CS267357B1 - Method of high-siliceous zeolite production - Google Patents

Abstract

A method for producing high silica zeolite of the formula NanAlnSi <) fJ_nOi92 · xH2O, where n is greater than 27, x = 0 to 20 (zeolite ZSM-5) is carried out by hydrothermal synthesis from starting mixtures containing mainly the source of silicon, aluminum and sodium, with the addition seeding high silica zeolite, predominantly in aqueous medium with addition at least two aliphatic alcohols C 1 to C 8 or mixtures thereof with at least one with another oxygenated organic compound with a number of carbons per molecule of 1 to 8, respectively. 2 to 10 (ketones, aldehydes, ethers, esters, acetals). They give to use the by-products of chemical, especially petrochemical but also biological processes containing mixtures of alcohols and others of said oxygenated organic components. The method is suitable for the production of synthetic zeolites and catalysts in the chemical industry.

Description

The invention relates to a process for the production of a high-silica zeolite of the ZSM-5 type by seeding the starting reaction mixture with targeted zeolites in the presence of technically readily available substances.

The ever-growing importance of high-silica aluminates themselves, but also as active supports for catalysts and catalyst systems, is growing by the need to increase production and simplify methods of producing such zeolites. Their composition in terms of the content of silica and alumina can vary, _w being in borderline cases can go to the zeolite without aluminum so. silicalite.

The original process of Mobil (U.S. Pat. No. 3,702,886) uses tetrapropylammonium compounds to form the crystal lattice of zeolite ZSM-5, which are, however, more technically difficult to obtain and are therefore sought to be a suitable substitute. These include the use of ethylamine and other aliphatic amines (Czech author's certificate 234 814), diamines, ammonia, pyridine and alkanolamines (Mravec D., Ilavský J .: Petroleum and Coal 28, 197 (1986); Seidl V .: ibid. P. 202; U.S. Pat. Nos. 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 ZSM-5 zeolites as crystallization nuclei and from an acetone-water mixture without further organic templates (Narita E. et al., Chern. Letters, 1984, p. 1,055; Narita E. et al. : Ind. Eng. Chern. Prod. Res. Dev. 24, 1985, p. 507). Even the hydrothermal synthesis of zeolites of the ZSM-5 is carried out in an aqueous medium with the addition of 0-30% by weight, of the aliphatic alcohol C ₈ to C (MS. Author's certificate 255 394). However, despite the above-mentioned evident progress of these latest solutions, not all technical possibilities for improving the production of silicalite zeolites, especially of the ZSM-5 type, have been exhausted. However, said extraction processes can be further modified using technically readily available organic intermediates, including by-products of mainly petrochemical processes.

Thus, the present invention is a method of making zeolites of the formula vysokokremičitého For _thick Al _{"_%} Si _n H | 9 _second 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, usually under vapor pressure at the operating temperature used, from a starting mixture containing mainly a source of silicon, aluminum and sodium, for adding 0.01 to 10% by weight, seed vysokokremičitého zeolite comprising a crystalline phase of 75 to 100%, at least predominantly in the aqueous medium, with the addition of an aliphatic alcohol C _t to C ₈ was accomplished by the addition in an amount of 0.1 to 40% mass, forms a mixture of at least two aliphatic alcohols C! to C _8, and / or a mixture comprising 50 to 95% by weight, of at least two aliphatic alcohols, C _t to C _8, and 5 to 50% by weight, of at least one other oxygenated organic compound selected from ketones of C ₃ to C _8, aldehyde C _(to C ₈ , C ₂ to C 10 dialkyl ethers of C ₃ to C ₇ esters and cyclohexanol.

An advantage of the production method of the present invention is the technical simplicity of formulating the components of the reaction system. Furthermore, the synergistic effect of a mixture of at least two C 1 to C ₈ aliphatic alcohols, as well as their mixtures with other oxygenated organic compounds, especially ketones, ethers and aldehydes, for the production of high silica zeolites with high crystallinity (90-94%) and finding new modification components production of those zeolites. The method makes it possible to technically use mainly alcoholic and by-products of chemical and especially petrochemical processes, for which processes of higher technical and economic recovery are often lacking. In addition, the low toxicity of the applied components of the process of the present invention and its feasibility on conventional manufacturing equipment is also advantageous. The high-silica zeolite thus produced can be freed of crystalline and adsorbed water at elevated temperatures.

