone and aldehyde or ketone-aromatic component condensations; condensation reactions producing cyclic lactam gold; isoprene production; alkylation (aromatic, e.g. benzene, toluene and phenol alkylation); isomerization ( xylene isomerization). One particularly preferred chemical conversion or reaction involves the production of olefins from non-olefin feedstocks, preferably feedstocks containing aliphatic heterocompounds.

Virtually any feedstock or combination of feedstocks can be used in the present invention. Such feedstocks, or reactant components, may be gaseous, solid, or liquid at ambient conditions, ie, 20° C. and atmospheric pressure. The feedstock may be inorganic, organic, or a combination of organic and inorganic components. The present reaction system is particularly applicable to organic feedstocks, preferably those having molecules containing carbon and hydrogen, preferably at least one other element. Preferably, the other elements are selected from the group consisting of F, sulfur, halogen, nitrogen, phosphorus and mixtures thereof, with oxygen being particularly preferred.

As previously mentioned, the present invention is particularly useful for converting feedstocks having relatively small molecules, ie, molecules with relatively small kinetic diameters. That is, the feedstock preferably contains from 1 to about 10 carbon atoms per molecule, preferably from 1 to about 4 carbon atoms per molecule.

Aliphatic heterocompounds are particularly preferred feedstocks for use in the present invention, especially when it is intended to produce light olefins, i.e. olefins containing from 2 to about 6, preferably from 2 to 4, carbon atoms per molecule. A preferred feedstock. When light olefins are the desired product, they are preferably produced as the predominant hydrocarbon product. That is, 50 moles or more of the hydrocarbon half is light olefin. The term "aliphatic heterocompounds" is used herein to include alcohols, halides, mercaptans, sulfides, amines, ethers and carbonyl compounds (aldehydes, ketones, carbonyls, etc.). The aliphatic moiety preferably has 1 to 1 carbon atoms.
The layer preferably contains from about 1 to about 4 carbon atoms.

Suitable reactants include lower straight chain acids, branched chain alkanols, their unsaturated counterparts and their nitrogen, halogen and sulfur analogs. Representatives of suitable aliphatic heterocompounds include: methanol; methyl mercaptan, methyl sulfide; methyl amine; dimethyl ether; ethanol; ethyl mercaptan; ethyl chloride; diethyl ether; methyl ethyl ether; formaldehyde; dimethyl ketone; vinegar; - Alkylamines; n-alkyl halides and n-alkyl sulfides in which the n-alkyl group has 3 to 10 carbon atoms; and mixtures thereof.

In one embodiment, for example, when light olefins are the desired product, the feedstock is methanol, ethanol,
Preferably it is selected from the group consisting of dimethyl ether, diethyl ether and mixtures thereof, with methanol being particularly preferred.

In some instances, feedstock/catalyst contacting conditions are preferred such that the contact temperature exceeds the critical temperature of the feedstock. In other words, in some embodiments it is preferred that the feedstock be in a supercritical state at the feedstock/catalyst contact conditions. Bringing the feedstock to a supercritical state means that the feedstock contains from 1 to about 10 carbon atoms per molecule, preferably from 1 to about 41 carbon atoms per molecule.
- It is particularly useful when it contains.

It goes without saying that the product obtained from the feedstock/catalyst will depend on, for example, the feedstock, catalyst and conditions employed.

As in the case of the feedstock, the product can be inorganic, organic or a combination of inorganic and organic components. Preferably, the desired product is organic. but,
It should be noted that even if the main product desired is organic, the necessary and therefore desired reaction by-products may be inorganic. This is exemplified by the conversion of methanol to light olefins plus water. The organic product preferably has molecules containing carbon and water. - In embodiments, the desired product preferably contains from 1 to about 10 carbon atoms per molecule, - preferably from 1 to about 4 carbon atoms per molecule. Preferably, the desired product has a kinetic diameter that causes it to be removed or escaped from the pores of the sieving catalyst.

