CS270530B1 - Preparation of catalyst - Google Patents

Abstract

Catalyst for the cleavage or condensation of organic compounds at a temperature of 60 to 250 °C (120 to 220 °C), based on a thermally highly stable organic cationite, supported on a thermally stable carrier (graphite, coke, 8102« Al2O3, aluminosilicates) is prepared by impregnation of the carrier with a solution of phthalic anhydride, maleic anhydride (phthalic and maleic acids) and after drying by thermal decomposition and polymerization to form fused high-molecular compounds (such as polyphenyl ketones from phthalic anhydride) at a temperature of » 350 to 550 °C and subsequent sulfonation. The catalysts have all the advantages of cationites, but in addition they are shape-sensitive, sufficiently strong and applicable at temperatures even above 150 °C. They effectively split olefin monomers, alkylphenols into alkenes and phenols, etc., and carry out condensation reactions, such as alkylation and aralkylation of aromatics, etherification, etc. The catalyst is useful mainly in the chemical industry.

Description

CS 270 630 B1

The invention relates to the preparation of a catalyst for calcium and / or condensation of organic compounds, such as the bonding of allgomers of olefinically unsaturated compounds, alkylphenols, arylphenols and aralkylphenols, alkylate and aralkylate of aromatics, mainly phenols, i.e. thermostable solids, modified sulfocations, applicable from 60 to 250 ° C, with high activity, long-term shape stability and life-catalyst.

Organic Ionomers have long been grounded as ionic catalysts in organic synthesis, even in analytical chemistry, in the eeparation of metal ions from polymetallic mixtures, by refining solutions from non-limiting primates and the like. / 0. Samualaon> Ion Exchange

Separatlon ln analytlcal Chemletry. Almqvist and Wikaell, Stockholm, Gothenburg, Uppsala;

Oohn Wlley and Sons, New York - London (1964) t E.E.Ergožin, B.A.Muchitdlnovat Redokslo-nlty. Izdateletvo "Nauka" kazachekoj SSR, Alma-Ata (1983); A. Knop, A. Scheibi Chemletry, and Application of Phenoi Redine. Spronger - Verlag, Berlin, Heidelberg, New York (1979), Russian translation of Penolnye pitch and materials on their oenove. "Chimija" Moekva (1983).

Ioniums represent a macromolecular organic substance, practically insoluble, capable of exchanging evident ions with an equivalent amount of ions in the solution, positive ion exchange resins are called clonlites and negative anionlons. 8, by their chemical nature, and by the ionicity of the high molecular weight compound, the acofenol formaldehyde resin, the styrene-long-benzylbenzene copolymers, the black coal, the styrene-butadiene rubber, and the like. they have functional groups that carry the exchange and catalytic properties of the ions (Pdljanekij N.G.t Katallz ionites). "Chimija" Moekva (1973).

Thus, the structure of the polymer includes groups - SOgH, - COOH, -SH, -P0 (OH) 2 or -AeO (OH) 2, and thus form catlonl or groups - NH2, ΝΗ2, Ν, which give the polymer properties snlonltov. the ions can be used as catalysts for the organic reaction of alkylene, arylae, alkyl lactic acid, esteriflica, depolymerization, hydrolysis, dehydration, condensation, cyanethylation and the like. However, the lack of ionite is low in thermal stability, the temperature of 160 eC (and 100 ° C in water) and 120 ° C anionics is low in catlonals.

The problem of low thermal stability of the catalyzed train is a method of preparing thermally stable temperature-dependent catalyzed polymers of polymers in the conjugated double bonds obtained on the one hand by the homopolycondensation of ketones, on the other hand, by polycondensal acetic anhydride, phthalic anhydride, meleic anhydride of phthalic acid and subsequent sulphonation with the usual sulfonaphthylimidine / APLunin and i .: Author's Certificates 398 677 and 418 498 /. Such thermally stable sulfocation can be applied at temperatures as high as 180 ° C in the alkyl, in the esterification and in the lime-catalytic reactors (Lunln A.F. and in Neftepererabotka 1 neftechlmlja, No 3, pp. 26-27 (1986)].

