CA2281773C - Multiautoclave for combinatorial synthesis of zeolites and other materials - Google Patents

Abstract

The invention relates to a multiautoclave and details of its design and a method for automated synthesis of zeolites in said multiautoclave and, furthermore, application of the multiautoclave for an automated synthesis which is optimized simultaneously with regard to several synthesis parameters in the synthesis of zeolites. The multiautoclave consists typically of a pressure vessel/autoclave lined with an inert material with from 10 to 10.000 small, separated chambers, each typically having a volume of 0,2-2 ml, the chambers preferably being formed as through-going perforations in a central block and the perforations are sealed by means of balls, septa, stoppers or such which are placed at the bottom and top of each through-going perforation, and metal plates are placed over and under the Teflon plate so that the closing mechanism is pressed against the edges of the perforations in the Teflon plate with sufficient load to enable the chambers to be filled with aqueous mixtures and to be heated to 200 ~C without the occurence of leakage.
Top-and bottom plates and closing mechanisms can be integrated so that all the perforations are sealed simultaneously when these are placed at the top and bottom sides of the central block.

Description

MULTIAUTOCLAVE FOR COMBINATORIAL SYNTHESIS OF ZEOLITES AND.
OTHER MATERIALS
FIELD OF THE INVENTION
s The present invention relates to a pressure and temperature reactor vessel, especially a multiautoclave and to details concerning the design of this equipment.
BACKGROUND OF THE INVENTION
Many materials, such as e.g. zeolites, are prepared by so-called hydrothermal synthesis at lo temperatures ranging from 100°C to 200°C requiring crystallization times of 1 hour or more. For syntheses being carried out at temperatures that are higher than the solvent's boiling point, it is necessary to use pressure vessels, and these have to be suitable for the temperature and pressure used during the operation. The pressure vessel has to be designed so that the handling of it does not represent any unnecessary hazard, provided it is is used according to working instructions.
Zeolite syntheses are usually performed in strongly alkaline media, often at pH>14, and the reaction mixture will often contain toxic chemicals, such as e.g.
fluoride.
Conventionally, syntheses that may be performed at temperatures lower than 110°C are carried out in polymer bottles, often Teflon, while reactions at higher temperatures require 2o steel autoclaves, perhaps lined with Teflon. The price of an autoclave of this type with the required safety details are typically of the order of NOK 10.000,- or higher.
Furthermore, such an autoclave will weigh from 1 kilogram and upwards, and all these elements represent limitations regarding the number of syntheses that may be performed in most laboratories in the course of one year.
Zeolite synthesis is often carried out by keeping the synthesis mixture at around 100°C for at least 6 h. At these moderate temperatures sealed chambers are necessary in order to avoid drying out of the synthesis mixture.
3o As an example of conventional zeolite synthesis, Zeolite Y can be prepared according to US 3.130.007, Example 1, by dissolving 5 g sodium aluminate containing 30 weight percent Na20 and 44 weight percent A1203 and 22 g sodium hydroxide containing 77.5 weight percent Na20 in 89,5 ml distilled water. This solution was added to 124.2 g of an aqueous colloidal silica sol with 29.5 weight percent Si02, so that the resulting mixture 3s had a composition corresponding to 13.9 Na20 : A12O3 : 28.2 Si02 : 471 H20, and the mixture was homogenized by stirring. The mixture was enclosed in a sealed glass vessel, placed in a water bath and heated at 100°C for 21 hours, after which the product was recovered by filtering, washed and dried. Common to all the synthesis procedures R~'11RED SHEET (RULE 97 ) mentioned and for all other known synthesis procedures for preparation of zeolites on.
laboratory scale with the purpose of discovering new zeolites or to optimize existing zeolites, is that these are performed in a cumbersome and expensive manner by having to separately prepare each reaction mixture, which typically consists of 4-7 reagents, and by s adding the reagents one by one.
In many other examples the synthesis of zeolites and other molsieves needs temperatures well above 100°C, so that steel pressure vessels or the like are required.
to Furthermore, each reaction mixture is typically prepared in batches of 5 to 100 g and crystallized in expensive and heavy autoclaves with internal volumes often in the range of 25 to 250 ml and with weights of up to 8 kg per autoclave, causing considerable expense due to a large consumption of often expensive reagents and due to the fact that the handling of the heavy autoclaves often makes it impossible to handle more than one 1 s autoclave at the time, and finally that the size of the autoclaves limits the number of autoclaves that may be placed in each oven or heating unit. The combination of all these elements are, according to known technology, making each zeolite synthesis a very resource intensive process, and there is a great need for greater efficiency, rationalization, downscaling and automation. Simple calculations have shown that by combining the 2o different variables which are involved in zeolite synthesis with narrow enough intervals in reagent concentrations, temperatures, reaction time, etc. to cover any phase formation based on known examples, it is feasible to make up 1018 recipes. With to-day's synthesis capacity, which on a global basis hardly exceeds 100.000 syntheses per annum, it would take 10.000.000.000.000 years to carry out all these syntheses in which each and every 2s one in theory has potential for the preparation of a new zeolite or other microporous material. The expenses involved in performing these syntheses according to known technology would obviously be formidable, and there is thus a great need for new and more cost efficient methods for zeolite synthesis.
3o In recent years new, automated methods for systematic preparation of new compounds, so-called "combinatorial techniques", have been developed, but equipment which may be used for liquid phase synthesis at temperatures above approx. 100°C has till now not been disclosed, because this requires that the synthesis takes place in a hermetically sealed vessel at elevated pressures. WO 95/12608-Al for instance, discloses an apparatus and a ss method for a) synthesis of several molecules on substrates, comprising distribution of the substrates in the reaction chambers, b) combination of the first addition of these molecules with different reagents in each of the reaction chambers, c) moving the substrates through tubing to separate mixing chambers where the substrates are mixed, d) SHEE1 (RULE 91) r _ , . _ __ . ~ , redistribution of the substrates by transport through tubing back to the reaction chambers, and e) combination of a second portion of different composition to the first portions of molecules in the different reaction chambers in order to prepare new mixtures.
