JPS58183942A - Production of synthetic molded replica - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION In many cases, it is preferable to utilize a variety of supports to form catalyst compositions containing materials useful for catalyzing various chemical reactions. It is usually preferable to use a support with a relatively large surface area, so that more catalytically active material can be deposited on the surface.
This type of support that has been used in the past is made of fire-resistant non-11# compounds such as Al-Sukuri and R-Al-Ken.
Other forms of alumina that have been used and have large surface areas as mentioned above include η-aluminum and #-alumina, and these inorganic oxides also have
It has a relatively large surface area of ypl/l. In addition to this type of catalytic support, U.S. Pat.
? No. 8 discloses an electrocatalyst that can be used to prepare electrodes for electrochemical fuel cells.

The support for the electrochemical catalyst used in this patent is carbonaceous neuro4sv-(pyrep@lym@r) powder or granules, on which the catalytic metal is impregnated. However, as explained, the support is in particulate form, in contrast to the shaped supports of the present invention. That is,
The support of the present invention can be spherical, plate-like, fibrous, monolithic (ms
msllth). The catalyst particulates are mixed with a Teflon powder, an inder material, and then a catalyst-containing sheet is formed by a calendering or arm-ring operation, followed by catalytic leaching of alumina from the electrode sheet. However, forming the sheet requires a Teflon 9 inder,
This formation is not a starting shape AM object, but is formed by calendering. The electrocatalyst powder of this patent, after being combined with a noninder, is shaped by mold Soles or other techniques, which has very different properties than the synthetic shaped replicas of the present invention. For example, the pore structure as measured by nitrogen adsorption or desorption or mercury penetration changes because the pore structure changes due to the presence of inders and defects in the pore structure caused by the physical bonding of individual particles to each other. to differ greatly. Other differences between the granules of this patent and the synthetic shaped replicas of the present invention include chemical properties, electrical properties, and termination properties (t・rmimilprop@rti
・S) and mechanical properties. The chemical properties of the two above are essentially different since the presence of the paddle inder changes the chemical properties of the powder. Since a nofinder is used, the termination characteristics differ in the following points. That is, the synthetic molded cake of the present invention is heated to 500C in a non-oxidizing atmosphere.
While stable above, the support of this patent is limited to use in reactions occurring at temperatures below 300C. Alternatively, while the crushing strength of a synthetic modeled replica is determined by the properties of the carbonaceous and e-iro I remer, the crushing strength of a composition that requires a noider for its modeling is primarily determined by the Determined by the crushing strength of the inner material. This patent discloses large-sized e-iropolymer granules made of crystalline alumina granules in which individual alumina crystals are chemically strongly bonded to each other, whereas aggregates of such granules are Comparatively large spheres, plates, rods, and other structures made of objects are carbonaceous materials containing repeating units containing at least carbon and hydrogen. - Successfully leached into a bale of heap of skin, a macroscopic synthetic shaped object of the original mineral tangible structure is obtained.

Furthermore, U.S. Patent Specification No. 3. *No. 64,133 describes carbon granules used as electrodes and a method for making them. However, this composition
Carzene (carbonaceous) 4 reamer deposited on the surface
(rather than) consisting of a non-conductive oxide. The amount of carzene deposited on the oxide surface is varied by extraction or leaching to obtain a material containing from 50 to about 90% carzene, the remainder of which consists of saponified matter.

As will be explained in more detail below, this is compatible with the compositions of the present invention.
The present invention relates to a novel support containing an auto-cation.

In particular, the present invention relates to novel materials for use as supports for chemically active metals, as molecular seeds, or as adsorbents used on their own in fixed bed adsorption processes.

It is important to use a wide variety of supports for catalytically active metals, thereby modifying or improving the reactions of various catalysts.

As previously mentioned, in many cases the surface area of the support on which the catalytically active metal is deposited is important, and a relatively large surface area is a desirable characteristic of the support. Catalytically active compositions are useful in a wide variety of chemical reactions and have been used in reforming reactions, hydrogenolysis reactions, and the like. A support consisting of a novel material structure and obtained by the process detailed below is used as a catalytic substrate for phosphoric acid to form solid phosphorus (used in the polymerization reaction).
It is also contemplated by the present invention that it may be used as a catalyst support for ammonia synthesis, as a support for metal phthalocyanines that form catalysts useful in sweetening petroleum products such as gasoline, or as a support for immobilized enzyme systems. Included in the scope of The shaped reproductions produced by the process of the present invention can take any of the forms detailed above, including surface area, porosity, and apparent bulk density (appa).
r@at bulkd@m5lty, AID)
, has favorable characteristics such as crushing strength, so that the synthetic shaped reproduction does not physically disintegrate to form powder, dust, or fine powder, and its use is not restricted. Can be used in fixed bed adsorption processes.

Therefore, it is one object of the present invention to provide a new structural material useful in the chemical industry. Another object of the invention is to provide a method for producing a novel structural material.

