CS267357B1 - A method for producing high silica zeolite - Google Patents

Abstract

The method of production of high-silicon zeolite of the general formula NanAlnSi<)fJ._nOi92 · xH2O, where n is greater than 27, x = 0 to 20 (ZSM-5 zeolite) is carried out by hydrothermal synthesis from starting mixtures, containing mainly sources of silicon, aluminum and sodium, with the addition of seed high-silicon zeolite, mainly in an aqueous environment addition of at least two aliphatic alcohols Ci to C8 or their mixture with at least one other oxygenated organic compound with a number of carbons in the molecule of 1 to 8, or 2 to 10 (ketones, aldehydes, ethers, esters, acetals). It is thus possible to use more advanced products of chemical, especially petrochemical, but also biological processes, containing mixtures of alcohols and other listed oxygenic organic components. The method is suitable for the production of synthetic zeolites and catalysts in the chemical industry.

Description

EN 267 357 B1

The present invention relates to a process for the production of ZSM-5 type high-zeolite zeolite by inoculating the starting reaction mixture with a targeted zeolite by the presence of technically readily available liquids.

Furthermore, the importance of high-silicon / colitics alone, as well as the active carrier of catalysts and catalytic systems, has been provoked by the need for production growth and simplification of the production of such zeolites. Their composition can vary in the content of aluminum and aluminum, while in the borderline case it can go as much as aluminum without aluminum, the so-called silicalite. The original Mobil process (U.S. Pat. No. 3,702,886) uses tetrapropylammonium compounds to form the ZSM-5 zeolite crystal lattice, but these are technically more difficult to obtain and are therefore suitable substitutes. Such include the use of ethylamine and other aliphatic amines ( Czechoslovak Authentication Certificate234 814), diamines, ammonia, pyridine and alkanolamines (Mravec D., Ilavský J .: Oil and Coal28, 197/1986 /; Seidl V .: ibid. 202; USAp. 3 702 886, 4 151 189, 4 046 859 and 4 139 600). In addition, zeolites of this type are synthesized using seed crystals of just zeolite ZSM-5 as crystallization nuclei and mixtures of acetone-water without other organic templates (Narita E. et al., Chem. Letters, 1984) 055, Narita E. et al., Ind Eng Eng Chem Prod.Res. Dev. 24, 1985, 507). Even the hydrothermal synthesis of ZSM-5 type zeolites is carried out in an aqueous medium with the addition of 0 to 30% by weight. aliphatic alcohol C1 to C8 (Certificate No. 255 394). However, despite the evident progress of these latest solutions, not all the technical possibilities of improving the production of silicite zeolites, especially of the ZSM-5 type, have been exhausted. However, these extractive processes can be further modified using the technically readily available organic intermediates, including mainly the petrochemical processes. Thus, according to the present invention, there is provided a process for the preparation of the high silica zeolite of the formula NatlAl / SiO2O2O2. xH2O in which n is greater than or equal to 0 to 20, the hydrothermal synthesis is at a temperature of 130 to 250 [deg.] C., generally at a vapor pressure at the working temperature used, from a feed mixture mainly comprising a source of coke, aluminum and sodium with the addition of 0.01 to 10 wt. high-zeolite zeolite with a crystalline phase content of 75 to 100%, at least predominantly in an aqueous medium, with the addition of an aliphatic alcohol C 1 to C 8 such that the addition is in an amount of 0.1 to 40% by weight. % of at least two aliphatic alcohols C8 and / or a mixture of 50 to 95% by weight. at least two aliphatic alcohols C 1 to C 8 and 5 to 50 wt. at least one further oxygen organic compound selected from C3 to C8 ketones, C (to C8, dialkyl ethers C2 to C10 aldehydes). esters of C3 to C7 and cyclohexanol. The advantage of the production method according to the invention is the technical simplicity of the formulation of the components of the reaction system. Furthermore, a synergistic effect of a mixture of at least two aliphatic alcohols C1 to C8, as well as mixtures thereof with other oxygenated organic compounds, in particular tetrachlorides, flavors and aldehydes, for the production of high-crystalline zeolites with high crystallinity (90 to 100% by weight). 94%) and find new components for modifying the production of said zeolites. The method makes it possible to technically utilize both predominantly alcoholic and by-products of chemical and especially petrochemical processes, for which processes of higher technical-economic recovery are rarely avoided. In addition, the low toxicity of the applied components of the process of the invention and the practicality of the conventional manufacturing equipment are also advantageous. The high silicon zeolite thus produced can be freed from the water at the elevated temperature of the crystalline adsorbed water.