Preferably, the product is in a form that is easily separable from the slurry after leaving the catalyst pores, and more preferably in gaseous form.

In addition to the feedstock, diluents may be used with the feedstock if desired and/or may benefit the overall process. Such diluents can be mixed with or combined with the feed prior to feed/catalyst contact, or may be introduced into the reaction zone separately from the feed. Preferably, both feed and diluent are fed substantially continuously to the feed/catalyst contact. Preferably, such diluents serve to moderate the rate of feed chemical conversion, perhaps even by as much as '! It can act to assist in temperature regulation. In some embodiments of the invention,
Diluent usage can be reduced compared to fixed catalyst and fluidized catalyst bed operations involving similar chemical conversions. a
It is clear that the suspension performs one or more of the functions of a diluent. Thus, less diluent may be required, resulting in savings in both capital investment and operating costs in commercial implementation.

Such diluent is preferably chemically substantially non-reactive at the feed/catalyst contacting conditions, but is clearly distinct from the suspension of the slurry.

For example, a diluent may be introduced in combination with or together with the feedstock and thus be considered a feedstock component. Often the suspension is not a feedstock component.

Suspensions are liquids, whereas diluents are often in the same phase as the feedstock. Also, the diluent preferably contains molecules sized to enter and exit the pores of the sieving catalyst, whereas the suspension preferably does not contain such molecules.

Representative diluents that can be used in this method are helium, argon, nitrogen, carbon oxide, carbon dioxide, hydrogen, water, hydrocarbons and mixtures thereof. When the feedstock contains from 1 to about 10 carbon atoms per molecule, the diluent, if any, may be selected from the group consisting of helium, argon, nitrogen, carbon oxide, carbon dioxide, hydrogen, water and mixtures thereof. Water, nitrogen and mixtures thereof, especially water are more preferred. The amount of diluent, if any, used can vary over a wide range depending on the particular application involved. For example, a#i of diluent can range in amount from about αi% or less of the moles of feedstock to about 99% or more.

Preferably, the catalyst is at least periodically contacted with a regeneration medium to substantially maintain or increase the effectiveness of the catalyst in promoting the desired chemical conversion. For example, a catalyst may become less effective due to the formation of carbonaceous deposits, or precursors of such deposits, in the pores or regions of the catalyst. In one embodiment, the regeneration medium serves to reduce the average kinetic diameter of molecules present within the pores of the catalyst. Such a reduction in the kinetic diameter of these molecules allows the forming molecules to evacuate or exit the catalyst pores, thereby providing more pores and/or pore volume for the desired chemical conversion. It is preferable that the If regeneration is required, the sieving catalyst is separated from the suspension and removed from the feed/catalyst contacting zone and preferably introduced substantially continuously into the withdrawal and regeneration zone, preferably continuously. The catalyst can then be regenerated, for example by fermentation in an oxygen-containing atmosphere to remove all carbon deposits. After such oxidative regeneration, the catalyst is preferably combined with the suspension and then reintroduced, preferably substantially continuously, into the feed/catalyst contacting zone.

If the suspension is sufficiently stable during catalyst regeneration, the regeneration medium/catalyst contact can be carried out while the catalyst is slurried in the suspension.

In one embodiment, the catalyst includes at least 1 fJ of additional components effective to promote the action of the regeneration medium. For example, the catalyst can include at least one metal component effective to promote oxidation of the carbon adsorbent. Of course, such metal components should not substantially adversely affect the desired chemical conversion. The specific additional catalyst components will depend on the requirements of the particular application involved. Examples of such additional components include: transition metals such as nickel, cobalt, iron, manganese, copper, etc.; platinum group metals such as platinum, palladium, rhodium, etc.; rare earth metals such as cerium, lanthanum. , etc. and mixtures thereof. If an additional metal component is used, this component should be present in a minimum amount of - about 1 of the weight of the catalyst used, preferably including the matrix material.
Heavy ppm ~ about 20 weight S (calculated as elemental metal)
Preferably, it exists as