In one aspect, an embodiment of the present invention is a method of making a synthetic shaped replica of a tangible, porous, and soluble support material. that is, a material of a tangible, porous, and soluble support material having a physical shape and size and an apparent bulk density suitable for use as an adsorbent in a fixed bed adsorption process. a carbonaceous PI W4 that replicates the physical shape and size of the support material and a significant portion of its porosity structure and has repeating units containing at least carbon and hydrogen atoms! -(pyropolym@r)
28N1009G of the apparent bulk density of said support material, comprising the steps of: Steps (a) to (e) of (a) treating the support material with a thermally decomposable organic precursor compound at a temperature of about 400 to 1.gooC in a reducing atmosphere; A carbonaceous pyropolymer having a repeating unit having at least carbon and hydrogen atoms by decomposition! - forming carbonaceous particles in the porous structure of the support material;
Continuing the process of step (a) until the 9 mer deposit is sufficient to produce a crushing strength of about Oa to 14 #. (and (e) contacting the product from the step with a dissolving agent for the support material under conditions selected to substantially dissolve all of the support material; Said Q
l) Leaching said support material from the product of step 1 to form a carbonaceous base material having repeating units having at least carbon and hydrogen atoms! - A method for producing a synthetic shaped replica of a tangible, porous and soluble support material, comprising the step of recovering a synthetic shaped replica containing:

Another embodiment of the invention is a synthetic figurative replica formed according to the method described above.

Another embodiment of the present invention is a method for producing a synthetic shaped article of a tangible, porous, and soluble support material, comprising the following steps (&) to (f).

(a) treating said support material with a thermally decomposable organic precursor compound at a temperature of about 400 to 1200 C under a reducing atmosphere, and thermally decomposing said organic compound to form said at least carbon and hydrogen atoms; (b) forming a carbonaceous material having a repeating unit in the porous structure of the support material; - continuing the process of step (a) until the deposit is sufficient to produce a crushing strength of about 0.5 to 14 kp; (e) substantially dissolving all of the support material; leaching the support material from the product of step (b) by contacting the product from step (b) with a dissolving agent for the support material under conditions selected to (d) recovering a synthetic shaped replica comprising a carbonaceous pyropolymer having repeating units having at least carbon and hydrogen atoms; (d) carbonaceous pyropolymer having repeating units having at least carbon and hydrogen atoms; - depositing at least one saponified refractory material on each surface of said synthetic shaped replica comprising (.) a carbonaceous pyropolymer having said repeating units by oxidation! (f) recovering the shaped replica of the refractory oxide obtained.

1. A method for producing a synthetic shaped replica of a tangible, porous and soluble support material, characterized in that the method comprises:

One more particular embodiment of the present invention is to treat the benzene to pyrolyze the benzene to at least carbon and hydrogen gas under a reducing atmosphere at a temperature of about 400 to 120 oC. A carbonaceous polymer having a repeating unit with atoms is formed in the pore structure of the alumina, and a carbonaceous polymer having a repeating unit with atoms is formed in the pore structure of the alumina. - continue the above treatment until the deposit is sufficient to produce a crush strength of about O, S to 14 #, then under conditions selected to dissolve substantially all of the alumina. in,
By contacting the product obtained above with a dissolving agent containing phosphoric acid, alumina is leached from the carbonaceous pyropolymer and a synthetic shaped replica of the carbonaceous pyro/limer is recovered in physical form. And has the size and fixed bed adsorption! This is a method for producing a synthetic shaped replica of Alunosu that has an apparent bulk density suitable for use as an adsorbent in Tanasu.

Another more specific embodiment of the present invention is to treat alumina with benzene at a temperature of about 400 to 1200 C under a reducing atmosphere, and to pyrolyze the benzene to have at least carbon and hydrogen atoms. Forming a carbonaceous pyromer in the pore structure of the alumina having units of carbonaceous pyrofluorocarbon in the pore structure of the alumina! −
The above treatment is continued until the deposit is sufficient to produce a crushing strength of about 0.6 to 114 degrees, under conditions selected to substantially dissolve all of the aluminum. By contacting the product obtained above with a dissolving agent containing phosphoric acid, alumina is leached from the carbonaceous Noro I remer, and the carbonaceous Noro I remer is leached out. - deposit fluminiram oxide on each side of the
The method of producing a synthetic shaped replica includes removing the carbonaceous filler 4 remer by oxidizing with c and then recovering the resulting refractory oxide shaped replica.

Other objects and embodiments of the invention will become apparent from the following more detailed description of the invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS As indicated above, the present invention relates to a synthetic shaped replica support and to a method of manufacturing this structure. This structure is
An inorganic support of the type detailed below, consisting of a synthetic shaped replica of a granular aggregate and having a desired shape such as a sphere, plate, pellet, red, phyno, monolith, etc.
Isopolymerization of Cpyr by treatment with a reamer precursor (pr.aursor) followed by treatment at an elevated temperature of 1400~tzO (I')
It can be obtained by forming a carbonaceous carbonaceous polymer having a repeating unit containing at least carbon and hydrogen on the surface of the inorganic support. The carbonaceous material deposited on the surface of this support! The amount of - is sufficient to replicate the physical shape and size of the starting material that serves as the mineral support and the equivalent portion of this pore structure. Additionally, the carbonaceous, e-iropolymer that forms the synthetic shaped replica eyelid has an apparent bulk density (ABD) of about 28 to 100 μm of the support material.