The addition is a mixture of at least two aliphatic alcohols C1 to C8 and at least one other oxygen organic compound, such as aldehydes, ketones, ethers, acetals and esters. They form, on the one hand, deliberately synthesized and manufactured products, such as Fischer-Tropsch synthesis from synthesis gas on iron ore. zinc-iron-chromate or zinc-copper catalysts, especially acetylene-activated catalysts, producing aliphatic alcohols C 1 to C 4 and even up to C 12, and mixtures of aliphatic alcohols formed as the next chemical, but most notably petrochemical and biochemical product -Mic processes. The most preferred alcoholic fraction of 2-ethylhexanol rectification (2-EHLP), typically a fraction of about 109-182.5 ° C (101 kPa), of oxoprocess, containing butanol, isobutanol, 2-ethylhexanol, isobutanol, 3-heptanone and 2-ethylhexanol as the main components, with admixtures of other oxygen species. Thereafter, the production of butanols and 2-ethylhexanol by oxosynthesis (from propene and synthesis gas followed by dehydration, n-butyraldehyde dehydration, hydrogenation to 2-ethylhexanol as well as n-butyraldehyde and isobutyraldehyde hydration to butanol and isobutanol), respectively . oxoproce-som, from organic scrubbing water, so-called. a stripole containing from 70 to 85% of a mixture of n-butanol with isobutanol; % n-butyraldehyde, 5 to 25 wt. water, admixtures of toluene, esters and other unidentified ingredients.

Then, a by-product of the production of cyclohexanol-cyclohexanone by catalytic oxidation of cyclohexane, in particular a forward alcohol product, isolated from the rectification (from the FK.-102 column) is predominantly a cyclohexanol-cyclohexanone mixture. The density of this colorless top product at 20 ° C is in the range of 840 to 865 kg. m J and 95% distillates in the range of 92 to 142 ° C / 101 kPa; acid number = 0.01 to 5 mgKOH / g; saponification number = 10 to 60 mg KOH / g; bromine number = 8 to 38 mgKOH / g; hydroxyl groups = 8-22%; % carbonyl groups = 2 to 8% by weight, typically 48 to 58% by weight; amylalcohol; 8 to 10 wt. n-butanol; 1 to 2% «. CS 267 357 B) 4 wt. butyl alcohol; 3 to 5 wt. isoa-alcohol; 4 to 20 wt. % of cyclohexanone; cyclopentanol; 0.1 to 6 wt. % of cyclopentanone and 0.5 to 3 wt. % water. Mixtures of Cyclohexanone, Cyclohexane and Ivona Cyclohexanol 0.1 to 2 wt.

Further, crude "synthetic" methanol, product-fishery Tropsch synthesis, respectively. catalytic hydrocondensation of synthesis gas, in particular alkyne-doped, and especially carried out on iron, zinc, medium and chromium catalysts.

Mixtures of alcohols and possibly also mixtures of alcohols and acetone produced by the fermentation processes may also be used.

Further details of how to carry out the process of the invention as well as other advantages will be apparent from the examples.