Despite the advantageous advantages of the so-called soft and temperature-resistant catlonals, their disadvantage is their powder form, they do not allow to be used in the catalytic bed and, when used in suspended state, to be difficult to isolate from the reaction products. In the case of granular powdered sulfocatlonl, the catalytically active surface is substantially altered. Thus, the preparation of catalysts on the catalyst and / or condensate organometallic compounds such as olefin oligomers of olefinically saturated compounds, alkylphenols and aralkylphenols, the alkylate and the aralkylate of the aromatics, preferably phenols, at 60 DEG-260 DEG C. of the present invention exhibits such that the thermally-compatible, porous carrier, the graphite, the granulated activated carbon, the alumina, the natural or synthetic aluminosilicate, and preferably with at least one of at least one of the cyelic organic compounds, of phthalic anhydride, maleic anhydride, phthalic acid, malelic acid, and the like. 270 530 31 of acetic anhydride, followed by thermal polycondensation at 350-550 ° C, preferably 400-400 ° C, was converted to entangled insoluble macromolecular substances, with the predominantly conjugated polyketones. This is followed by sulfonation of a temperature of 20 to 200 ° C, preferably 60 to 140 ° C, by charging the reacted sulfonating agents selected from sulfur trioxide; olea, concentrated sulfuric acid and chlorosulfonic acid. An advantage of the catalyst according to the invention is the possibility to carry out cationic catalyzed reactors and hence organochemical processes even at temperatures above 150 ° C on heterogeneous catalysts in the bed, optionally in suspension or in a catalyst, whereby the catalyst has to be removed from the crude product which it does not contaminate and aninekatalysts the subsequent reaction, reducing process selectivity. In technological applications where the catalyst is a high molecular weight sulphation cation suspended in the crude product, due to the coarse grain size, it is easily removed by sedimentation, filtration or blasting. The advantage is that the specific surface area of such a catalyst and, in practice, does not swell, its spreading stability, the low hydraulic resistance and the range of combs that can be performed thereon compared to conventional commercial organic sulfonates.

The high molecular weight sulfocation compound of the present invention is prepared by sulfonating a conveniently sampled macromolecular substance deposited on a temperature-stable carrier such as graffiti, including crushed coke from high temperature carbonylation of hard coal, granular activated carbon, molded silica, alumina, molded synthetics. aluminosilicates, crushed natural aluminosilicates and the like, granules of the most common size are from 1 to 10 mm.

These carriers are usually repaired by the mite! phthalic anhydride, maleic anhydride, phthalic acid, maleic acid, the solvent being alkylarornates such as toluene, xylenes and other alkylbenzenes, alkylnaphthalenes, but also acetone and ketones, cyclohexanone, cyclohexanol, and the like. Particularly suitable is both the solvent and the components of the synthesis of the macromolecular substance acetanhydride, optionally with the addition of an organic peroxide or hydroperoxide.

Suitably, the impregnated support is desirably freed from the solvent, preferably at low pressure, and up to the thermal polycondensation at a temperature of 350 to 550 ° C, most often at a temperature of 400 to 500 ° C for 3 to 5 hours. In an inert atmosphere, in an enclosed autoclave to prevent loss of phthalic anhydride or maleic anhydride by sublimation. Positive pressure increased pressure, eg 0.3 to 2 MPa. It should be appreciated that also carbon monoxide and carbon dioxide are released by thermal polycondensation. In the process of polycondensation of monomers (phthalic anhydride, maleic anhydride, etc.), crosslinking of polymer chains and particles occurs. The decoupling products formed by both low molecular weight and polymorphic fragments are usually separated and difficult to recycle in further polymer syntheses. These polymers deposited on the thermostable carriers and SalI will use as the matrix the formation of sulfocations.