The apparent bulk density is the bulk density when filled without vibration. Additionally, the thrift has a crushing strength of about OS to 14 kF or more, with the crushing strength depending on the particle size and size of the replica.

In a preferred embodiment of the invention, the inorganic support material serving as support is
It is characterized by a porous structure containing both macropores and macropores, and a surface area of about 1 to so Orrl/I. For purposes of the present invention, micropores have pores of nooi or smaller, while matarobore have pores of diameter aooi or greater. The pore strength of the shaped reproduction substantially duplicates the pore structure of the support material, and this applies in particular to the pore structure of the mataro.

Additionally, the synthetic build replica retains the original pore arrangement of the support material, and furthermore, the pores II1 wrinkles occupied by the support become available to the synthetic build object after removal of the support material. Become. Illustrative examples of inorganic supports include refractory oxides such as alumina in various forms such as r-alumina, dar-alumina, -mono-alumina, zeolite, silica-alumina, silica-zirconia, zirconia. Included are mixtures of inorganic refractory oxides such as titania, zirconia-alumina, and the like. As mentioned above. like,
The shape of the inorganic support as support material includes any preferred shape. The specific form or shape of the support material is! Le〆Rising (marmm@risimg)
It is obtained by conventionally known methods such as pelletizing (p@ll@tliimg), agglomeration (modulisimg), whereby a support material with a constant pore size is obtained.

In one method of obtaining this composition, an inorganic support, such as a refractory oxide, is heated at a temperature of about 400-1200 G under a reducing atmosphere containing an organic thermally decomposable compound. The most commonly and preferably used organic pi-11-mer precursors for the purposes of this invention include the following groups: That is, aliphatic hydrocarbons, aliphatic halogen derivatives, aliphatic oxygen derivatives, aliphatic sulfur conductors, aliphatic nitrogen derivatives, organometallic compounds, alicyclic compounds, aromatic compounds, and heterocyclic compounds. Among the aliphatic hydrocarbons, the more common for practicing this invention are alkanes, alkenes, alkynes and alkadienes (alkmdl@sn). Alkanes conveniently used for the practice of this invention include ethane, butane, pentane.

Similarly, satisfied alkenes include eden, propene, l
-! Includes thene, 2-zotene and 1-pentene.

Advantageously employed alkynes include edene, pulvin, 1-cutin, 2-zotin, 1-pentyne, 1-hetinine.

Among the alkadienes that can be utilized are 1,3-citadiene and isoprene. Among the aliphatic Hagen derivatives that satisfy the purpose of the present invention, monohaloalkanes are included, and Yuta lumethane, bromomethane, 1-W-dozolopane, and 1-chlorobutane are used. Other tetrahaloalkanes such as carbon tetrachloride, tetraloform, 1,2-shitaruethane, and 1,2-dichlorobutane can also be utilized.

An example of an unsaturated compound that can be used is chlorotetraprene.

Aliphatic oxygen derivatives suitable for use in the present invention include alcohols, ethers, hal@hy
drld・I) and alkene oxides (alk@m
oxld@s), saturated aldehydes or ketones, unsaturated aldehydes or ketones, ketenes, acids, esters, salts and carbohydrates. Among the various alcohols that may be utilized are ethanol, 2-butanol, l-pro-benol, and glycols (e.g., !fl, !).
- such as propanediol) and glycerin. Ethers utilized include ethyl ether and isozorobyl ether. Suitable halohydrins and alkenes include ethylene chlorohydrin, propylene chlorohydrin, ethylene oxide, brypylene oxide. Preferred saturated aldehydes and ketones include formaldehyde, acetaldehyde, ethyl methyl ketone. Unsaturated aldehydes and ketones used include propenal, *-2-butinal, butenone.

Ketenes can also be conveniently used as thermally decomposable organic compounds, salts such as calcium chloride, as well as various carbohydrates. Preferred aliphatic sulfur derivatives include alkanethiol@ (alkmn・tbt・l■), alkylthioalkane tR (alkylthlealka
m@s ), sulfonic acid II (5w1f@ml* a
@lds), alkyl sulfates (alkyl
5w1f false tsi) and alkyl metallic sulfate Ill (alkyl m@talligau
lfat@s). Among the preferred alkanethiols are ethyl mercaptan and 1
-zovxd lumercabutan.

Among the thioalkanes that can be used are thioethers, furkyl sulfides, methyl sulfide, ethyl sulfide, and methyl sulfide. Ethylsulfonic acid and 1-propylsulfonic acid are conveniently used sulfonic acids.