Example I Preparation of high silicon zeolites of general formula Na &quot; Al Si &lt; 5 &gt; (&lt; 92.9 &gt; 16 H2O (type ZSM-5) is carried out in 130 cm &lt; -1 &gt; steel coated ampoules placed in a heating block 25.2 g of silicic acid hydrosol at a concentration of 29.75% by weight of silica, to which an aqueous solution of aluminum (0.83 aluminum sulphate in 30 cm) was added dropwise was added to each flask. water) and then an aqueous solution of sodium hydroxide (1.50 g of hydroxide solution in 33 cm @ 3 of water). In addition, a seed of zeolite ZSM-5 of module 28.1 in quantities of 0.33 g and 4 each is added to each vial. 50 g of a mixture of at least two aliphatic alcohols with the addition of at least one further oxygen-containing organic compound, The prepared mixture of each vial is homogenized at room temperature (20 ° C) for 20 min. in the molar ratio of oxides: SiO2 / Al2O3 = 100; Na2O / SiO2 = 0.15; 1120 / SiO2 = 35.90. The hydrothermal synthesis is carried out at 190 ± 3 ° C for 14 h. After cooling, the crystalline fraction is filtered off, washed with distilled water and then dried in a vacuum oven for 4 h at 110 ° C. The product obtained is weighed and analyzed. In addition to the determination of the components, their crystals were determined by x-ray diffraction analysis of the samples of the ZSM-5 type thus produced (in%). The results obtained are summarized in Table 1. In each experiment, the addition of a mixture of oxygenated organic compounds is used. Thus, experiment 1a is a forward alcoholic product from the cyclohexane oxidation process to cyclohexanol and cyclohexanone isolated from the rectification (from an FK-102 column, hereinafter referred to as FK-102, predominantly cyclohexanol-cyclohexanone mixture. FK-102 (colorless liquid) is such that the density at 20 ° C = 855 kg / m 2 95% is distilled in the boiling range 106 to 142 ° C / 101 kPa, average mole weight = 109.4 g. mole 1 kinetic viscosity at 20 ° C = 3.86.10 "nP.s"; water content = 3.6% w / w OH = 14.25% w / w bromine = 27.8 g Br / 100g; CHO = 4 Acid value = 0.95 mg KOH / g, saponification number = 21.0 mg KOH / g, n-amyl alcohol = 51.9% w / w isoamyl alcohol = 3.7% w / w; n-butanol = 9.5 wt% sec butyl alcohol = 1.1 wt% isobutyl alcohol = 5.6 wt% isopropyl alcohol = 0.2 wt% cyclohexanone-4-methyl mixture 1-pentanol = 19.7% by weight and 9 admixtures mainly of oxygenated organic compounds Further, in Experiment 1b, this is the leading alcoholic component of the rectification of 2-ethylhexanol (hereinafter referred to as 2-EHLP) in the oxosynthesis process (propylene wasroformylation to n-butyraldehyde mixture, with isobutyraldehyde, aldolysis of n-butyrolaldehyde associated with aldoluCs dehydration) and hydrogenating it to 2-ethylhexanol, a fraction of about 109-182.5 ° C / 101 kPa; density at 20 ° C = 812.2 kg. m1; n% = 1.4088, OH = 19.4%; CHO = 0.24 wt% CHO bound = 0.25 wt%; bromine number = 1.3gBr / 100g; acid value = = 1.26 mg KOH / g; saponification number = = 2.50 mg KOH / g; water content = 0.4 wt%, isobutanol = 20.3 wt%; n-butanol = 50.7%; isoamyl alcohol = 4.1%; 3-heptanone = 4.1%; 2-ethylhexanol = 2.0% by weight; 2-ethylhexanol = 15.3 wt. and the remainder is at least 3 unidentified oxygenated organic compounds. In Experiment 1c, it is again a heavy fraction of 2-ethylhexanol in oxoprocesis to produce butanol and 2-ethylhexanol, hereinafter referred to as 2-EHTP, at a density of 20 ° C - 896kg.m ~ 3, with a distillation of 184 ° C and at 86 ° C / 101 kPa (86% distillation), containing 36.3% by weight of 2-ethylhexanol, a mixture of dodecanol with diolC12 = 44.1% by weight, butyraldehyde diisobutyl acetate = 0.7% by weight , alcohols C6 = 0.2% by weight, ether alcohols C8 = 0.4% by weight, the remainder being at least 7 additional constituents, mainly oxygenated organic compounds. In Id, it is a mixture of organic matter from wastewater from the butanol-2-ethylhexanol production plant by oxoprocess, the so-called stri-pol, containing 11.5 wt. water, 4.1 wt% butyraldehyde, 32.7% isobutanol; 45.8 wt. n-butanol; 1.1 wt. isobutyraldehyde; 0.1 wt. triisobutylamine; 4.9% hmottoluene and other unidentified components; acid value = 1.33 mg KOH / g; deletion number = 5.1 mg KOH; OH = 17.95 wt% CHO = 0.89 wt%;