Instead of oxidizing catalyst regeneration, a reducing medium can be used to regenerate the catalyst. Preferably, such reducing medium is selected from the group consisting of hydrogen, carbon monoxide and mixtures thereof, in particular hydrogen, and for example, the reducing medium is selected from the group consisting of hydrogen, carbon monoxide and mixtures thereof, in particular hydrogen. It is used to react with molecules that have a reduced kinetic diameter so that the resulting nine molecules can exit the pores of the catalyst. −
In an embodiment, the reducing medium is hydrogen and the catalyst comprises at least 1 fi of components effective to promote the aqueousization and/or hydrogenation Mk of the molecules present in the pores of the catalyst under the conditions of reductive regeneration. contains metal components.

The use of reducing media for catalyst regeneration can provide advantages. For example, if the suspension is stable enough to be substantially inert to reducing media, it can be regenerated in the catalyst slurry, preferably in the feed/catalyst contact zone. A combination of oxidative and reductive catalyst regeneration can be employed.

For example, a reducing medium can be used as a diluent, such as as discussed herein, to at least partially regenerate the catalyst, thereby extending its useful cycle life before the catalyst is subjected to more complete oxidation. Sexual regeneration may also take place. It is of course possible to use both oxidative and reductive regeneration of the catalyst alone, rather than in combination, in any suitable sequence.

The method can be carried out in batch, semi-continuous or continuous mode;
Continuous operation is preferred. The process can be carried out in a single feed/catalyst contacting zone or in multiple zones arranged in series or parallel. After the desired product is separated from the slurry, it can be recovered or purified using a variety of techniques, such as distillation, adsorption, and the like.

The conditions for feedstock/catalyst contacting can vary widely depending on, for example, the particular feedstock, suspension and catalyst used and on the particular product desired.

Preferably, such conditions are such that the suspension remains substantially in the liquid phase. The process is performed at a feed/catalyst contact temperature of greater than about 200° C., preferably greater than about 500° C., and of greater than about 10 pmlg (α7 kg/cm”G), preferably about 50 pmig (15 ky /cm
” G
The feed/catalyst contact temperature is preferably from about 2001' to about 600°C or even 700°C, preferably from about 250°C to about 250°C.
° to about 550 °C, preferably about 300 ° to about 5
In the range 00°C, the feed/catalyst contact pressure is approximately 15
Preferably it is as low as 00 pmlg (105 kf/iG). The use of relatively high pressures in the present process can be advantageous compared to fixed or fluidized catalyst bed processes. In fixed or fluidized catalyst bed processes, high pressures can lead to operational difficulties and/or can adversely affect catalyst performance, such as selectivity to the desired product. The residence time of the feedstock and catalyst in the feedstock/catalyst contact zone may be chosen independently depending on, for example, the particular feedstock, suspension and catalyst used, and the particular product desired.

The following examples are given to better explain the invention and are not intended to limit it.

Example 1 Powder chaba f with average particles as s o t talin
4 tons and 25 grams were used as catalyst. Chabazite is a small pore molten nitrate and is sold under the trademark W500 by Union Carbide Co., Ltd. Chabazite was originally published in 1974 by Willie and Sons and Neurology in ``Seven Orite Molecule Error Sheep'' by Donald Duplier and Plett.
It is described in detail on the page. The Dow Chemical Company has applied the trademark Dowtherm (Devth@r) to this chabazite.
Liquid 2 mainly containing diphenyl ether sold by m)
Mixed liters. The total mixture was placed in an autoclave with a lid of about 4 liters. The inner surfaces of the autoclave were stainless steel. Pressurize the inside of the autoclave with nitrogen to about 500 pm 1g (55 kg/+ is C4'), then start the heater and stirrer attached to the autoclave. When the autoclave reached a temperature of 575°C and was about to die, the internal pressure was 980 psig (69 kpH2G
)Met.

Pour 50 milliliters of a mixture of 50 volumes of methanol and 50 volumes of water into an autoclave over a period of about 12 minutes. After 5 minutes, a sample of the product was removed into a stainless steel sample bong. Table 1 shows the analysis of the sample.
Listed below.