Ethyl sulfate and sodium lauryl sulfate are also suitable for use.

A wide range of aliphatic nitrogen derivatives include nitroalkanes, intermediates, amines, diyls and isocyanides (ear
bylam1m@s). Nitroethane and 1-etrobutylene are suitable examples of nitrialkane, and acetamide and fluoride are included among suitable compounds. Amines such as dimethylamine, ethylmethylamine, nitriles such as acetolyl, silyl, and isocyanides such as ethyl isocyanide are also organic thermally decomposable metal compounds used in the present invention. .

Tetraisopropyl titanate, nacilazotyl titanate,
Organometallic compounds such as tetra($!-ethyl)hexyl titanate can also be used.

Particularly suitable and also preferred for use as the thermally decomposable (pyr@1ysaNe) organic compound of the present invention are alicyclic compounds. Yak stomach hexane and sitahexene are important among these. Aromatic compounds are also available and are subdivided into subclasses including hydrocarbons, metal halides, oxygen vJ derivative ethers, aldehydes, ketones, aromatic acids, aromatic sulfur derivatives, and aromatic nitrogen compounds. being classified.

Among the preferred hydrocarbons, benzene, naphthalene, 7
Siracene and silene are preferably used. Benzyl chloride and benzal chloride are preferred metal halides;
Furthermore, phenol, .-cresol, benzyl alcohol, and hydroquinone are examples of preferred oxygen derivatives. Aldehydes, ketones, such as anisole, fuerate root, unaether, pensfulde, ace)phenone, benzophenone, benzoquinone-anthraquinone, etc.
Quinones can also be used. Aromatic acids such as benzoic acid, acetylic acid, and sulfuric acid can also be utilized, and aromatic sulfur derivatives such as benzenesulfonic acid can also be advantageously utilized. Nidobenzene, l-a)ws7talen,
Aromatic nitrogen compounds such as 7-minobenzene and toluene can also be used as thermally decomposable organic compounds in the present invention. As examples of heterocyclic compounds, S-membered cyclized metal compounds such as 7-tene, male loline, coumaron, thionaphthene, indole, indigo, cal/zole can also be conveniently used. -Ran, Ri! Six-membered ring compounds such as phosphorus and acridine can also be effectively used.

As mentioned above, a wide range of thermally decomposable organic metal compounds can be used. Any organic material that evaporates, decomposes, and polymerizes on a refractory compound when heated satisfies the present invention. However, the resulting carbonaceous polymers will have repeating units containing at least carbon and hydrogen, depending on the selected N4 remer precursor, such as nitrogen, oxygen, sulfur or phosphorus. It can also contain metals.

Other embodiments may also be obtained by impregnating the refractory inorganic oxide with a carbohydrate solution such as pork strose, sucrose, fructose, starch, etc. and then drying the impregnated support.・After drying, the immersion support deity is subjected to the above-mentioned pyrolysis (pyrvlysls).
) sieved at 14 degrees, thereby forming at least a molecular film of carbonaceous 11-mer essentially similar to that described above on the surface of the refractory inorganic oxide support.

The resulting composition has a sufficient amount of a carbonaceous polymer having repeating units containing at least carbon and hydrogen on the surface of the support such that the carbonaceous polypolymer has a weight of about 0 to 14 kg. average crushing strength of crush
str@ngth) and about 2s to 1 of the ABD of the support.
It has a BD of 00 attacks. Moreover, the obtained composition is about 1
Contains the carbon rumored to be IS-60.

Furthermore, the porosity structure of the carbonaceous NeuH/IJY- replicates the porosity of the support material (essentially both macro-4A and micro-pore).

Next, the inorganic support is carbonaceous material! - chemically leached from Leaching is accomplished by treating the composition with a salt or base, resulting in a high surface area carbonaceous atomosphere polymeric support that is a shaped replica of the original mineral support. Leaching of support materials of the type described above is carried out over a wide range of conditions, with temperatures ranging from about ambient temperature (20-25C) to 250C or more, and times ranging from less than 1 hour to about 72 hours or more. . It will be readily appreciated that the operating parameters of the leaching process vary over a wide range and depend on a combination of time, temperature, strength of the leaching solution, etc. Examples of acids or bases that can be used to leach support materials, i.e., inorganic supports such as refractory inorganic oxides, include phosphoric acid,
Inorganic acids such as sulfuric acid, nitrogen oxide, hydrochloric acid, etc.; organic acids such as methylsulfonic acid, ethylsulfonic acid, propylsulfonic acid, toluenesulfonic acid; sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, Examples include strong bases such as cesium hydroxide. Of course, the above-mentioned leaching agents are merely examples of usable leaching agents, and any agent that can remove the refractory inorganic oxide while maintaining a large surface area of the carbonaceous Noiro 4 remer can be used. .

As mentioned above, the i-shaped booklet of granular aggregates has large surface species, favorable pore volume and AlID, as well as high crushing strength, which results in carbonaceous nano-oil vinegar! A shaped replica having - can be used as a catalyst support, immobilized enzyme, or even as a molecular sheep or adsorbent.