The additive consists of a mixture of at least two C 1 to C ₈ aliphatic alcohols and at least one other oxygenated organic compound, such as aldehydes, ketones, ethers, acetals and esters. These consist of intentionally synthesized and manufactured products, such as Fischer-Tropsch synthesis from synthesis gas on ferrous, resp. iron, zinc or chromium, zinc-copper catalysts, particularly activated acetylene to form the aliphatic alcohols, C _t to C ₄ Cl 2, and even up to, first, a mixture of the aliphatic alcohol produced as a product of chemical-based side, especially the petrochemical processes and biochemical processes. The most suitable is the leading alcohol fraction from the rectification of 2-ethylhexanol (2-EHLP), usually a fraction of tv 109 to 182.5 ° C / 101 kPa, from oxoprocess, containing n-butanol, isobutanol, 2-ethylhexanol, isoamyl alcohol, 3 -heptanone and 2-ethylhexanol as main components, with admixtures of other oxygenated organic substances. Then also from the production of butanols and 2-ethylhexanol by oxosynthesis (from propene and synthesis gas followed by aldolization of n-butyraldehyde by dehydration, hydrogenation up to 2-ethylhexanol, as well as hydrogenation of n-butyraldehyde and isobutyraldehyde to butanol and isobutanol), respectively. oxoprocess, from the organic part of the washing water, the so-called stripol containing 70 to 85% of a mixture of n-butanol with isobutanol, 1 to 5% by weight, n-butyraldehyde, 5 to 25% by weight, water, toluene admixtures, esters and other unidentified additives.

Then the by-product of the production of cyclohexanol-cyclohexanone by catalytic oxidation of cyclohexane, in particular the leading alcohol product, isolated from the rectification (from column FK.-102) of a predominantly cyclohexanol-cyclohexanone mixture. The density of this colorless by-product at 20 DEG C. is in the range from 840 to 865 kg. m ^J and distills 95% in the range 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 mg KOH / g; hydroxyl groups = 8 to 22% by weight; carbonyl groups = 2 to 8% by weight; usually contains 48 to 58% by weight of amyl alcohol; 8 to 10% by weight of n-butanol; 1 to 2 wt. check. butyl alcohol; 3 to 5% by weight of isoamyl alcohol; 4 to 20% by weight of cyclohexanone; 2 to 10% by weight of cyclopentanol; 0.1 to 6% by weight of cyclopentanone and 0.5 to 3% by weight of water. Admixtures of cyclohexanone, cyclohexane and cyclohexanol (from 0.1 to 2% by weight).

Furthermore, crude "synthetic" methanol, products of the 1'ischer Tropsch synthesis, resp. catalyzed hydrocondensation of synthesis gas, in particular initiated by alkynes and carried out in particular on catalysts based on iron, zinc, copper and chromium.

It is also possible to use mixtures of alcohols and, if appropriate, also mixtures of alcohols and acetone produced by fermentation processes.

Further details of carrying out the production method according to the invention, as well as further advantages, are apparent from the examples.

Example 1

The preparation of high-silica zeolites of the general formula Na "Al Si _{M (>} " O _{) 92.} ~ 16 H ₂ O (type ZSM-5) is carried out in steel poteflonated ampoules with a volume of 130 cm 3, placed in a heating block equipped with temperature control and conventional accessories. 25.2 g of silica hydrosol with a concentration of 29.75% by weight of silica are metered into each ampoule, to which an aqueous solution of aluminum sulphate (0.83 g of aluminum sulphate in 30 cm * of water) is added dropwise, followed by an aqueous solution sodium hydroxide (1.50 g of sodium hydroxide in 33 cm 3 of water). Next, a seed seed of zeolite ZSM-5 with a modulus of 28.1 is added to the mixture of each ampoule in an amount of 0.33 g and 4.50 g of a mixture of two aliphatic alcohols with the addition of at least one other oxygenated organic compound.

The prepared mixture of each ampoule is homogenized at room temperature (20 ° C) for 20 minutes. The reaction mixture in each ampoule has the following composition expressed in molar ratios of oxides: SiO ₂ / Al ₂ O ₃ = 100; Na ₂ O / SiO ₂ = 0.15; II ₂ O / SiO ₂ = 35.90. The hydrothermal synthesis is performed 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 at 110 DEG C. for 4 hours. The product obtained is weighed and analyzed. In addition to the determination of the components, their crystallinity (in%) is determined by means of X-ray diffraction analysis of the samples of zeolite ZSM-5 thus produced. The results obtained are summarized in Table 1.

In each experiment, the addition of a different mixture of oxygenated organic compounds is used. Thus, in Experiment 1a, it is the leading alcoholic by-product of the process of oxidation of cyclohexane to cyclohexanol and cyclohexanone, isolated from rectification (from the FK-102 column, hereinafter referred to as FK-102 predominantly cyclohexanol-cyclohexanone).