Table 1 CH4117? C,I(,3485 C,H6515 C,H@16.40C,)t,
24.30CaHa
402C@a
(L35COO, 16 CO1 (LP8 1) where carbon selectivity, as used with respect to a given product, is the percent of carbon atoms of the total listed product present in the given product.

The conversion of methanol to the above product is about 63%,
Approximately 57% of the methanol feed produced dimethyl ether.

Example 2 5 grams of loose crystals of 8mm PO-34 were mixed with a mixture of 200 barrels of water and 2 liters of Dauphum A and charged into an autoclave as described in Example 1.

The autoclave was extensively purged with nitrogen for 50 minutes to remove air and then heated to 37.5°C. At this point the pressure is 500 pslg (55kf/cIA'
G). Equal volume mixture of methanol and water 5
0 ml was discharged from the autoclave over 26 minutes, during which time the slurry in the autoclave was stirred. 5
After minutes, a sample of the product was taken into a stainless steel sample bomb. Analysis of the samples is listed in Table 2VC.

Table 2 Csl(s 9-1404B,
1&28COα07 CO8 Engineering80 1 where carbon selectivity, as used with respect to a given product, is the percent of carbon atoms of the total listed product present in the given product.

The conversion of methanol to the above products was 7415≦, with about 24.5% of the methanol feed forming dimethyl ether.

Example S 445 grams of ground Chabaite were mixed with 2 liters of Dausamite and charged into the autoclave described in Example 1. Purge the autoclave with nitrogen to 200 pslg
(14ky/al"G) Pressurized at 4C and heated the autoclave to 200°C and purged again to remove any remaining air. Return pressure with nitrogen and add 1g of 100p glue (7
kg/cm”G) K and autoclave 37
Heat to 5℃.9.

300 milliliters of methanol was discharged into the autoclave over 19 minutes. After 5 minutes, a sample of one product was taken into a stainless steel sample cylinder. Analysis of the samples is listed in Table 3.

Table 3 Component Carbon selectivity 1 C1'1.27.94 C,! ! 4 3419 C,H,t44 C,Hl &11CsH,14
113 C4Hs 427CO3,25 Co, 4611 where,
Carbon selectivity, as used with respect to a given product, is the percent of carbon atoms of the stated total product that are present in the given product.

The conversion of methanol to the product was >1464, with approximately 81% of the methanol feed forming dimethyl ether.

Example 4 Materials containing catalysts for the conversion of methanol to olefins used in some of the following examples were prepared as follows.

A first slurry of 50 parts by weight of BAPO-54 crystals and 50 parts by weight of water was prepared and continuously mixed. In a separate vessel, a second aqueous slurry 1 of kaolin clay and aluminum hydroxychloride (containing the equivalent of 254 parts by weight of alumina, calculated as AlsOs) was prepared. The first slurry was added to the second slurry to form a combined slurry, which was mixed for about 10 minutes. The combined slurry was then stone milled to obtain a substantially uniform particle distribution.

The milled slurry is then spray dried to an average particle size of about 7
Circle the particle with 0 micron. 6 spray dried particles
It was baked at 00°C for 2 hours.

The composition of the first and second slurries is such that the final particles are 8APO-
3460% by weight, kaolin clay 23% by weight, AllO
s was chosen to contain 17% by weight.

Example 5 A slurry of 220 ml of Dauphum A, 5 ml of quinoline, and 30 grams of 9 particles prepared in Example 4! i00ml was placed in an autoclave.

740 milliliters of feed containing 66 volumes of water and 34 volumes of methanol were fed to the autoclave over a 6 hour period. Keep the reaction concentration at about 400℃ and the pressure at about 3
259aig (22-9ky/cm"G)K was maintained. After this period, a sample of raw material was taken into a stainless steel cylinder. Listed in Table 4 for analysis.