The most commonly used sulphonate is oleum (25%), concentrated sulfuric acid at 100%, but can also be used at a concentration of 97%. Salts sulfur trioxide and chlorosulfonic acid. From the technical point of view, the simplest is the use of olea and concentrated sulfuric acid. The sulfonation time can be from 1 to 100 hours, from 20 to 200 ° C, but typically from 4 to 5 hours from 40 to 80 ° C is sufficient. In this case, a sulfonating reagent is used, which is then removed from the heterogeneous sulfocyanite produced by filtration and washing with demineralized water. The thus obtained sulfocation exudates the latent capacity most frequently in the range of 2.8 to 5.1 mg / kg / g.

The thermally stable cation according to the invention is particularly suitable for carrying out CS 270 530 B1 with a cationic acid which is based on strong acid-catalyzed organic processes running at a utilizable rate at temperatures of 100 to 120 cC, and long-lived skulls can be woven at temperatures of 150 to 180 ° C and in both short and high temperatures. Such cleavage cation-catalyzed reactions and the base-based process include, but are not limited to, dimeric C-styrene-styrene n-methyl stearate. cleavage of cumylphenols to <X-methylstyrene phenol. Bonding of dimethylphenylcarbinol to OC-matyletyrene and water, Stiepanle of divalent alkylphenols to diphenylphenols, staple of the dye product - "phenol pitch" from the production of phenol and acetone by the so-called polymeric epoxy, to produce mainly phenol and OC-matylstyrene.

Ca lajution catalysed condensation reaction, such as alkylate, especially target. of phenol, cresols and cumylphenols to the corresponding target. butylated phenols, arylation and aralkylation of phenol and alkylphenols, such as phenal aralkylation, methyl styran, alaphenylphenylcarboline, as well as oC-methylstyrene dimers to 4-cumylphenol and 2-cumylphenol, aralkylation of phenol by styrene to methylbenzylphenols; pre-esterified by alcohol alcohol or by acids and p.

The process for preparing the catalyst of the present invention can be carried out either in a continuous or semi-continuous manner.

Selilo data on the implementation of the method of the invention as a benefit are obvious from the examples. Example 1 Prepare a 1 liter flask equipped with a stirrer. 300 g of toluene solution phthalic anhydride at a concentration of 40% by weight. To this solution at a temperature of about 2 to 4 mm and crushed and grinded to a temperature of 200 g of crushed black coal coke. After 1 h and with toluene solution of phthalic anhydride attached coca! free solution by filtration and then under reduced pressure (2.67 kPa) at 60-70 ° C. After the weight of the crushed impregnated coke has stabilized by evaporating the toluene, the weight of the impregnated coke is 243 g. The latter is then placed in a 1 dm 3 stainless steel rotary autoclave. At the same time, 80 g of powdered calcium oxide (burnt lime) is added to the autoclave in the cloth slipper and fixed to a thermowell. Then the auto-clutter closes. blows dmslkoa, starts rotation and heating. Rotation a and after 15 min stop and then every 30 min and rotate for 5 min. The autoclave is heated to 430 to 460 [deg.] C. for 1.5 hours and kept at this temperature for 4.5 hours. The outoclave is then cooled and the " impregnated " 450 g of acid and concentrate 100% by weight. and the entire contents of the flask and are heated to 100 ° C. It is kept for 1.5 h at this time. The entire contents of the flask are then left to cool at 45 DEG C. and the bulk of the sulfuric acid is filtered off on a ceramic filter. Thereafter, the " impregnated " crushed coca is poured into 300 cm @ 3 of distilled water and the ceramic filter is carefully dispensed, and washed with distilled water until neutral. The impregnated crushed coke and sulphonated polymers, mainly sulfopolyphenyl ketones, were deposited at 70 to 80 DEG C., and thus mainly the sulfopolyphanyl carboxy coating catalyst (catalyst A) with a exchangeable capacity of 4.7 mg-eq./g.