The Neuro-I reamer structure can be used as such and, if desired, also as a support on which at least one inorganic oxide is deposited. A solution containing the desired refractory oxide or combination of refractory oxides can be used to impregnate the carbonaceous pyropolymer.

Impregnation of the carbonaceous Aite 1-mer structure is accomplished by treating the structure with a soluble oxide of the desired metal or its sol. A contrast-enhancing compound composition of particle aggregates, comprising at least one type of refractory oxide deposited on substantially the entire surface of a carbonaceous arm A4 reamer having repeating units containing at least carbon and hydrogen. In order to obtain
For example, carbonaceous paddle W/su! - is treated with alumina sol, zirconium oxide sol, titanium oxide sol, etc., or a mixture thereof. Refractory oxides deposited on carbonaceous carbonaceous polymers include aluminum, boron, cerium, iron, nickel, chromium, molybdenum, zirconium, titanium, hafnium, nanodium, tungsten, magnesium, and silicon. , tin, lead, and other oxides. Another method of impregnating carbonaceous Noiro 4 remer structures is to utilize an aqueous solution of the desired metal salt, which salt can then be converted to the corresponding oxide by conventional conversion means such as oxidation. I can do it. Transition metals that can be used
Typical examples of chemical compounds include aluminum acetate, aluminum propionate, and arse succinate. ☆Aluminum sulfate, zirconium acetate, zirconium proionate, zirconium sulfate, its zirconium, titanium acetate, titanium sulfate, titanium succinate, titanium sulfate, vinegar #ni, silicon propionate, succinic acid There are organic gold II4 salts such as silicon and silicon sulfate. In addition, aluminum acetylacetonate, silicon acetylacetonate, zirconium acetylacetonate, titanium acetylacetonate, cerium acetylacetonate, cerium acetylacetonate, copper acetylacetonate, nickel acetylacetonate, chromium acetylacetonate, Of course, organometallic complexes such as molybdenum heptatonate, molybdenum acetyl acetate, or complexes formed between the above-mentioned transition metals and ethylenediaminetetraacetic acid are also included within the scope of the present invention. Such soluble compounds and complexes are then converted to the desired metal compounds by conventional methods such as oxidation at elevated temperatures. Of course, the above-mentioned transition metals and their salts are only representative examples of compounds that can be used to impregnate the carbonaceous J-Irolymer 4111 structure, and the present invention is not limited thereto.

The resulting support has a modified porous f# silkworm, and the final porous structure is characterized by the inorganic support as the starting material, the properties of the carbonaceous/metallic Iromer 1int+ structure, and the impregnated refractory oxide. It is determined by a combination of the layer thickness and the fact that substantially all of the surface of the carbonaceous pyropolymer structure is coated with the refractory oxide.

Optionally, a composition for a sculptural reproduction of a granular metal collection is prepared by coating substantially the entire surface of a carbonaceous resin polymer containing a hydrogen atom and a hydrogen atom as a repeating unit with at least one kind of refractory oxide. It can be effectively used as a catalyst by impregnating it onto a refractory oxide that is a catalytic metal, or by encapsulating it in a refractory oxide.

Addition of the catalytic metal can be done by co-impregnating, pre-impregnating, or post-impregnating the carbonaceous I/'J-mer. For example, about 0.1 to 20
Carbonaceous with the amount of heavy attack! # in an amount sufficient to deposit at least one catalytically active metal on the surface of the Iro I reamer support;
Impregnation is achieved by treating the carbonaceous phyllostructure-molded material with an aqueous or organic solution of the desired at least one metal or combination thereof.

For example, platinum-rhenium, platinum-ruthenium, platinum-ruthenium
Tungsten ζ Platinum-Nickel, Platinum-Rhodium, Platinum-Ship, Platinum-Germanium, /Platinum-Rhenium,
Carbonaceous pyropoly is a mixture of radium-rhodium, tungsten, nickel, ruthenium, radium-lead, and aluminum. - Can be used for impregnation. The solutions available for impregnating the carbon reamer are preferably aqueous in nature; some specific examples of these aqueous solutions include dichloroplatinic acid, dichloroplatinic acid, platinum bromide. acids, sodium platinate, potassium platinate, lithium platinate, platinum chloride, platinum chloride, and the corresponding bath solutions of radium, ruthenium, tin, tungsten, gelconium, and rhodium, as well as their Examples include mixtures. After impregnating the structure, the solvent is removed by heating to a temperature of about 100-400C. This temperature evaporates the solvent and coats the surface of the carbonaceous pile polymer structure with metal or metal-
Sufficient humidity to leave the mixture. Next, the structure is about Zo.

Drying is carried out at an elevated temperature of ~200C for about 2-6 hours or more. The metal-impregnated carbonaceous polymer is then dried in the presence of a reducing atmosphere, i.e., in the presence of a medium such as hydrogen, at a temperature of 200° C.