Claims (4)

CS 267 357 Bl 5 6 Table 1 l Ika / verifier Experiment No. llb Is Id Mixture of oxygen-organic compounds FK-102 2-EHLP 2-EHTP Stripol Product composition (% by weight) SiO2 91.04 91.06 92.77 89 , 60 ai2o, 3.51 3.20 3.20 3.23 Na2O 1.67 1.77 1.95 2.10 annealing losses 3.80 4.00 2.00 5.07 Product obtained, (g) 6 , 6 6.6 6.0 6.3 Molar ratios of oxides: SiO2 44.09 48.34 49.28 47.19 AkO, 1.00 1.00 1.00 1.00 Na7O 0.78 0.91 1 EXAMPLE 2 The procedure is similar to that of Example 1, except that a neutral proportion of the hydro-condensation product of the UOH is applied to the hydrogenated organic compounds, mainly on ferrous and zinc-copper, while the oxygenated organic compounds are still present. catalysts. SUBJECT OF THE INVENTION A method for producing a high silicon zeolite of the general formula NanAlnSi, b_n. xH 2 O, in which n is greater than 27 and x = 0 to 20, by hydrothermal synthesis at a temperature of 130 to 250 ° C, generally at system vapor pressure at the working temperature used, from a starting material comprising mainly a silicon source % of aluminum and sodium, including 0.01 to 10 wt. seeding siliceous zeolite having a crystalline phase content of 75 to 100%, at least predominantly in the aqueous medium, with the addition of an aliphatic alcohol CžgC, characterized in that the addition of 0.1 to 40 wt. it consists of a mixture of at least two aliphatic alcohols C, C8 to C8 and / or a mixture consisting of 50 to 95% by weight. % of at least two aliphatic alcohols C 1 to C 8 and 5 to 50 wt. at least one further oxygen organic compound selected from ketones C, C 8, C 1 to C 8 aldehydes, C 2 to C 10 dialkyl ethers, C 3 to C 7 esters, and cyclohexanol. 2. Process according to claim 1, characterized in that the addition of the aliphatic alcohol is a further alcoholic product from the production of butanol and 2-ethylhexanol by oxoprocess, with a content of alcohols C4 to Cg of 70 to 96% by weight, the remainder being further oxygenated organic substances such as aldehydes, ketones, acetals, ether esters. 3. Process according to claim 1, characterized in that the addition of the aliphatic alcohol forms a predominant alcoholic product isolated from the rectification of the predominantly cyclohexanol-cyclohexanone mixture resulting from the procoxidation of cyclohexane to cyclohexanol and cyclohexanone characterized by the hydroxy content % to 8 to 22 wt. and a saponification number of 3 to 60 mg KOH / g. 4. A process for producing the compounds of claim 1, wherein the mixture of aliphatic alcohol-oxygenated organic compounds forms a mixture of alcohols C, C5 to C5 at a concentration of 74% by weight. and ethers, ketones, and aldehydes of a C2 to C20 concentration of 26% by weight, preferably a crude reaction mixture of hydrogen carbon dioxide hydrocondensation. Severografia, n. P., MOST Price 2,40 Kcs