The method of obtaining a mixture of diacetoxyscirpenol

 

(57) Abstract:

Usage: chemical technology, oxidative acetoxysilane conjugated dienes, TRANS-diacetoxyscirpenol. The essence of the invention: 1,3-cyclopentadiene acetoxyethyl in the medium of acetic koloti using oxygen and intermetallic Rh2Te as a catalyst. The process is carried out at a temperature of 80 - 85°C and the pressure 8,5 - 9,0 MPa on catalyst, wt.%: telluride rhodium Rh2Te 2,8 - 3,6, activated charcoal else. Yield 89%. table 4.

The invention relates to the field of organic synthesis, namely acetoxysilane 1,3-cyclopentadiene (CPD) in a mixture of CIS - and TRANS-3,4(3,5)-diacetoxyscirpenol (DACP).

DACP are components of fuel for strategic purposes, as well as potential new raw materials in the synthesis of dicarboxylic and multifunctional carboxylic acids. Currently DCP obtained by mixing the individual components obtained by substitution of the bromine atoms in the respective dibromopropane cyclopentene, such syntheses are time-consuming, hazardous and environmentally unfriendly processes.

In the literature contain almost no information about what the ATA or their binary mixtures.

The known method is the prototype of a mixture DATP by acetoxysilane JRS for 0.5 h at 10aboutWith in a mixture of 100 mmol of hydrocarbon, 60 ml of acetic acid, 2 ml of acetic anhydride in the presence of catalyst (50 mmol acetate thallium (III). Output DCP 57%, based on the amount of thallium (III) - 87%.

< / BR>
The ratio of the isomers 1+ 2+ 3+4=8+ +21+44+27, i.e. 1:2,6:5,5:3,4. When the ratio of 3,4 - and 3,5-isomers 29:71.

The disadvantages of this method:

low output DACP;

other than required, the ratio of the isomers in the catalyzate 1:2,6:5,5:3,4 when the optimal 1-1,5:2-3:1-1,5:1-2;

the difficulty of separating non-regenerating homogeneous catalyst from the reaction products;

stereometrical synthesis, which stops at the irreversible stage of transition Tl3+_ Tl+and consuming thallium (50% of the original diene).

The aim of the invention is to increase the output DACP at the optimum ratio of the isomers.

This goal according to the claimed method is achieved by the process of oxidative acetoxysilane 1,3-cyclopentadiene in the liquid phase at 80-85aboutC and air pressure 8,5-9,0 MPa in the presence of acetic acid and catalyst containing the active part of the ü - the rest of it.

The hallmark of this method is the execution of the process at 80-85aboutIn the presence of air and its pressure 8,5-9,0 MPa and the use of intermetallic catalyst of the above composition.

The advantages of the proposed method, compared with prototype:

the increase in the output of DATP to 89% conversion of raw materials 99%;

the mixture of isomers of the desired composition- 1,0:2,3:1,0:1,3;

the use of the catalyst to be regenerated and can be used in an industrial environment.

The invention is illustrated by the following examples.

P R I m e R 1. Acetoxysilane 1,3-cyclopentadiene is carried out in an autoclave with a capacity of 0.5 l, in which load 20 g JRC, 300 g of glacial acetic acid, a reagent and solvent, and 10 g of catalyst containing 3.6% Rh2Te. The autoclave is pressurized, the mixture is heated to 80aboutWith, then pump air to 8.5 MPa and stirring carried out the synthesis during the 5 o'clock

The catalyst was prepared as follows. Powdered activated carbon (mark AR-5) in an amount of 10 g is treated with 60 ml of 15% nitric acid, evaporated on a water bath to dryness. In Ura. The resulting solution impregnated treated (see above) activated carbon, with stirring, evaporated on a boiling water bath to dryness. The catalyst is placed in a vertical tubular reactor, calcined in air at 150about1 h and restore in a stream of moist hydrogen at 250aboutWith 2.5 hours and at a temperature of 420aboutWith - for 1.5 h

Analysis of the catalyst by the method of XPS showed that it corresponds to the composition of Rh2Te in the amount of 3.6 wt.% to the weight of the catalyst.

Physico-chemical topochemical catalyst properties: specific surface 890-910 m2/g; data micrograph mode RES - uniform particle size with the size of the globules to 50 nm; the distribution of elements along the pellet - preferential concentration in the upper layers korechkovogo type of the order of 20 nm.

The balance of the experiment are shown in table. 1.

The catalyst is filtered off, washed with glacial acetic acid and recovered by the method of re-activation, as described in the method for the preparation of the catalyst (see above), starting with the ignition.