The metal compound is reduced to particulate metal at an elevated temperature of C or higher for 0.5 to 4 hours or more. Prior to impregnating the carbonaceous bilorimer with a solution or sol of the refractory oxide, metal impregnation can be used to encapsulate the catalytically active metal in the refractory oxide. Conversely, the specified metals can be deposited by utilizing a co-impregnation method or by subsequent impregnation of a carbonaceous pyropolymer composition with a small amount of a refractory oxide on its entire surface. Impregnation can be carried out, thereby
The catalytically active metal is impregnated onto the refractory oxide.

Optionally, after depositing at least one refractory oxide on substantially the entire surface of the carbonaceous pyro-4 reamer structure in the presence or absence of a catalytic metal, the carbonaceous pyro-polymer Sakaki structure is removed. It is therefore within the scope of this invention to replicate this carbonaceous A4 reamer structure, leaving a refractory oxide with a surface area up to several times that of the original mineral support. Carbonaceous pyropolymers can be treated by treating the shaped reproduction composition described above at elevated temperatures in the presence of an oxidizing gas, such as an oxygen-containing gas. Treatment of this composition with an oxidizing agent is approximately 200 to 80%
Under the temperature increase of 0C, the oxygen temperature in the atmosphere is about 0.1-21%
This can be carried out using an oxygen-containing gas. Frugal Pyropoli! - The removal of the carbonaceous pyropolymer is carried out continuously over a period of 1 hour or less to 10 hours or more, and the operating parameters of temperature, time, and acid removal are determined based on the chemical or physical properties of the carbonaceous pyropolymer. Of course, it depends on the film thickness and degree of carbonization. For example, one method for removing the above structure is as follows. That is, at a predetermined time the above composition
c, the temperature is then increased at a predetermined rate to reach the upper range of operation, and then the carbonaceous polyester as described above is treated. - Maintain the above temperature for a sufficient time to remove all of the structure. The shaped replica of the refractory oxide or mixture thereof can then be used as a catalyst support, molecular sieve, adsorbent, etc., and if the replica contains a catalytically active metal as already described, it can itself be used as a catalyst. .

The figurative reproduction can be prepared by any suitable method,
This includes both patch operations and continuous operations. For example, when using a notch operation, an inorganic support such as alumina, as previously detailed, is dried and placed under a reducing atmosphere.

The pyropolymer precursor is then deposited on the inorganic oxide-support at a temperature of about 400-1zOOC, also under a reducing atmosphere.
The precursor is impregnated with the support at an elevated temperature of 12/s! - for a sufficient period of time to cause Alternatively, an inorganic support such as a refractory oxide is impregnated with an aqueous solution of a carbohydrate such as sucrose or dextrose, the impregnated support is dried at elevated temperature, and the dried support is then The carbonaceous resin may be heat treated at a temperature for a predetermined period of time sufficient to form at least a molecular layer of carbonaceous fibers on the support. After recovering the mineral support having at least a monolayer of carbonaceous Nochilo I remer containing repeating units of carbon and hydrogen, the composition is then subjected to a leaching step. In the present invention, carbonaceous polymers having a thickness ranging from one to a few molecular layers are used, depending on various operating parameters such as the amount of carbonaceous carbonaceous polymer precursor used to impregnate the support, the time used, and the temperature. A Nonoiro polymer is formed. The composition is then heated in a suitable device for a predetermined period of about 50 minutes.
It is leached by immersion in an acid such as 96% phosphoric acid at an elevated temperature of 0 to 115 OC or higher. Following the leaching step, the shaped replica of the granular collection with carbonaceous pyropolymer is recovered, washed, and then dried.

After recovering the carbonaceous pyropolymer structure, it is optionally impregnated again with a refractory inorganic oxide or mixture thereof in the form of a sol or a soluble salt, so as to coat the entire surface of the refractory inorganic oxide. An oxide or mixture thereof is deposited.

If the refractory oxide is a soluble salt, it is treated at elevated temperatures so that the boundary is converted to the corresponding oxide.

This conversion can be accomplished by conventionally known methods such as heat treatment and oxidation. The resulting composition has a carbonaceous pyropolymer structure coated on all surfaces with a refractory oxide layer, which itself also constitutes an fI-type replica of the original inorganic support, but with a porous mi is changing. The final porosity structure depends on (1) the pore structure and size of the initial support, (2) the nature of the carbonaceous fibropolymer structure, and (3) the pore structure and size of the initial support.
(4) the thickness of the reamer structure and (4) the thickness of the impregnated refractory oxide coating. In many cases, the surface area of the original starting support is usually increased since both sides of the carbonaceous/irobolimeric structure are coated with a refractory oxide.

The above composition comprises a shaped hard article of a particulate aggregate of carbonaceous/gyropolymer containing repeating carbon and hydrogen atoms, the surface of which is coated with at least one refractory oxide. The carbonaceous pyropolymer is oxidized at elevated temperature in the presence of an oxygen-containing gas, thereby removing the refractory oxide (single or in mixtures) that coated the surface of the carbonaceous pyropolymer structure. ) is left behind.