This publication describes only a system for mixing and distribution of different molecules and s not a system for hermetical sealing of the reaction chambers which would make it . possible to operate at high temperatures, and this system would thus not be suitable for the synthesis of zeolites. In WO 96/11878 there is a description of extensive use of a combinatorial arrangement for synthesis of new materials, including zeolite synthesis at 100°C. Even though this patent application presents a detailed description of ~o instrumentation and equipment developed for different purposes, autoclave systems required for performing the syntheses under the prevailing physical conditions (elevated pressure and temperatures exceeding 100°C) are not described.
Prior art teaches autoclaves with several chambers for special purposes, and there is for ~s instance in US 5.505.916 a description of a metal cassette which can be opened and closed like a suitcase, and which has an interior with compartments intended for placement of the different instruments used by dentists, where these may be sterilized by autoclaving. Furthermore, large autoclaves intended for instance for the growth of crystals, are known, examples are described in US 5.322.591, US 5.312.506 and US
20 5.476.635, but the purpose of these and similar autoclaves is to make it possible to carry out large-scale syntheses, for which there is a great need when a synthetic procedure has been established and scale-up is desired, or when the purpose is to grow single crystals as large as possible. The autoclave described in the earlier mentioned US
5.312.506 is designed to withstand temperatures up to 1500°C for growth of crystals from metal melts.
is Another feature in connection with work with autoclaves is energy savings, and this is addressed in EP 0.434.890 A1, with description of a system for insulation of the autoclave walls and for the design of such insulating layers in the walls, which could be useful for large-scale autoclaving, but is of no relevance when working with small laboratory autoclaves which are heated in ovens.
Furthermore, there is a series of known equipment intended for synthesis of proteins and biopolymers, where the design comprises sheets with a large number of chambers intended for screening of syntheses and crystal growth, in its simplest form as described in US 5.096.676. US 5.400.741 describes a diffusion cell for growth of the largest and the 3s most perfect crystals possible of macromolecular compounds by a technique called the "hanging drop" technique. Several patents, e.g. US 5.013.531, US 5.531.185, US
5.362.325 and EPA 0.553.539 A1, deal with cells for growth of proteins and biopolymer crystals in spacecrafts. Common for the latter patents is that the designs described are very sophisticated and thus vJex-y expen:~ive, because they are intended for use in spa~ecrafts. Cammon for all equipment designed for synthesis :end cry:~tal growth <:~f proteins and biopolymers is that they are meant for_ use at low vemperatures, or typicalllr temperatures in the range of 0°C
vo 65°C, and that they ~onse{:luently are nat designed t:c withstand conditions ty_~ical far hydrathermal synthesis. In addition, many of these prio:_r art syntriesi> cells are not :lined with 'Teflon or c~t:zer similarly inert materials, something that almost without exceptions is required for ;synthesis of zeol.ites and thf~ like. ~lherr is, e.g., a known design called "multiblo~~~" (Krchnak, V., Vagner, J.; Peptide Res. , 182 (1990) ) cansisti,zg of i) a Teflon black holding 42 reactors, polypropyl~~rne syringes equip,~ed with polymer filters, ii) a vacuum adapter connecting each reactor to vacuum line (not descri:oed i:~:i c~etai:l.,' whiclu enables rapid ~Nashing i.n an apparatus for ~:ontinuaus flow, iii) two Teflon plates with 42 stoppers to which the Teflon block is fastened during use and ivj x glass cover 'used during ;~romogenization. The problem with this design is that the :reactors which are made oz glass and whicr~ do not have protected sidewalls~ may -»~ u~ec3 only <3t 1~::~~a pressures and :zot in strongly alkalinsolutions. There is thus no ,available literature describing equiprr~ent that: might be used for practical work with ~~vcombinatorial zeolit.e synthesis, in as much as such syntheses almost without exception require :zydrothermal treatment sf: a ~a:l.ution or c~e:~ wi.th relatively :nigh content of water and often high contents of organic ~~ompounds in a closed charrcber, and almost all methods for , ~reparati.on of zeolites kn cwn so far require such conditions during synthesis, and this is true without exception for ail methods which have proved to be cc>mmerci.ally applicable.
'the synthesis of zeolit°s is thus normally performed under :aydrothermal conditions which require elevated pressures and :?2949-31G
high temperatures in pe:r:iods up to several weeks without :Leakage. The problem has so far been the c:osts involved in i:his type of work, estimated tU an avezwage of NOK 5.000,-per synthesis, including recovery of- the product and XRD
<analysis. An important feat-~.~re when dealing with large ;series of syntheses is ~~here~or-e how the product can be recovered and washed in a rational way without :insurmountable expense, something that. is root disclosed in prior art.. As far as known, tYnis type of work is performed .in the same manner by a:ll synthesis laboratories engaged in :synthesis of zeolites and non-carbon-based molecu:Lar sieves.
The present invEmt:..oru provides ~ complete system nor screening of synthesis c«nditions for preparation of ~eolites and other norm-carbon nuaterials zequiring hydrotherma:l conditions in tine ternpe:ratvurf_ range 100°C to 250°C in a more cost efficient manner, and it has thus been of interest to improve a ser ~e~7 of par--amet~~rs, which means making them more cost a Ef a cif:~nt . Some of these parameters are 1. Reduced size o~ the separate reaction chambers and increased number of read°:_iC>n chambers what is called a multiautoclave.
This will lead t:o :~~educed use of reactants and thus cheaper synthesis.
2. Automated addi~,~ion of reactants, for instance by having 100 reaction chambers present: in one multiautoclave and by enabling this to b~ connected to a a?ipetting machine which rnake:~ quick arid E::x<~ct addition of <~11 liquid reactants po5siblr~.
3. Simple and eas~,~-t.o-use mechanism for the closing and opening of the multiautoclav~:.

E, 4. Simple re,cover~~ and washing of the synthesis product and simple cleanizog of the multiautoclave after use.