CS 267 357 B1 new mixture. The characteristics and composition of FK-102 (colorless liquid) are as follows: density at 20 ° C = 855 kg. m ’; 95% distills in the boiling range 106 to 142 ° C / - / 1 () 1 kPa; average mol. weight =

109.4 g. (iiol ¹ kinetic viscosity at 20 ° C = 3.86.10 nd.s'; water content = = 3.6 wt%; OH = 14.25 wt%; bromine number = 27.8 g Br / 100 g; CHO = 4.50% by weight, acid number = 0.95 mg KOH / g, saponification number = 21.0 mg KOH / g, n-amyl alcohol = = 51.9% by weight, isoamyl alcohol = 3.7% by weight. n-butanol = 9.5% by weight, sec-butyl alcohol = = 1.1% by weight, isobutyl alcohol = 5.6% by weight, isopropyl alcohol = 0.2% by weight, a mixture of cyclohexanone and 4-methyl-1. -pentanol = 19.7% by weight, and 9 admixtures mainly of oxygenated organic compounds not yet identified.

Next, in experiment 1 b is a front alcoholic the proportion of the rectification of 2-ethylhexanol (hereinafter referred to 2-EHLP) in the process of oxo synthesis (hadroformylácia propylene to a mixture of n-butyraldehyde with isobutyraldehyde, aldolisation of n-butyroialdehydu associated with dehydration of the aldol _C, and the hydrogenation of the 2-ethylhexanol, fraction of mp 109-182.5 ° C / 101 kPa, density at 20 ° C = 812.2 kg, m ¹ , O 2 = 1.4088, OH = 19.4% by weight, CHO = 0.24% by weight, CHO bound = 0.25% by weight, bromine number = 1.3 g Br / 100 g, acid number = 1.26 mg KOH / g, saponification number = 2.50 mg KOH / g, water content = 0.4% by weight, isobutanol = 20.3% by weight, n-butanol = = 50.7% by weight, isoamyl alcohol = 4.1% by weight, 3-heptanone = 4.1% 2-ethylhexanol = 2.0% by weight, 2-ethylhexanol = 15.3% by weight, and the remainder consists of at least 3 unidentified oxygenated organic compounds.

In Experiment 1c it is again a heavy fraction from the rectification of 2-ethylhexanol in the oxoprocess of the production of butanols and 2-ethylhexanol, hereinafter referred to as 2-EHTP, with a density at 20 ° C = 896 kg.m ~ 3, with the start of distillation 184 ° C and the end at a temperature of 285 ° C / 101 kPa (distills 86%), with a content of 36.3% by weight. 2-ethylhexanol, mixtures of dodecanol with diol C ₁₂ = 44.1% by weight, butyraldehyde diisobutyl acetate = 0.7% by weight, alcohols C ₆ = 0.2% by weight, ether alcohols C ₈ = 0.4% by weight, the remainder consists of at least 7 other components, mainly oxygenated organic compounds.

In experiment Id, it is a mixture of organic substances stripped from wastewater from the production of butanols and 2-ethylhexanol by an oxoprocess, so-called stripol, containing 11.5% by weight of water, 4.1% by weight of n-butyraldehyde, 32.7% of isobutanol; 45.8% by weight of n-butanol; 1.1% by weight, isobutyraldehyde; 0.1% by weight, triisobutylamine; 4.9% by weight of toluene and other components not further specified; acid number = 1.33 mg KOH / g; saponification number = 5.1 mg KOH; OH = 17.95% by weight; CHO = 0.89 wt.

CS 267 357 Bl ^{5 6} .

Table 1

l Indicator Experiment number la 1b le Id Added mixture of oxygenated organic compounds Product composition (% by weight) SiO ₂ ALO, Na ₂ O losses by annealing Product obtained, (g) Molar ratios of oxides: SiO ₂ A1, O, Na ₂ Ó Crystallinity, (%) FK-102 91.04 3.51 1.67 3.80 6.6 44.09 1.00 0.78 91 2-EHLP 91.06 3.20 1.77 4.00 6.6 48.34 1.00 0.91 95 2-EHTP 92.77 3.20 1.95 2.00 6.0 49.28 1.00 1.00 91 Stripol 89.60 3.23 2.10 5.07 6.3 47.19 1.00 1.07 90

Example 2

The procedure is the same as in Example 1, except that a neutral portion of the product of the hydrogen condensation of carbon monoxide with hydrogen, predominantly on ferrous and zinc-copper-chromium catalysts, is applied as a mixture of oxygenated organic compounds.

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