Table 4 Component Carbon selectivity 1 CH4 (L76 Cut, s504C, H, 16
2 C, H・ 50.35 C, H, 2
,21 C,H@9.86C@'m
118CO Trace CO, Trace 1 where carbon selectivity, as used for a given product KIIL, is the percent of carbon atoms in the total products depicted present in a given product.

The conversion rate of methanol to the above product was 92.8%.

Examples 6-9 In Example 4, 200 milliliters of a liquid mixture of isomeric dibenzylbenzene, sold by Chemiach@W@rk@Ht+ls Ag, under the trademark Mmrloth.rm S, and 10 milliliters of quinoline, The prepared slurry with 25 grams of nine particles was placed in a 300 milliliter autoclave.

The composition of the continuously fed raw materials was 87.08% by volume of water and 12.92% by volume of methanol. The temperature within the autoclave was maintained at approximately 390''' to 410°C and the pressure was maintained at 605 pair (42,5ky/11G) K. The product from the autoclave was analyzed on a substantially continuous pace at various times. The results of some of these analyzes taken are shown in Table 5.

There was raw methanol in each product.

Among these products, dimethyl ether (L10 weight!
None contained more than Ik%. In commercial embodiments, untreated methanol can be separated and recycled.

After Examples 6-9, the slurry was removed from the autoclave and treated to separate the catalyst from the liquid.

The catalyst is then placed in contact with 1 c of air at 500° C. for 12 hours to regenerate the catalytic activity of the catalyst. The catalytic activity of the catalyst is
After treatment, the catalyst was considerably recovered and used for another series of experiments, such as Examples 10-16 described below.

Examples 10-16 A slurry of 200 milliliters of Mer4sum S prepared in Example 4 and regenerated as described above with 9 particles and 10 grams was placed in a 300 milliliter autoclave.

This slurry was quinoline-free and fed continuously for 90 minutes and had a composition of 87.08 volume percent water and 12.92 volume percent methanol. The temperature inside the autoclave was maintained at a temperature of 355° to 575°C, and the pressure was maintained at about 615 to about 635 pmir (452 to 447 k).
The product from the autoclave was analyzed on a substantially continuous basis. The results of several of these analyzes taken at various times are shown in Table 6.

Among the products, dimethyl ether is α3 None contained more.

Table 5 1% by weight 2.77 2.91 2.77 2.91 2α59 24.21 2&25 t93 7ρ4 75.7 73.7 3&0 Table α53 α92 O6 α92 2α50 12.32 2521 19.4 8t5 B7 .6 84.0 76.7 6 α97 1Q, 56 7 Q, []5 1176 8 1.52 12L12 9 α98 1t49 t03 4157 17.02 t23 44.94 14.5M 2,. 30 4142 D80 t03 44.61 14.71 t64 20.17 18.65 20,! 59 C,S,-Carbon Selectivity where carbon selectivity as used with respect to a given product is the percentage of carbon atoms in the depicted dead metal product that are present in the given product.

10 162 7.27 11 to2 482 12 t40 7.56 15 t2+s 934 14 α94 9.26 15 t43 9.39 16 2.21 14.47 α46 1!1.04 0.55 1? , 71 0.85 25.66 [1,5137,38 α52 39.59 (L96 37.05 (L78 4 (171 34,575α7B 556B 2B, 67 52.56 24.13 22.59 21.68 2α64 2179 2 & 78 2(L55 2CL13 [27 C,S, - Carbon Selectivity where carbon selectivity as used for a given product is the percentage of carbon atoms in the total products depicted present in the given product) It is F.