5. Devices allowi::ng automated analysis with X-ray diffraction and automatic identification of known c~rystalli.ne phases by combination of an aut:omatie sample ;~witcher, a structure librar~.r stored in a database and :software that can monitor sa;np7.e ;~wit:ct~in~ anc~
:identification.
The present i:nvent:ion also provides an automated c=quipment for larger synthesis series and prepares :Formulations based on mixtures of different:
:Liquids/solutions with varying reactant. z-at.ios .
These and Othar aspects are attained by the ~~resent invention, which rep::_resents a break-through in terms of cost reduction for e.g. zeolite synthesis in that the :reaction mixture crystalls.ze;~ in ~:, vo:l.ume reduced typically '.0 1/100 of what has been used convent:~or~a:~, thereby achieving reduced consurnpt: iom.~f c eact:ant s and cheaper syntheses, and further by enab7.ing automated addition of :reactants, e.g. by having 10.:) or naox~e available reaction chambers in one single :-nultiautoclave, and that the multiautoclave plates can be connected tc~ a pipetting machine that makes quick and exact. addition of all liquid reactants possible, and by baizug able t~c~ p:iace several such plates with reaction chambers on top of each other without ~3ifficulty. Furthermor, an impartant fF=ature of the present invention is the simple and not very time-consuming operation of the multiautoclavc=.
The present invention relates t:o a pressure and Temperature reactor vessel comprising:

:?2949-310 6a a) a central cl.c;ck having a mul t.v.t:ude of perforations, wherein said pr~rforations are through-going perforations, or cavities cr other form cf holes permanently closed at one end, b) cover means, opc_rativea.y associated with a sealing means, for enga<~ement= with said central block to ;peal the open ends of said perforations forming a multitude cf chambers, c) a sealing means, operatively associated with t:he covers means, to fo~~rn a x~r a ssure t i ght seal when said cover means is brought into j.aosit:ion boy a locking means, d) a locking means acting in concert with the cover means to engage tine se~:~li.n~~ means s~ as to define a multitude of reaction chambex.~s .
In one aspect. the invention provides a rnultiautoclave reactor vesserf:o:r use at elevated pressures, comprising: a central b:lc>ck having a plur,.~' ity of perforations, wherein said perforations are through-going perforations; a cover means on both sides of said central block, operatively asso<~i.ated with a c.~E.aling means, for Engagement with said central block to seal open ends of said perforations forming ~~ plu.ra:~ity of react ic>n chambers; the sealing means, operatively a~~saciated with the cover means, forming a pressure tight: sear when said cover means is brought into position by a lc:ocking means; and the locking rneans acting in concert wi. th tree c~ovex~ rr~,e~;~rm t o engage the ;peal ing means so as t c> de f inE~ a pi ural.. l ty c_of react ion chambers.
Applications for tine p:r:esent in°~ention rnay, in addition to zeolite synt~hesi~, be in any field of activities within research and development connected to products where 6b at least one production-step comprises thq~ mixing of_ different liquids, e.g. in the fi..elds of ~orwganic and inorganic syntheses, paint product.ior., fo_~mulation of fuels, food industry, etc., and, furthermoze, ap~~lications within clinical testing, disso~:ut.ion a.nd dagesti:~r~ of samples with acid, etc. where a liquid reGZctant i.s added tc a liquid or :solid. The invention is in L~articular aimed at applications inhere open vessels cannot. be used, and mo:n-E= specifically for ~rpplications where it i;~ reqLrirec~ tc~ cpers:~te at. temperatures which will cause elevated pressures in th~~ liquid part of t:he mixture .
DESCRIPTION OF THE PREFF~RRED EMBODIMENTS
Further advantages and characte:r~sstic features of t:he present invention are illustrated in t:he following description by referring to the dz:awings ~,,ahich, as mere exampa-es without limit_.at:ions, show ;game designs related to this invention, where Figure ~ present. a Side-view of the multiautoclave with the singue components disassembled, and E'igure 2 shows a top-view of the mul.tiaut:.~clave, while E'igure 3 shows an alternat ivf~ desigr~~ c::f t::m~ multiautoclave ;side-view). Figure 4 shows a section of one of the chambers of the mult~~autocla~~e (side-view' equipped with a Teflon liner and disc-stuaped lids. F'iqur~:~ 5a shows a :section of the multiautaclavE~ in "exploded" view, and in Figure 5b in closed mode .
Figure 6 presents an example of different chemical compositions covered in one single experiment using the rzultiautoclave.
More specificall:yr, the invention comprises a unit containing a multitude of pressure verse l , also referred to as a multiautoclave. Thys mvrltiautoclave has typically from 10 to 10,000 or more small, separate chambers (1), each :22949-310 6c Typically with a volume of 0.001.-10 mi.. The multiautoclave is composed of a set of platt~s (2 and '~) and optionally thin laminae (3) which are stacked ~~o that: they form a matrix of ;~mal l chambers ( 1. ) , as sA~own in Figures 1 - 5. The thickness of the different plates and laminae may vary, always keeping in mind that a maximum number of small chambers with optimal size is desired, and that the chambers must be leak tight and dimensioned such that no excessive degree of deformation will take place under the operational conditions which the equipment is designed for. The central block consisting in a perforated plate (2), with a multitude of perforations, serve - when sandwiched between the plates (7a and 7b) and closed - as the frame of the pressure chambers, and may for use at higher temperatures (150 -250°C) be made from stainless steel, aluminium, titanium or other rigid material s.a.
PEEK or the like, with perforations of e.g. 10 mm diameters, where each perforation is lined with a ~o segment of Teflon tubing or tubing made from another suitable polymer material, and where the walls of the linings e.g. can have a thickness of 1-3 mm. For use at temperatures below 150°C, the central block can be made entirely of Teflon, and for use below 130°C it can be made of polypropylene, and for use below 105°C it can be made of polyethylene. In the separate pressure chambers, balls (4) made from Teflon or other ~s suitable material s.a. steel, PEEK, Nylon or glass may be used as a bottom-and toplid, also referred to as sealing means or septa (5) made from an elastomer or from another appropriate material s.a. Teflon in the shape of circular disks which will give the advantage in the form of reduced weight and volume. Septa should be made from an elastomer, preferably Viton, or other suitable material that can withstand temperatures of 2o at least 200°C, and they may be equipped with Teflon lining {13) on the side facing the chamber as shown in Figures 4 and 5. Furthermore, said septa (5) should have a thickness considerably larger than the depth of immersion, as shown on Figure 3, in order to ensure a tight fit when assembling the different elements. As an alternative, septa or balls may be fastened on the bottom and top plates or on separate polymer films or a thin metal plate in Zs such a way that they may be put in place and removed in a simple manner.
The bottom and top plates (7) thus hold balls, septa, stoppers or other types of suitable cover means in place as the central block (2) is squeezed between the bottom and top plates.
In order to avoid the use of balls, septa, stoppers or loose parts, the bottom and top plates can also be designed with a structure that has conical or hemispheric protrusions that fit into the 3o perforations. Another design comprises polymer f lms moulded or otherwise shaped to cover all the perforations. In yet another design, the central block has been machined so that sharp edges (14) protrude around each perforation or well, as shown in Figure 5. The advantague of this design is that one smooth polymer sheet can be used as a lid or sealing device for all the chambers because the sharp protrusions cut into this polymer sheat so 3~ that leakage between adjacent chambers does not occur when the rection vessel is closed with its locking mechanism. Said sharp protrusions ( 14) could alternatively consist of rings or e.g. a rectangular grid that are either welded onto the central block (2) or fastened by any other suitable method. These said protrutions may optionally be part of the insides of the top (7b)- and bottom plates (7a) or the central block (2). The important point here is that the load used when assembling the different elements is concentrated just at the edges of the perforations and lids, so that liquid or vapour cannot leak out during heating.
s In one embodiment, all plates and laminae have a series of holes drilled through (6) for locking means, which can be bolts which are used to assemble the multiautoclave and ensure a sufficient counter-pressure to prevent leakage when the liquid in the chambers is heated to high temperatures, and the bolts are placed in such a manner and their number is adjusted so that a sufficiently distributed even load is obtained in order to ensure that all lo the chambers are tight when in use. The multiautoclave may alternatively be closed by pressing the plates against each other employing a clamping or squeezing mechanism that makes through-going bolts unnecessary. The squeezing mechanism may include springs or the like, which ensure the maintenance of a suitable pressure. A frame made of a rigid material that ensures good tightness in the outer chambers may enclose the entire ~ s multiautoclave, also counteracting deformation of plates made of pure Teflon or another ductile material. Bolts and frames or whatever other locking mechanisms used are tightened with a torque wrench in order to ensure correct load throughout. A
possible feature of the design is that a large number of plates may be placed on top of each other forming layers of reaction chambers according to the desired capacity. As an example, 10 2o plates with pressure chambers can be placed on top of each other without requiring a total multiautoclave thickness of more than typically 25 - 40 cm. Another important feature of this invention is that the large number of chambers which are created by the described assembly of the various described parts subsequent to performing e. g. a number of syntheses can be opened in both ends. This makes simple and efficient recovery and Zs washing of the synthesis products possible, and as an example on how this can be performed, the top plate with associated lid ( e.g. septum) is removed first, and a filter paper placed over it and pressed against the plate with a sponge or another suitable absorbent or a filter supported by a rigid grid connected to a pump. The multiautoclave is then turned upside-down, and the bottom plate with associated lid is removed.
The liquid so in the reaction chambers can then drain through the filter, and the synthesis product can be washed by flushing down through the perforations. As a result, the final, washed synthesis products are each in its own position on the filter paper, and these positions correspond to the positions of the perforations of the mainblock in the multiautoclave, so that identification of the synthesis products can be achieved. The samples are placed in a well-ss defined matrix that, in principle, in a simple manner can be transferred to an automatic sample-switching unit for analysis, e.g. by X-ray diffraction. It is often desirable to calcine inorganic samples after synthesis, and for this purpose the samples can be washed from the multiautoclave and into the perforations of another block which is made of a material suitable for performing calcination s.a. stainless steel or quartz.
Whenever the perforations, which on closing form the pressure chambers are going s through the central block, the bottom has to be closed before charging with liquid or other reactants. This can be achieved in a simple manner by placing the perforated plate (2) on top of a plate (7a) with balls, septa or other sealing devices between them.
The two plates (2 and 7a) are then bolted together with a set of bolts (9) with lengths somewhat less than the combined thickness of the two plates, so that no part of the bolts is protruding from ~o the plate assembly. In the example shown in Figure 2, six bolts placed as illustrated have been found to be sufficent to hold the bottom plate sufficiently tight to the central block.
After the chambers have been charged, the top plate (7b) with its sealing devices is put in place, and another set of bolts ( 11 ), which are considerably longer than the thickness of the entire muitiautoclave, is put through a separate set of through-going holes (6) and ~ s tightened with nuts { I 2) at the bottom side with a torque wrench and with a load sufficient to keep the multiautoclave tight under the prevailing synthesis conditions it is going to be exposed to. Springs adjusted to a suitable pressure can, for instance, be put on the bolts before placing the nuts on them.
2a The advantages of the present invention are primarily related to the large rationalization gain that gives a correspondingly large economic saving. The saving is estimated to be from 90 to 99%. In other words, either the cost related to a given synthesis program is reduced by 90 - 99%, or it is possible for a given amount of money to perform times as many syntheses. Such an automated layout will make it possible to perform e.g.
2s 1000 syntheses/formulations simultaneously, and it will thus be very useful for all research laboratories, in industry as well as in research institutions/
universities.
Multiautoclaves suited for the purposes mentioned above might be designed as described in the following examples, but the descriptions are to be considered merely as examples 30 of possible designs and the given measurements and other details shall not be considered to be limitations to the invention.
Example 1 A multiautoclave is built from S layers as shown in Figure I. The different layers are 3s placed on top of each other and bolted together so that 100 hermetically sealed chambers ( 1 ) are formed. By stacking several layers in a suitable way, it is possible to make a multiautoclave with, e.g. 1000 chambers or more. A decisive element in the invention described here is the combination of steel balls (4) and a thin polymer film (3) for the closing of the small chambers in the multiautoclave. In as much as the contact between the edge of the perforation and the steel ball is exposed to the total pressure developed by tightening the bolts, the multiautoclave will be tight aided by slight deformation of the ductile parts.