In an embodiment of the invention, a shaped replica of the particulate mass coated with at least one refractory oxide is impregnated with an aqueous solution of a catalytically active metal.

This impregnation is carried out prior to, in conjunction with, or after the impregnation of the refractory oxide. The carbonaceous pyrolymer structure is impregnated with an aqueous solution of a catalytically active metal by placing the carbonaceous pyrolymer structure in the aqueous solution and conducting the impregnation for a period of 0.5 to 10 hours or longer. This can be carried out by soaking the impregnated structure and drying it at a temperature of about 100 mA for a sufficient time to remove the water after recovery.

Following drying, the impregnated structure is dried for about 25 hours for about 1 to 4 hours.
It is subjected to a reduction treatment using hydrogen at a temperature of 0 to 400C, whereby the metallic portion of the impregnating solution is reduced to elemental metal. If desired, any other method of applying the catalytically active metal to the surface of the refractory oxide, such as by depositing it, can be used and is also within the scope of the invention.

In addition to the above-detailed/mechanical operation, shaped replica supports can also be obtained in a continuous operation. for example,
In cases where this type of operation is employed, an inorganic support, preferably one with a large surface area, is suitable for:
! The carbonaceous reamer containing carbon and hydrogen atoms is repeatedly passed through a heat treatment zone where it is contacted with the pyropolymer precursor at an elevated temperature of about 400 to 400 tzooc so that the carbonaceous reamer containing carbon and hydrogen atoms forms on the surface of the support. deposited on top. By varying the operating parameters such as time, temperature, or properties of the noyl polymer precursor, the thickness of the carbonaceous pyripolymer on the surface of the inorganic support is adjusted to a predetermined size. After obtaining a predetermined thickness of carbonaceous Iro I remer on the oxide support surface, it is withdrawn from the heat treatment zone and then fed to the leaching tank. In a leaching tank, the inorganic support is leached from the above composition at an elevated temperature within the above range using a suitable strength alcohol such as phosphoric acid or a strong base such as sodium hydroxide. After the leaching is complete, the carbonaceous oleopolymer structure, which is a shaped replica of the initial mineral support, is continuously removed from the leaching vessel and, in one embodiment of the invention, is treated with a transition metal salt. continuously supplied with a sol or solution, the carbonaceous A41 reamer support is coated with at least one refractory metal oxide platform;
The entire surface of the carbonaceous A iropolymer is coated. As with the heat treatment (pyrolls) steps of the process, the thickness of the refractory oxide (-bridge or mixture) can be varied and preset by operating parameters of time and solution concentration of the transition metal soluble liquid. After passing through a bath, that is, through a sol, the shaped replica composition of a granular gold collection made of a carbonaceous carbonaceous polymer having at least one refractory oxide deposited on its entire surface is taken out and dried. It is sent to a furnace to remove solvents such as water. The composition may then optionally be recovered and used as a catalyst substrate, adsorbent, molecular sieve, etc., or it may be further continuously fed to an oxidation zone where an oxidizing agent such as water or an oxygen-containing gas such as air or oxygen is added. Approximately 200 ~
An oxidation step at an elevated temperature of 5 ooc removes the carbonaceous Pyro I remer, leaving behind a shaped replica of the refractory metal oxide(s). This i-shaped replica has the same shape as the original mineral support and several times the surface area of the original support.

In another embodiment of the invention, after the inorganic support has been leached to form the carbonaceous pyro-I reamer structure, at least one ear of refractory oxide is passed through a sol or solution to deposit it on the surface. Previously, the structure can be impregnated with the catalytically active metal by continuously feeding it into an aqueous solution of the catalytically active metal. Other variations or embodiments of the invention include passing a carbonaceous pyropolymer support coated with a refractory oxide through an impregnating solution of catalytically active metal, and then: drying the impregnating composition. be. In both instances utilizing pre- or post-impregnation methods with catalytically active metals, the composition is passed continuously through a reduction zone where the impregnated composition is contacted with hydrogen at an elevated temperature. The catalytically active metal is reduced to its elemental state.

By utilizing the above-described process, new compositions with desired physical properties such as crush strength, pore volume, and pore size are obtained, which combat many of the chemical reactions already mentioned. It is used as a catalyst support, molecular sheath, adsorbent, etc.

The following examples are illustrative of the novel composition of the invention and the method for obtaining it, but are not intended to limit the invention.

Example 1 Surface area 147 mγ11 pore size 0.42 a; t/l and ABDo, 37? , 9 1/8 inch (approximately 3.2 haze) diameter alumina spheres were calcined at 482C to obtain a support for the shaped replica. The spheres were then placed under an inert atmosphere and in the presence of the spheres in a reducing atmosphere at a temperature of 788C, the cyclohexane was pyrolyzed to deposit a layer of carbonaceous pyropolymer on the sphere surface.