The fraction "phenol pitch" having a melting point of 30 to 160 ° C / 2.67 kPa has this composition (in X by weight) of? -Methylstyrene »1.5; acatophanone> 50.6; dlmethylfanylcarboline 23.9; phenol 18,1,1,1,3-triaethyl-3-phenylindan 0.4; 2,4-dibloro-4-methyl-1-pentane 0.9; trans-2,4-diphenyl-4-methyl-2-pentane 0.2; 2-cumylphenol · 0.9; 4-cumylphenol 0.03.

After addition of the phenol to the molar ratio of phenol / dlmethylphenylcarboline 3.58 m, the feedstock is fed to the aralkylene catalyst this composition (in% by weight): v-styrene-ethylene »1.2; 4 CS 270 530 B1 acetophenone »36,3j dimethylphenylkerbinol» 16,4; phenol 40.7; 1,1,3-trimethyl-3-phenylaluminum 0.01; 2,4-diphenyl-4-methyl-1-pentene * 0.71; trans-2,4-diphenyl-4-methyl-2-pentene 0.01; 2-cumylphenol 0.68 and 4-cumylphenol> 0.01. This feedstock was arylalkylated phenol with dimethylphenylcarbinol both on the sulfonated copolymer styrone-divinylbenzene resin (Katex Oetion KS) in H-form, with an exchange capacity of 5.59 meq / g, and on catalyst A, which was heated in EXAMPLE 1. The effect of temperature on said aralkylation of dimethylphenylcarbinoloyl phenol in said fraction with a molar ratio of &lt; 3 &gt; -phenol / dimethylphenylkerbinol of 3.584, catalyst loading of 0.085 kg.a. . »S and flow« 3 3 - 3 - 1 Cat · Nitrogen 4,67.10 "· β" * The time of each continuous experiment is 6 h.

The results are shown in Table 1. However, at 170 ° C, the cation exchanger in H-forms is "knocked down" for 5 hours by blocking the bed and decreasing the selectivity of dimethylphenylcarboline to 4-cumylphenol to 57.3%, while on the catalyst And it holds virtually unchanged selectivity for 4-cumylphenol reaches 86.3 to 89.9%.

Table 1

Catalyst Thermaralkylation (° C) Conversion (%) Carbol selectivity Dimethylphenyl - (%) to: Phenylphenylphenylcarbol phenol x4-4ówyl-phenol methyl-dl-methyl-styrene Catex in H-form 90 43,3 96 , 9 31.6 22.2 39.3 Hexagonal cation exchanger 115 73.8 99.6 53.7 0.0 31.8 Hexagon cation exchanger 130 100.0 100.0 80.8 0.0 17.7 Cation exchange resin in H-form 140 100.0 100.0 88.2 0.0 1.2 Cation exchanger H-form 170 100.0 100.0 88.0 0.0 1.7 A 90 58.1 98 2 42.8 11.0 35.2 A 130 100.0 100.0 82.0 0.0 16.9 A 140 100.0 100.0 89.1 0.0 0.5 A 170 100.0 100.0 89.8 0.0 0.4 Example 3

The fraction of phenol pitch with tv 160 - 210 ° C / 2.67 kPa after phenol addition to achieve a molar ratio of phenol / long-C-ethylstyrene 1.54 by composition (in% by weight): CC-methylstyrene 0, 2; acetophenone «1,2; dimethylphenylcarbinol 0.8; phenol »24.9; 1,1,3-trimethyl-3-phenylindan 0.7; 2,4-diphenyl-4-ethyl-1-pentane-31.3; trans -2C4-diphenyl-4-methyl-2-penone 5.3; 2-cumylphenol 8.4; 4-cumylphenal-23.0 in addition to the arylalkylation of the phenol CC-methylstyrate on the sulphonated copolysis styran-divinylbenzene resin (Ostion KS cation exchanger) in H-form, with an exchange capacity of 5.59 meq / g and on catalyst A The effect of temperature on said arylalkylation of the phenol dimethyl phenyl carbinoloa in said fraction at a molar ratio of phenol / dimer-methylstyrone of 1.54, loading of a catalyst of 0.086 k? The duration of the individual continuous experiments is 6 h. The results obtained are shown in Table 2. EN 270 530 81