The multiautoclave is from bottom to top built up from the following elements as shown in Figure 1. Bottom plate (7a) made from aluminium or steel, with 100 symmetrically positioned cavities (8), each with a diameter of 13 mm. Each cavity has a depth of 8 mm, and stainless steel balls (4) with diameters of 13 mm are placed in each cavity. In ~o addition, the plate has 9 smaller, through-going holes (6) for bolts that are used to keep all the plates bolted together. Furthermore, a thin polymer film {3a) made of Teflon, and the purpose of this film is to tighten against the perforations in the perforated plate (2) and to avoid direct contact between the steel balls (4) and the synthesis mixtures.
The polymer film has 9 smaller holes (6) through it for bolts used to keep all the plates together.
~ s Further, a 2 cm thick Teflon plate {2) with 100 symmetrically positioned perforations with diameter 8 mm. In addition, the plate has 9 smaller holes (6) going through it for bolts used to keep all the plates together. There is also another set of holes (10) through the bottom plate (7a) and the perforated plate (2) that is used to keep these two plates with the corresponding balls tightly together while adding liquid. Furthermore, another thin 2o polymer film (3b) made from 0.5 mm Teflon, and the purpose and design of this film is the same as for (3a). A top plate (7b) is placed above this, identical to the bottom plate (7a), but inverted in relation to it.
A frame ensuring good tightening of the outer chambers by preventing lateral deformation Zs of the Teflon block {2) is fastened around the multiautoclave (not shown).
Example 2 In another embodiment, a multiautoclave was designed and built as shown in Figure 3. In this case, Teflon-lined septa (5) type "MICROSEP F138" from Alltech which are stable 3o up to 250°C were used as bottom- and top-lids for each of the small chambers.
The multiautoclave was constructed from the following elements according to Figure 3. A
bottom aluminium plate (7a), 2 cm thick with 9 smaller, through-going holes for bolts (11) used for holding all the plates bolted together. Above this plate a 2 cm thick Teflon ~ plate with 100 symmetrically positioned perforations with diameters 8 mm is mounted.
Further, above and below each perforation there is a I mm deep recess with diameter 13 mm where Teflon-lined septa {5) with thickness of 2 mm are placed. This plate also has 9 smaller, through-going holes for bolts used to keep all the plates bolted together. There is _~. .. w _..._.... .. , ~ .

also a set of 6 holes (10) with associated bolts (9) used to hold the bottom plate (7a) and the central block (2) together.
An upper aluminium plate (7b), 2 cm thick, is placed on top. This plate also has 9 smaller, through-going-holes for bolts ( 11 ) used to keep all the plates bolted together.
In order to test the designed multiautoclave, the bottom plate (7a) and the central block (2) (Figure 3) were bolted together so that a plate with 100 wells and solid bottom embedding the septa (5) was formed. The resulting were each filled with 0.5 ml water, ~o and a top plate with the associated septa was fastened to it by bolts. The multiautoclave was then placed in a heating cabinet at 150°C for three days. When the multiautoclave was opened after three days, the liquid levels in the 100 chambers were unchanged.
Example 3 is In yet another embodiment, a heavy duty multiautoclave was designed and built essentially as shown in Figure 3, but in this case the 20 mm thick central block (2) was made of 316-stainless steel with 13.75 mm wells which were 19 mm deep. The remaining 1 mm of the plate was drilled through with a diameter of 12.45 mm resulting in a design, essentially, as displayed in Figure 4. The 13.75 mm perforations were lined with Teflon 2o cylinders (13) with 2.75 mm wall thickness and 18 mm length so that above and below each cylinder there is a 1 mm deep recess with diameter 13.75 in one end and 12.45 in the other end. 3 mm thick Teflon disks with 13.75 mm and 12.45 mm diameters, respectively, (5) were used as bottom- and top lids for each of the small chambers.
is Example 4 The bottom plate (7a) and the central block (2) of the multiautoclave described in Example 2 with septa (5) embedded were bolted together so that a plate with 100 wells with solid bottom was formed. This plate was then connected to an automatic pipetting machine of the "Tecan miniprepTM" type which was programmed to dispense the desired 3o amounts from 4 different solutions to each of the 100 wells, so that a total of 100 reaction mixtures with different compositions was prepared in about 30 min.
Example 5 A multiautoclave as described in Example 1 was used for 64 zeolite syntheses based on ss 56 different gel compositions derived from 4 different solutions, including water, so that it covered the composition range for the Na - Si - Al system shown in Figure 6. The matrix had 64 points, but 8 of these were excluded because they appeared outside the desired range. The 8 spare chambers were instead used for reproductions, so that the total number of different compositions were 56, and these 56 compositions are given as molecular ratios in Table 1 and as volume units in Table 2, and the last 5 columns in Table 2 are volume units adjusted so that each small synthesis chamber will contain an exact volume of 0.5 ml synthesis mixture.
s The four solutions were prepared so that all Si is dissolved in solution no. 4 and all A1 is dissolved in solution no. 1. Solution no.l also contains an amount of NaOH
sufficient to keep A1 dissolved as well as water as solvent. Solution no. 3 was used to make-up the NaOH concentration (corrected for Na content in solutions no. 1 and no. 4), and finally, io water was used to make-up the amount of water required for the recipe. All solutions were normalized to 500 p.1. The compositions of the four solutions were:
1. 100 g NaA102 + 8.5 g NaOH + 391.5 g water 2. 21.8 g NaOH + 100 g water is 3. Water 4. Ludox LS-30 which is 30% silica sol in water The solutions were prepared in the order and amounts given in Table 1, and automatic pipettes were used for charging the multiautoclave chambers with the solutions. Four gel 2o compositions were chosen as reproductions, and three parallels of these were made in the multiautoclave and, in addition, a larger scale (approx. 40 g gel) synthesis was performed in a separate plastic flask as a control of the possible effects of down- or up scaling. The four reproductions were chosen so that they represented points in the range of the four zeolitic phases FAU, CHA, GML and LTA given in Figure 4.5.c on page 70 in "Zeolite zs Molecular Sieves, Structure Chemistry and Use" by D. W. Breck, 1974, Wiley and Sons, New York.
The multiautoclave was placed in a heating cabinet after being kept over-night at room temperature. It was opened after 93 hours of crystallization at 100°C, and it was so established that all 64 chambers had stayed tight without leakage, and a large filter paper was placed so that it covered the 64 perforations and a moisture absorbing material was pressed against the outside of the filter paper so that remaining moisture was separated from the crystalline products. The products were washed by adding a small aliquot of water (ca. 0.5 ml) to each perforation for washing. Thereafter, when the solid material was 3s transferred to the filter paper, the perforated Teflon plate was removed and the 64 filter "cakes" were transferred to 64 separate glass sample vials. The samples were then dried at 100°C in a drying cabinet.