Analysis of the reaction mixture by GLC showed that the isomers DACP in catalyzate distributed as follows: 1+2+3+4=17,9+49,0+17,9+�eficacia allocate DACP with the following physicochemical characteristics: I. instrumentation. 119-121aboutWith 10 mm RT.art., nD201,4670; d4201,1400.

The total yield DCP equal and 86.8% (48,92 g), the purity of the end product of 99.5%.

Elemental analysis: C9H12ABOUT4.

Calculated, %: From 58.7; H 6,6; 34,7.

Found, %: From 56.4; H 8,9; 34,7.

The molecular mass determined osmoticheski method: 184 (calculated 184,19).

P R I m m e R 2. Acetoxysilane JRC carried out in the autoclave as described in example 1, except that the catalyst contains 2.8 wt.% Rh2Te, the temperature of the experience 85aboutWith the pressure of 9.0 MPa. Physico-chemical characteristics of the catalyst, as in example 1.

The balance of the experiment are shown in table. 2.

Analysis of the reaction mixture by GLC showed that the isomers in catalyzate distributed as follows: 1+2+3+4= =20,0 + 41,7 +21,7 +16,6, i.e. sustained ratio of 1.2:2,5:1,3:1,0. Conversion of the JRC is 99,3%, output DACP reaches of 89.1%. The catalyst is filtered off, the rectification produce a mixture DATP, which has physical and chemical characteristics: I. instrumentation. 118-120aboutC./10 mm RT.article; nD201,4687; d4201,1400.

The total yield DCP equal 88,0% (49,11 g), the purity of the end product of 99.7%. Elemental analysis as described in example 1, only the catalyst contains 3.2% Rh2Te, the temperature of the experience 83aboutWith the pressure of 8.7 MPa. Physico-chemical characteristics of the catalyst, as in example 1.

The balance of the experiment are shown in table. 3.

Analysis of the reaction mixture by GLC showed that the isomers in catalyzate distributed as follows: 1+2+3+4= =21,2+30,3+22,7+25,8, i.e., sustained a ratio of 1.4:2,0:1,5:1,7. Conversion of the JRC is 99.1%, output DACP is 89.0%. The catalyst is filtered off, the rectification produce a mixture DATP with the following physico-chemical characteristics tics: T. bales. 120-122aboutC./10 mm RT.article; nD201,4625; d4201,1400.

The total yield DCP equal 88,0% (49,1 g), the purity of the end product is 99.8%.

Elemental analysis: C9H12ABOUT4.

Calculated, %: From 58.7; H 6,6; 34,7.

Found, %: C 57,3; H 8,0; 34,7.

The molecular mass determined osmoticheski method: 184 (calculated 184,19).

Free table. 4 acetoxysilane 1,3-cyclopentadiene on intermetallic catalyst Rh2Te (medium charcoal) is presented below.

The METHOD of OBTAINING a MIXTURE of DIACETOXYSCIRPENOL oxidative acetoxysilane 1,3-cyclopentadien the selection of the target product by distillation, characterized in that, to increase output , the process is carried out at a temperature of 80 - 85oAnd pressure 8,5-9,0 MPa catalyst of the following composition, wt.%:

Telluride rhodium Rh2Te - 2,8 - 3,6

Activated carbon - Other

 

Same patents:

The invention relates to the field of organic synthesis, namely the selective acetoxysilane 1,3-cyclopentadiene (CPD) in CIS-3,5-diacetoxyscirpenol (DACP)

The invention relates to the primary organic synthesis, and in particular to catalysts for diacetoxybiphenyl S-CIS-1,3-pen - tadiene in diacetoxybiphenyl

The invention relates to the field of organic synthesis, namely the selective acetoxysilane 1,3-cyclopentadiene (CPD) in CIS-3,5-diacetoxyscirpenol (DACP)

The invention relates to the primary organic synthesis, and in particular to catalysts for diacetoxybiphenyl S-CIS-1,3-pen - tadiene in diacetoxybiphenyl

The invention relates to the field of organic synthesis, namely the selective acetoxysilane 1,3-cyclopentadiene (CPD) in CIS-3,5-diacetoxyscirpenol (DACP)

The invention relates to the primary organic synthesis, and in particular to catalysts for diacetoxybiphenyl S-CIS-1,3-pen - tadiene in diacetoxybiphenyl

The invention relates to the production of catalysts for reforming of gasoline fractions

FIELD: organic chemistry, chemical technology, catalysts.