Examples 6-9 demonstrate some of the advantages of using quinoline in the slurry when compared to Examples 10-16. If quinoline is present in the slurry, the desired product,
That is, high selectivities to ethylene and propylene are typically achieved at a given methanol conversion level. Thus, the quinoline in step 2 modifies the catalytic properties of the solid particles from Example 4. Since catalytic binders and fillers are known to promote non-selective reactions, quinoline may serve to reduce this undesirable effect. These non-selective reactions catalyzed by the catalyst binder and filler can be eliminated by removing the binder and filler from the catalyst. The present slurry system accommodates the use of sieved catalysts without binders or fillers. Improved selectivity to the desired product can be obtained. Additionally, the present slurry system provides significant temperature control, ease of catalyst handling and catalyst/product separation. In summary, the present invention provides considerable advantages over fixed beds, such as temperature control and overall control, and over fluidized catalyst beds, such as flexibility in catalyst composition and reduced catalyst handling problems.

Examples 17-22 Using 10 grams of catalyst, the temperature in the autoclave was approximately 4
00° to approximately 410°C, and the pressure was set to 315p (22
, 2 kj force 1 G) were repeated. The results of several analyzes taken at various times are shown in Table 7.

None of the products contained more than α15 weight of dimethyl ether.

Table 7 1? 315 152 1/1.20 t45 19.53 t45 9.16 t45 1α82 152 12.46 L45 1155 858 80.8 9 (L7 89.1 8 & 4 17 164 19.12 and 1 517
? 7.81 158118 120
19.18 169 5168 7.0?
14.5619 t65 2t52
2J) 5 5152 664 12.7720
165 2 [1992, 1250, 96478
111221t66 2 (L95 2.34
5α61 4155 i&5522 17
5 2t08 234 5 (LSI 1
86 1&12C,S, - Carbon Selectivity Here, carbon selectivity as used with respect to a given product is the percentage of carbon atoms in the total product depicted present in the given product.

Example 23 This example demonstrates the use of the present slurry system to convert methanol to gasoline boiling range hydrocarbons.

A slurry of 10 milliliters of Marotherm 82 and 20 grams of solid particles having an average size of about 50 microns comprising a crystalline aluminosilicate having a substantially uniform pore range of about 6 angstroms was placed in a 300 milliliter autoclave.

The slurry was continuously stirred to keep the solid particles suspended in the Marptherm S.

The autoclave was heated to 500 pmig (21ky) with nitrogen.
/aw"G)K pressurization and a nitrogen purge were established. The slurry was then heated in an electric heater attached to the autoclave to approximately 375°C. When the temperature reached 375°C, 50 volume bar cent. A mixture of 50 volumes and 111 percent water was fed at a rate of 60 milliliters/hour until the entire 100'' liter of methanol/water mixture was fed.

All products left the autoclave as gas.

After partially condensing the product, a gas stream consisting primarily of benzene and hydrogen (not including purge nitrogen) remains.

The condensate contains water and hydrocarbons in the gasoline boiling range.

Claims (1)