Si021A1203Na20/A1203Si02/Na20sum Si02 Na20 AI203 H20 1.0 1.5 0.654 3.53 0.2830.4330.283 19.0 1.0 1.9 0.526 3.90 0.2560.4870.256 19.0 1.0 2.4 0.417 4.40 0.2270.5450.227 19.0 1.0 3.0 0.333 5.00 0.2000.6000.200 19.0 1.0 . 4.0 0.250 6.00 0.1670.6670.167 19.0 1.5 1.5 0.980 4.03 0.3720.3800.248 19.0 1.5 1.9 0.789 4.40 0.3410.4320.227 19.0 1.5 2.4 0.625 4.90 0.3060.4900.204 19.0 1.5 3.0 0.500 5.50 0.2730.5450.182 19.0 1.5 4.0 0.375 6.50 0.2310,6150.154 19.0 1.5 5.3 0.283 7.80 0.1920.6790.128 19.0 1.5 8.0 0.188 10.500.1430.7620.095 19.0 2.3 1.5 1.503 4.83 0.4760.3170.207 19.0 2.3 1.9 1.211 5.20 0.4420.3650.192 19.0 2.3 2.4 0.958 5.70 0.4040.4210.175 19.0 2.3 3.0 0.767 6.30 0.3650.4760.159 19.0 2.3 4.0 0.575 7.30 0.3150.5480.137 19.0 2.3 5.3 0.434 8.60 0.2670.6160.116 19.0 2.3 8.0 0.288 11.300.2040.7080.088 19.0 2.8 1.5 1.830 5.33 0.5250.2870.188 19.0 2.8 1.9 1,474 5.70 0.4910.3330.175 19.0 2.8 2.4 1.167 6.20 0.4520.3870.161 19.0 2.8 3.0 0.933 6.80 0.4120.4410.147 19.0 2.8 4.0 0.700 7.80 0.3590.5130.128 19.0 2.8 5.3 0.528 9.10 0.3080.5820.110 19.0 2.8 8.0 0.350 11.800.2370,6780.085 19.0 4.0 1.5 2.614 6.53 0.6130.2340.153 19.0 4.0 1.9 2.105 6.90 0.5800.2750.145 19.0 4.0 2.4 1.667 7.40 0.5410.3240.135 19.0 4.0 3.0 1.333 8.00 0.5000.3750.125 19.0 4.0 4.0 1.000 9.00 0.4440.4440.111 19.0 4.0 5.3 0.755 10.300.3880.5150.097 19.0 4.0 8.0 0.500 13.000.3080.6150.077 19.0 4.0 12.0 0.333 17.000.2350.7060.059 19.0 6.0 1.5 3.922 8.53 0.7030.1790.117 19.0 6.0 1 .9 3.158 8.90 0.6740.2130,1 19.0 6.0 2.4 2.500 9.40 0.6380.2550.106 19.0 6.0 3.0 2.000 10.000.6000.3000.100 19.0 6.0 4.0 1.500 11.000.5450.3640.091 19.0 6.0 5.3 1.132 12.300.4880.4310.081 19.0 6.0 8.0 0.750 15.000.4000.5330.067 19.0 6.0 12.0 0.500 19.000.3160.6320.053 19.0 ' 10.0 1.5 6.536 12.530.7980.1220.080 19.0 10.0 1.9 5.263 12.900.7750.1470.078 19.0 10.0 2.4 4.167 13.400.7460.1790.075 19.0 10.0 3.0 3.333 14.000.7140.2140.071 19.0 10.0 4.0 2.500 1 0.6670.2670.067 7 5.00 9.0 10.0 5.3 1.887 16.300,6130.3250.061 19.0 10.0 8.0 1.250 19.000.5260.4210.053 19.0 10.0 12.0 0.833 23.000.4350.5220.043 19.0 20.0 1.5 13.072 22.530.8880.0680.044 19.0 20.0 2.4 8.333 23.400.8550.1030.043 19.0 20.0 4.0 5.000 25.000.8000.1600.040 19.0 20.0 5.3 3.774 26.300.7600.2020.038 19,0 20.0 8.0 2.500 29.000.6900.2760.034 19.0 20.0 12.0 1.667 33.000.6060.3640.030 19.0 volume units of solution microliter solution ludox soln soln vann sum factorludox soln soln vann sum 46.82415221.88.803280.2 357.681.39865.45573310.12212.306112.117500 42.38186200.844.78267.85355.811.40559.55614282.17 62.92895.3453500 37.56574178 83.78854.46353.791.41353.08987251.534118.4176.963500 -33.05785156.6120.341.92351.91.42146.97017222.539170.9259.566500 27.54821130.5164.9226.6 349.591.43 39.40061186.676235.8838.0473500 61.52206194.37.555795.47358.871.39385.71586270.74110.527133.016500 56.34861178 39.55183.24357.121.4 R 78.89315249.19155.374116.541500 R

50.59875159.875.1169.64355.171.40871.23129224.99 105.7498.0404500 45.07889142.4109.2556.59353.31.41563.79643201.507154.6180.0876500 38.14367120.5152.1440.19350.951.42554.34291171.647216.7557.2603500 31.7864100.4191.4525.16348.81.43345.56532143.922274.4536.0653500 23.6127574.58242 5.832346.031.44534.11934107.769349.688.42692500 78.70917162.16.0969113.3360.271.388109.2369225.0228.4616157.279500 73.10871150.633.273101.7358.691.394101.9118209.93346.382141.773500 66.69566137.464.39388.4 356.871.40193.4441 192.49 90.218123.848500 60.3437124.395.21675.22355.081.40884.9719 175.038134.08105.913500 52.07744107.3135.3358.06352.751.41773.81736152.06 191.8282.3009500 44.2052791,06173.5341.73350.521.42663.05645129.893247.5359.5215500 33.6429569.3 224.7819.81347.541.43948.4018799.7054323.3928.4998500 86.83113146.95.4075121.8360.931.385120.2887203.5417.4911168.68500 81.19472137.430.245110.6359.441.391112.9455191.11542.072153.867500 74.64676126.359.09997.66357.727.398104.3381176.55182.606136.505500 68.06028115.288.12384.63355.981.40595.59593161.758123.78118.871500 59.3346100.4126.5767.37353.681.41483.88217141.937178.9495.2423500 50.8582386.06163.9350.6 351.441.42372.35622122.434233.2271.9928500 39.2211866.37215.227.58348.381.43556.2915995.2511308.8739.5881500 101.2492119.94.1838136.7362.11.381139.8085165.5995.7771188.815500 95.81986113.524.767126.7360.811.386R 132.7847157.28 34.322175.614500 R