Table 2 5

Catalyst Temperature Alkylation (° C) Conversion (%) Selectivity of the dimer-methvletrafene reaction Extraction of 4-cumylphenol in excess of methylstyrene (%) phenol dimers of α-methyl-ethyran to 4-cumylphenol (%) Phenol ( %) Cation exchanger in H-form 90 26.8 27.1 71.9 98.2 19.5 Cation exchanger H-form 100 27.6 27.6 73.6 98.8 29.3 Cation exchanger H-form 120 32.4 28.1 85.9 99.0 24.2 Cation exchange in H-form 140/44; 9 36.7 91.9 100.0 33.7 Cation exchange in H-form 150 47.5 38.7 94 , 6 100.0 36.6 Catex in H-form 170 50.4 40.8 95.2 100.0 38.8 A 100 29.6 30.2 72.6 98.6 21.9 A 120 35, 6 31,8 85,2 99,0 27,1 A 140 48,5 40,2 92,5 100,0 37,2 A 150 52,2 42,8 93,6 100,0 40,1 A 170 59 , 6 47.5 96.2 100.0 45.7

Similar to Example 2, when warming above 170 ° C and H-form cation exchanger, so as to clog the ampoule to decrease the elution of the dimer of dimeric β-methylethyrene to 4-Kunylphenol, the So on catalyst A decomposes practically unchanged and selectivity to 4 -cumylphenol is high. Example 4

The products from the production of phenol and acetone by cumane epoeob "phenolic pitch" deposition (in% by weight); N-methylethyran 0.2} acetofanone 10.8; dimethylphenylcarbinol 7.9; phenol 4.5; 1,1,3-trimethyl-3-phenylindan 1,2; 2,4-dimethyl-4-methyl-1-pentane 15.9; trane-2,4-dimethyl-4-methyl-2-pentane 3,4; 2-kuaylphenol 5.1; 4-cumylphenol - 27.9; with the remainder forming a heating element, and leading to the catalytic decomposition of dimethylphenylcarboline to X-methyllethyran and water, as well as dimar-C-methylstyrene to OC-methylatyrene, as well as cumylphenols naphthylmethyranes and phenol; in the H-form with an exchange capacity of 5.59 meq / g, on the catalyst A which is prepared as described in Example 1. At a temperature of 180 ° C, a catalyst load of 0.086 kg · m 2 · t. e &apos; ' &apos; &apos; &apos; &apos; &apos; &apos; &apos; &apos; &apos; &apos; &apos; &apos; s &lt; tb &gt; &lt; tb &gt; ______________________________________ &lt; tb &gt; t to--methylethyran 86.4% e to phenol 93.2%. The cation exchanger is dark-colored and partially agglomerated after use, as is the ongoing degradation process. When using catalyst A prepared as described in Example 1 under conditions similar to those of the previous catalyst, conversion of dimethylphenylcarbinol to 92.3%, dimar (-methylethane 81.4% and cumylphenols 99.8%, eelectivity to t-methylstyrenate 98.9% and phenol 96.3% No changes were observed on catalyst A. Example 5

The procedure is similar to that of Example 4, except that the "phenol pitch" is a phenol pitch fraction of 160-190 ° C / 2.67 kPa in the composition (in% by weight); phenol 0.1; 1,1,4-trimethyl-3-phenyl-indane 1.0; 2,4-diphenyl-4-methyl-1-pentene »66.8; trans-2,4-diphenyl-4-methyl-2-pentene 11.4; 2-cumylphenol 16.8; 4-k

I CS 270 530 B1 Mylphenol 0.7, obtained by rheification of phenolic amols to a column of column efficiency with an effective 20 theoretical, pressure of 2.67 kPa and a 5: 1 reflection ratio. H-formapri, 180 ° C, conversion of dimer-methylatyrene 71.8% and kaylfanols 92.0% with selectivity to XX-methylethyran 93.2% and to phenol 94.8% is achieved.