The resulting composition was then incubated at 16'OC for 24 hours at 9
The resulting shaped replica of the spherical aggregate, immersed and leached in a 6% phosphoric acid solution, consists of a carbonaceous arborobolimer having carbon and hydrogen as repeating units, and analysis shows an alumina content of 0. 27%, indicating that substantially all alumina was removed during leaching.

The spherical carbonaceous arm rimmer is 656m1 and the current BIT
It was found to have a surface area, an ABD of 0.17jl~, and a crushing strength of 7kp. To further clarify the differences between the original inorganic support and the shaped object in the form of a carbonaceous polymer structure replicating the form of the original refractory inorganic oxide, the following Table 1 summarizes its characteristics.

Table 1 Composition Alumina
Carbonaceous Nonoiro I Rimmer ^ Density o:ssywara
0.17 & size V8 inch sphere V8 inch sphere hole - <600f
t, 1o Shire 7 1.84N
N1 hole noodles >600K O, 17 Scream 1.26 Scream Stone J Road 11/Susu Rad 9 Misaki - Togu 600K O, 42 Shoes ffd
0.31 -m-nme de $ll[)600
i 0.07 - 0.21
Rin 4/sha! Total 0.49
0.152 surface area
14th rd/I/ 656 nVI1
Surface Dan surface good body 8! ! , 9 rrl
/kl 111.5m7a solid fraction body/bed body a to 1 filtration value 0.0741al similar Table 1 shows the following. The shaped granular spheres of carbonaceous pyropolymer containing at least carbon and hydrogen as repeating units have the same size and bulk density as the original support. Also, the amount of pores has increased, and the surface area is about 4.15 times that of the original support.

The increased surface area increases its importance as a support for depositing catalytically active metals and makes it more useful as a catalyst for complex carbohydrate reactions.

Example 2 A shaped replica of the granular mass obtained according to Example 1 was then impregnated with a refractory oxide. Impregnation was carried out as follows.

First, the spherical shaped replica is heated at a temperature of 100C under vacuum to remove adsorbed water, and then left to cool.
100% of titanium-2-p4I oxide under vacuum
Multi-stage impregnation with liquid. After approximately 2 hours of impregnation, excess liquid was drained and the spheres were then cleaned with 2-propertool under a phonetic atmosphere. Next, the spheres were air washed and hydrolyzed to obtain a shaped reproduction composition made of carbonaceous pie.

Example 3 The titanium dioxide clad sphere obtained in Example 2 was heated at a temperature of about 540 to 750 C in an oxygen-containing atmosphere to about 8
Oxidized for hours. Spheres were collected during the rut stage of the process and analyzed for crystal structure. The titanium dioxide spheres consisted of a mixture of rutile and anatase; no titanium, titanium carbide, or carbon was detected. From the above, it can be seen that the following can be obtained by using the method of the present invention.

(1) A figurative replica of the original support. This replica is also a globular collection of repeating units of carbon and hydrogen atoms (
(depending on the pyropolymer precursor used).

(2) Refractory oxide molded replica of granular aggregate.

The thickness of the refractory oxide depends on the particular refractory oxide used and the number of impregnations.

(3) Carbonaceous pyro/lj mama - A shaped replica made only of refractory oxide, removed by normal oxidation treatment.

Patent applicant: N.O.B. Continuation of page 1 M. M. Lawrence Brianne Welsh Illinois, USA anston lincolnwood 2203 address

Claims (1)

[Claims] 1. A tangible, porous, and soluble support having a physical shape and size and an apparent bulk density suitable for use as an adsorbent in a fixed bed adsorption process. a carbonaceous nanoW4 reamer of a material that replicates the physical shape and size of the support material and a significant portion of its porosity structure and has repeating units containing at least carbon and hydrogen atoms; A method for producing a synthetic shaped replica of a tangible, porous and soluble support material consisting essentially of: , the following (a) to (e)
Step (a) treating said support material with a thermally decomposable organic precursor compound at a temperature of about 400 to 12 Oar under a reducing atmosphere and thermally decomposing said organic compound to release said at least carbon and hydrogen atoms; Carbonaceous material with repeating unit/#Ilobori! - forming carbonaceous particles in the porous structure of the support material;
continuing the process of step (a) until the reamer deposit is sufficient to produce a crushing strength of about O.S to 14 kl; and (e) substantially all of the support material is removed. said (-) by contacting said support material solubilizing agent with the product from said step (-) under conditions selected to solubilize said (
b) leaching said support material from the product of step to recover a synthetic form Il replica comprising a carbonaceous arm a4 remer having repeating units with at least carbon and water bulk atoms. A method for producing a metal molding material of a tangible, porous and soluble support material. 2. A synthetic shaped reproduction obtained by the method described in claim 1. 3.・Synthetic shaped reproduction according to claim 2, wherein at least one refractory oxide is deposited on each side of the synthetic object. 4. At least one type of refractory oxide deposited on the surface of the refractory oxide. 4. A synthetic shaped replica according to claim 3, comprising one catalytically active metal.