89.34554105.849.312114.8359.271.392124.3431147.28168.629159.748500 82.6446397.8974.717102.4357.681.398115.5296136.841104.45143.182500 73.4618987.01109.5385.49355.491.406103.3234122.384154.05120.24500 64.19 76.03144.6868.39353.291.41590.84579107.604204.7696.788500 50.8582360.24195.2243.8 350.121.42872.6292686.0273278.7962.5493500 38.8915946.07240.5921.73347.281.44 55.9949166.3244346.431.2843500 116.264491.812.9093152.3363.321.376160.0031126.3464.0038209.647500 111.43187.9918.92143.9362.271.38 153.7963121.44526.114198.645500 105.503883.3138.554133.6360.981.385146.1356115.39653.402185.067500 99.1735578.3159.523122.6359.61.39 R 137.8934108.88782.762170.457500 R

90.1577871.1989.388106.9357.641.398126.044999.531 124.97149.456500 80.6289163.67120.9590.32355.571.406113.38 89.5303170.08127.007500 66.115752.21169.0365.06352.411.41993.8043374.0723239.8192.309500 52.1966141.22215.1340.84349.391.43174.6976958.9848307.8858.4422500 131.914862.5 1.581168.6364.591.371180.908185.71222.1682231.212500 128.131260.7112.665162.3363.831.374176.087183.428 17.406223.079500 123.350258.4426.672154.4362.871.378169.966380.528136.751212.754500 118.063855.9442.159145.6361.81.382163.160677.303658.262201.274500 110.192852.2165.217132.6360.221.388152.953172.467490.525184.055500 101.404548.0490.964118 358.451.395141.449167.017 126.89164.649500 86.9943541.22133.1894.16355.551.406122.338657.9626187.29132.411500 71.8648934.05177.569.09352.51.418101.935648.2959251.7797.9937500 146.728134.760.3237184 365.791.367200.561147.51180.4424251.485500 141.272933.4714.739175.3364.761.371193.650745.874720.203240.271500 132.231431.3238.63160.9363.051.377182.111143.141153.201221.546500 125.695329.7855.901150.4361.811.382173.701141.148877.25207.9 500 113.992627 86.824131.8359.61.39 R 158.498837.5475120.72183.231500 R

100.175323.73123.33109.7356.991.401140.306833.2379172.74153.712500 R = point reproduced Example 6 In another embodiment, pre-mixed gels of aluminumphosphate, silicoaluminumphosphate and cobaltaluminumphosphate were prepared and administered by means of the "Tecan s MiniprepTM~~ to the 100 cavities of the multiautoclave of example 3.
Thereafter 6 different organic compounds were added according to the molar ratios specified in Table 3. The multiautoclave was then closed and was heated for 48 h in an oven at 200°C. The solid synthesis products were recovered as described in example 5 and were dried overnight at ambient temperatures. The products were characterised by X-ray diffraction using a ~o Siemens D-5000 diffractometer equipped with PSD detector and an automatic sample shifter. Several different crystalline phases were identified among the products including those of the structures AFI, ERI and CHA.

Mols Mols Mols PositionAIPO SAPO CoAPO R1 Mols R2 Mols gel gel gel R1 R2 2 1 _ 0 0 MORPHOLIN1 - 0 8 0.25 0.75 0 CYCLOHEXY1 - 0 9 0.5 0.5 0 CYCLOHEXY1 - 0 11 0.25 0.75 0 MORPHOLIN1 - 0 12 0.5 0.5 0 MORPHOLIN1 - 0 14 0.25 0.75 0 TRIPROPYL1 - 0 0.5 0.5 0 TRIPROPYL1 - 0 17 0.25 0.75 0 DI-N-PROP1 - 0 18 0.5 0.5 0 DI-N-PROP1 - 0 0.25 0.75 0 TEAOH 1 - 0 21 0.5 0.5 0 TEAOH 1 - 0 23 0.25 0.75 0 TRIETHYLA1 - 0 24 0.5 0.5 0 TRIETHYLA1 - 0 26 0.25 0 0.75 CYCLOHEXY1 - 0 27 0.5 0 0.5 CYCLOHEXY1 - 0 29 0.25 0 0.75 MORPHOLIN1 - 0 0.5 0 0.5 MORPHOLIN1 - 0 32 0.25 0 0.75 TRIPROPYL1 - 0 33 0.5 0 0.5 TRIPROPYL1 - 0 0.25 0 0.75 DI-N-PROP1 - 0 36 0.5 0 0.5 DI-N-PROP1 - 0 37 0 0 1 TEAOH ~ 1 - 0 38 0.25 0 0.75 TEAOH 1 - D

39 0.5 0 0.5 TEAOH 1 - 0 41 0.25 0 0.75 TRIETHYLA1 - 0 42 0.5 0 0.5 TRIETHYLA1 - 0 43 0 0.25 0.75 CYCLOHEXY1 - 0 44 0 0.5 0.5 CYCLOHEXY1 - 0 0 0.75 0.25 CYCLOHEXY1 - 0 46 0 0.25 0.75 MORPHOLIN1 - 0 47 0 0.5 0.5 MORPHOLIN1 - 0 48 0 0.75 0.25 MORPHOLIN1 - 0 49 0 0.25 0.75 TRIPROPYL1 - 0 I