They observe and also deep dagression catalyst changes and rapid decline in activity. When the catalyst A is used, it is as described in Example 1, at 180 ° C and at a temperature of 85.7%, a cumene phenol of 97.1% and a selectivity of--methyl-styrene of 96.7% and 180%, respectively. phenol 98.7%. No degradation catalysts are observed, nor does the activity decrease.

In conditions similar to those prepared by Catalyst A in Example 1, Catalyst B is prepared by impregnating the molds (4 aa diameter and 6 mm lengths) of creme with a mixture of xylene-acatan hydride solution (80:20) by phthalic anhydride with a conc. 42 wt. (30 wt% phthalic anhydride and 12 wt% maleic anhydride). Further, the procedure is similar to that of Catalyst A and Alarm A of Example 1.

Oaho exchange capacity is 5.1 meq / g.

This catalyst (B) is initiated at 180 ° C and the conversion of the diastereo-styrene 92.1%, cumylphenol 98.3%, with selectivity, is achieved by otherwise similar conditions to those of catalyst A and the cation exchanger H-form. to OC-methyletyrene 96.1% and to phenol 99.2%. Example 6

The catalyst A targeted in Example 1 was subjected to a target reactor. butyl-4-cumylphenol methyl tert. butylate at mol. methyl-target ratios. butyl ether: 4-cumylphenol »2: 1, while the catalyst is loaded with a solution of 4-cumylphenol in methyl ether. butylate 0,28,8- ^ 4 * -1 1,0 - «- 1 - 1 - 1 - 1 - at a temperature of 110 to 160 ° C and at a constant flow rate of 0,26 0Λη · 8Β | Simultaneously, and for comparison, they make experiments with otherwise similar conditions, but using sulphonated copolymer styrene-divinylbenzane resin (H-form Osti-KS). The results obtained are summarized in Table 3. The hydraulic resistance increases at 160 ° C and at the H-form cation exchanger, however, after 2 hours.

Table .3

Temperature Conversion (%) Selectivity (%) to

Methyl tert-butylation catalyst. butyl ether of 4-cumylphenol 2-tert. butyl-4-kumylphenol 2,6-di-tert. butylphenol phenol dimers o6-matyl · styrene Catex in H-form 110 69.8 13.4 58.4 15.9 2.9 22.6 A 110 69.3 14.2 60.9 15.8 2.8 20 , 4 Katax in H-form 130 84.2 18.2 65.4 12.7 2.9 12.6 A 130 85.1 18.9 67.1 11.3 2.6 10.1 Catex in H-form 160 94.3 69.8 88.1 5.3 3.6 1.9 Catex in H-formapo 2 h 160 86.9 65.9 81.3 5.5 4.8 6.7 A 160 99.8 84.2 89.3 4.5 3.4 1.5 A after 2 h 160 99.7 84.3 89.4 4.5 3.4 1.6

Claims (1)

OBJECT OF THE INVENTION Process for the preparation of a catalyst for the cleavage and / or condensation of organic compounds, such as the cleavage of oligomers of olefinically unsaturated compounds, alkylphenols and aralkylphenols, alkylation and aralkylation of aromatics, and preferably phenols, at a temperature of 60 to 250 ° C, characterized in that the support, such as graphite, granular activated carbon, alumina, natural or synthetic aluminosilicate, is preferably impregnated with at least one of the oxygenated organic compounds among phthalic anhydride, maleic anhydride, phthalic acid, maleic acid, acetic anhydride and subsequent thermal polycondensation at 350 to 550 ° C, preferably at 400 to 500 ° C, is converted to soldered insoluble macroasecular substances, and preferably predominantly conjugated polyketones, which are subsequently sulfonated at a temperature of 20 to 200 ° C, preferably 60 to 140 ° C, by treatment with at least one sulfonating agent selected among sulfur dioxide, oleum, concentrated sulfuric acid and acid chlorine sulfone. '