[Claims] 1. Contacting a feedstock with a crystalline microporous three-dimensional solid catalyst capable of promoting conversion under conditions effective to convert the feedstock to a product. A process for the catalytic conversion of a feedstock to a product, the catalyst being in a slurry with a liquid different from the feedstock or product and less reactive than the feedstock. 2. The method of claim 1, wherein said feedstock is more soluble in said liquid than said product at said conditions. 3. The method of claim 2, wherein said product is substantially insoluble in said liquid at said conditions. 4. The method of claim 1, wherein said liquid includes at least one component effective to improve at least one property of said catalyst. 5. The method of claim 4, wherein said component is effective to improve the selectivity of said catalyst. 6. The method of claim 4, wherein said component is a base and substantially prevents its molecules from entering the pores of said catalyst. 7. The base is pyridine, pyridine derivative, quinoline,
5. The method according to claim 4, wherein the method is selected from the group consisting of quinoline derivatives and mixtures thereof. 8. The method according to claim 1, wherein the feedstock is in a supercritical state under the conditions. 9. The method of claim 1, wherein the catalyst is contained in solid particles containing up to 35% by weight of other solid materials. 10. The method of claim 1, wherein the catalyst is contained in solid particles that are substantially free of other solid materials. 11. The method of claim 1, wherein the catalyst is comprised in solid particles having improved smoothness compared to solid particles of similar composition obtained by mechanical grinding. 12. The method of claim 1, wherein the catalyst is contained in spray-dried solid particles. 13. The method of claim 1, wherein said catalyst is at least periodically contacted with a regeneration medium to substantially maintain or increase the effectiveness of said catalyst in promoting said conversion. 14. Claim 13, wherein said catalyst comprises at least one component effective to promote the action of said regeneration medium.
The method described in section. 15. The method according to claim 13, wherein the at least periodic contact is performed while the catalyst is in the slurry state. 16. The method of claim 13, wherein said regeneration medium serves to reduce the average kinetic diameter present within said pores. 17. The method according to claim 13, wherein the regeneration medium is a reducing medium or an oxidizing medium. 18. The method of claim 17, wherein said reducing medium is selected from the group consisting of hydrogen, carbon monoxide, and mixtures thereof. 19. The method of claim 13, wherein said catalyst comprises at least one additional component effective to enhance the action of said regeneration medium. 20. The method of claim 19, wherein the additional component is a metal component. 21. Claim 19, wherein said regeneration medium is hydrogen and said component is effective to promote hydrogenation of molecules present within the pores of said catalyst under conditions of said at least periodic contact. Method described. 22. The method of claim 1, wherein the liquid is substantially non-reactive. 23. The method of claim 1, wherein the liquid includes molecules having a kinetic diameter sized to substantially prevent the liquid from entering the pores of the catalyst. 24. The method of claim 1, wherein the liquid is organic. 25. The method of claim 23, wherein the liquid comprises carbon, hydrogen and at least one other element. 26. The method of claim 1, wherein said liquid is selected from the group consisting of dibenzylbenzene, diphenyl ether, and mixtures thereof. 27. Claim 1, wherein the feedstock is organic
The method described in section. 28. The method of claim 27, wherein said feedstock contains from 1 to 10 carbon atoms per molecule. 29. The method of claim 27, wherein said feedstock contains from 1 to 4 carbon atoms per molecule. 30. The method of claim 27, wherein the feedstock comprises carbon and hydrogen. 31. The method of claim 27, wherein the feedstock comprises carbon, hydrogen and at least one other element. 32. The method of claim 27, wherein said feedstock comprises at least one aliphatic heterocompound. 33. The method of claim 27, wherein said feedstock is selected from the group consisting of methanol, ethanol, dimethyl ether, diethyl ether, and mixtures thereof. 34. The method of claim 27, wherein the feedstock is methanol. 35. The method of claim 1, wherein said product is organic. 36. The method of claim 35, wherein said product contains from 1 to 10 carbon atoms per molecule. 37. The method of claim 35, wherein said product contains 2 to 6 carbon atoms per molecule. 38. The method of claim 35, wherein said product comprises carbon and hydrogen. 39. The method of claim 37, wherein said product is at least one light olefin. 40. The method of claim 1, wherein said contacting is carried out in the presence of at least one diluent. 41. The method of claim 40, wherein the diluent comprises molecules having a kinetic diameter suitable for forcing the diluent into the pores of the catalyst. 42. The method of claim 40, wherein said feedstock and said diluent are both substantially continuously fed into said contact. 43. The method of claim 40, wherein said feedstock and said diluent are brought together and then contacted. 44. The method of claim 40, wherein said diluent comprises water. 45. The method of claim 1, wherein said catalyst is selected from the group consisting of layered clay, zeolitic molecular sieves, non-zeolitic molecular sieves, and mixtures thereof. 46. The method of claim 1, wherein said catalyst is selected from the group consisting of non-zeolitic molecular sieves and mixtures thereof. 47. The method of claim 1, wherein said catalyst has a substantially uniform pore size. 48. The method of claim 1, wherein said catalyst is selected from the group consisting of silicoaluminophosphates and mixtures thereof. 49. Claim 4, wherein said catalyst is selected from the group consisting of SAPO-34, SAPO-17 and mixtures thereof.
The method described in Section 6. 50. The method of claim 46, wherein said catalyst is SAPO-34.