WO 98/36826 PCTlN098/00051 Table 3, gel compositions for MeAPO syntheses, continued.
Mols Mols Mols Position AIPO gel SAPO gel CoAPO gel R1 Mols R1 R2 Mols R2 50 0 0.5 0.5 TRIPROPYL 1 - 0 51 0 0.75 0.25 TRIPROPYL 1 - 0 52 0 - 0.25 0.75 DI-N-PROP 1 - 0 53 0 0.5 0.5 DI-N-PROP 1 - 0 54 0 0.75 0.25 DI-N-PROP 1 - 0 55 0 0.25 0.75 TEAOH 1 - 0 56 0 0.5 0.5 TEAOH 1 - 0 57 0 0.75 0.25 TEAOH 1 - 0 58 0 0.25 0.75 TRIETHYLA 1 - p 59 0 0.5 0.5 TRIETHYLA 1 - 0 60 0 0.75 0.25 TRIETHYLA 1 - 0 61 0 0 1 CYCLOHEXY 0.25MORPHOLIN0.75 62 0 0 1 CYCLOHEXY 0.25TRIPROPYL0.75 63 0 0 1 CYCLOHEXY 0.25DI-N-PROP0.75 64 0 0 1 CYCLOHEXT 0.25TEAOH 0.75 65 0 0 1 CYCLOHEXY 0.25TRIETHYLA0.75 66 0 0 1 MORPHOLIN 0.25TRIPROPYL0.75 67 0 0 1 MORPHOLIN 0.25DI-N-PROP0.75 68 0 0 1 MORPHOL1N 0.25TEAOH 0.75 69 0 0 1 MORPHOLIN 0.25TRIETHYLA0.75 70 0 0 1 TRIPROPYL 0.25DI-N-PROP0.75 71 0 0 1 TRIPROPYL 0.25TEAOH 0.75 72 0 0 1 TRIPROPYL 0.25TRIETHYLA0.75 73 0 0 1 DI-N-PROP 0.25TEAOH 0.75 74 0 0 1 DI-N-PROP 0.25TRIETHYLA0.75 75 0 0 1 TEAOH 0.25TRIETHYLA0.75 76 0 0 1 CYCLOHEXY 0.75MORPHOLIN0.25 77 0 0 1 CYCLOHEXY 0.75TRIPROPYL0.25 78 0 0 1 CYCLOHEXY 0.75DI-N-PROP0.25 79 0 0 1 CYCLOHEXY 0.75TEAOH 0.25 80 0 0 1 CYCLOHEXY 0.75TRIETHYLA0.25 81 0 0 1 MORPHOLIN 0.75TR1PROPYL0.25 82 0 0 1 MORPHOLIN 0.75DI-N-PROP0.25 83 0 0 1 MORPHOLIN 0.75TEAOH 0.25 84 0 0 1 MORPHOLIN 0.75TRIETHYLA0.25 85 0 0 1 TRIPROPYL 0.75DI-N-PROP0.25 86 0 0 1 TRIPROPYL 0.75_TEAOH 0.25 87 0 0 1 TRIPROPYL 0.75TRIETHYLA0.25 88 0 0 1 DI-N-PROP 0.75TEAOH 0.25 89 0 0 1 DI-N-PROP 0.75TRIETHYLA0.25 90 0 0 1 TEAOH 0.75TRIETHYLA0.25 91-100 Reproductions compositions chosen 1 - 90 at random from CYCLOHEX = Cyclohexylamine MORPHOLI = morpholine s TRIPROPYL = tripropylamine DI-N-PROP = dipropylamine TEAOH = tetraethylammonium hydroxide TRIETHYLA = triethylamine ~o

Claims (16)

CLAIMS:

1. A multiautoclave reactor vessel for use at elevated pressures, comprising:
a central block having a plurality of perforations, wherein said perforations are through-going perforations;
a cover means or both sides of said central block, operatively associated with a sealing means, for engagement with said central block to seal open ends of said perforations forming a plurality of reaction chambers;
the sealing means, operatively associated with the cover means, forming a pressure tight seal when said cover means is brought into position by a locking means; and the locking means acting in concert with the cover means to engage the sealing means so as to define a plurality of reaction chambers.

2. A multiautoclave reactor vessel according to claim 1, wherein said sealing means is wholly or partly constructed of a compressible or deformable material.

3. A multiautoclave reactor vessel according to claim 1 or 2, wherein said central block is wholly or partly constructed of a compressible or deformable material.

4. A multiautoclave reactor vessel according to claim 1, 2 or 3, wherein said sealing means is permanently fixed to the cover means.

5. A multiautoclave reactor vessel according to any one of claims 1 to 4, wherein said cover means, acting in concert with the sealing means, has a multitude of protrusions of spherical shape, form or profile, either in part or wholly, presenting a curved surface towards the openings of the plurality of perforations in the central block.

6. A multiautoclave reactor vessel according to any one of claims 1 to 4 , wherein the sealing means consists of spherical shaped bodies or similar shaped components, permanently fixed to the cover means, such that they present a curved surface towards the plurality of perforations in the central black.

7. A multiautoclave reactor vessel according to any one of claims 1 to 4, wherein the sealing means consists of circular disks or other similar circular-shaped components that may be fastened to the cover means.

8. A multiautoclave reactor vessel according to any one of claims 1 to 4, wherein the sealing means consists of flat plate or membrane , covering all the plurality of perforations which may be permanently fastened to the cover means.

9. A multiautoclave reactor vessel according to claim 7 or 8, wherein the circular disks, or the flat plate or membrane, respectively, are permanently fastened to the clover means.

10. A multiautoclave reactor vessel according to claim 7 or 8, wherein the circular disks, or the flat plate or membrane, respectively, may be put in place and removed in a simple manner.

11. A multiautoclave reactor vessel according to any one of claims 1 to 10, wherein the cover means is a single cover said locking means acts in concert with the single cover on one side of the central block to define a multitude of cavities.

12. A multiautoclave reactor vessel according to any one of claims 1 to 11, wherein the cover means comprises an upper cover means and a lower cover means and said locking means consists of a plurality of fasteners passing by means of appropriate hales from an upper surface of the upper cover means through the central block through to a lower surface of the lower cower means.

13. A multiautoclave reactor vessel according to any one of claims 1 to 12, wherein the cover means is comprised of rigid flat plate.

14. A multiautoclave reactor vessel according to any one of claims 1 to 13, wherein said cover means acting in concert with the sealing means, has a multitude of protruding profiles of dimensions sufficiently larger than the dimensions of the perforations in the central block and of cross sectional shape such that in concert with the sealing means through the action of the locking means, a pressure tight seal is formed over and around each of the plurality of perforations in the central block.

15. A multiautoclave reactor vessel according to any one of claims 1 to 13, wherein said central block, acting in concert with the sealing means, has a multitude of protruding profiles of dimensions sufficiently larger than the dimensions of the perforations and of cross sectional shape such than in concert with the sealirng means and through the action of tile locking means on the cover means, a pressure tight seal is formed aver and around each of the multitude of perforations in the central block.

16. A multiautoclave reactor vessel according to any one of claims 1 to 15, wherein the sealing means consists of a polymer film shaped to cover all the perforations.