SUBSTANCE: invention relates to a method for preparing acetic acid by gas-phase oxidation of ethane and/or ethylene with oxygen using catalyst comprising molybdenum and palladium. For realization of method gaseous feeding comprising ethane, ethylene or their mixture and oxygen also are contacted at enhanced temperature with catalyst that comprises elements Mo, Pd, X and Y in combination with oxygen of the formula (I): MoaPdbXcYd wherein X and Y have the following values: X means V and one or some elements optionally taken among the following group: Ta, Te and W; Y means Nb, Ca and Sb and one or some elements optionally taken among the following group: Bi, Cu, Ag, Au, Li, K, Rb, Cs, Mg, Sr, Ba, Zr and Hf; indices a, b, c and d mean gram-atom ratios of corresponding elements wherein a = 1; b = 0.0001-0.01; c = 0.4-1, and d = 0.005-1. Niobium is added to the catalyst structure using niobium ammonium salt. Preferably, niobium ammonium salt is used as the niobium source. The continuance of contact time and composite values of the parent gaseous mixture are so that taken to provide output value by acetic acid to be above 470 kg/(m3 x h). The selectivity of oxidation reaction of ethane and/or ethylene to acetic acid is above 70 mole %. Invention provides enhancing stability and output of catalyst.

EFFECT: improved preparing method.

14 cl, 1 tbl, 6 ex

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: catalytic reforming of gasoline fractions is accomplished in a system constituted by several in series connected reactors at elevated pressure and hydrogen-containing gas circulation, wherein temperature of gas at first reactor inlet ranges from 380 to 470°C and in the other reactors 470-540°C. Reforming catalyst comprises alumina-supported platinum, fluorine, and optionally rhenium. In the first reactor, catalyst additionally contains 0.02 to 1.5% of fluorine.

EFFECT: increased yield and improved quality of product.

2 cl, 7 tbl, 7 ex

FIELD: chemical industry; methods of manufacture of the deposited polymetallic catalytic agents.

SUBSTANCE: the invention is pertaining to the methods of manufacture of the oxidation catalytic agents based on any solid carriers by deposition on them of the metals solid solutions. The catalytic agents may be used in the various fields of the catalysis, for example, for realization of the photocatalytic, electrocatalytic, catalytic and other reactions. The invention presents the description of the method of manufacture of the deposited polymetallic catalytic agents by deposition of the metals on ceramics, plastics materials, metals, composite materials, oxides of the transition metals, the carbonic material, which includes the sequential stages of deposition of the previous layers carrying the cationic and anionic parts and for recovery. In the capacity of the previous layer carrying the cationic part use the substances of the following composition: [М(NH3)xАyz, where M - Cr, Со, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Cd, Ir, Pt, Au; А - ОН, Н20, C1, Br, I, NO, NO2; В - OH, F, Cl, Br, I, NO2, NO3, SO4; and as the previous layer carrying the anionic part use the substance of the following composition: Еx2[M'Dy2Cz2], where М' - Ti, Cr, Со, Ni, Cu, Zn, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg; С - ОН, Н20, F, SCN, Cl, Br, I, NO, NO2; D - ОН, Н20, F, SCN, Cl, Br, I, NO, NO2; Е - Н, Li, Na, К, Rb, Cs, NH4; or as the previous layer carrying the cationic part use the substances having the following composition: [М(NH3)xАyz and/or [М1(NH3)x1Аy1z1, where M AND M1 - Cr, Со, Ni, Cu, Zn, Ru, Ag, CD, Ir, Pt, Au; А - ОН, Н20, C1, Br, I, NO, NO2; В - OH, F, Cl, Br, I, NO2, NO3, SO4; and as the previous layer carrying the anionic part use the substances having the following composition: Еx2[M'Dy2Cz2] and/or Еx3[M'1Dy3Cz3], where М' and М'1 - Ti, Cr, Со, Ni, Cu, Zn, Zr, Nb, Mo, Tc, Ru, Ag, Cd, Hf, Ta, W, Os, Ir, Pt, Au, Hg; С - ОН, Н20, F, Cl, Br, I, NO, NO2; D - ОН, Н20, F, Cl, Br, I, NO, NO2; Е - Н, Li, Na, К, Rb, Cs, NH4; or as the previous layer carrying both the cationic part and then anionic part use the substance having the following composition: [М(NH3)xАy]x1[M'Dy1Cz1]z, where: M - Cr, Со, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Cd, Ir, Pt, Au; А - ОН, Н20, C1, Br, I, NO, NO2; М' - Ti, Cr, Со, Ni, Cu, Zn, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, 0s, Ir, Pt, Au, Hg; С - ОН, Н20, F, Cl, Br, I, NO, NO2; D - ОН, Н20, F, Cl, Br, I, NO, NO2. The technical result of the invention is the high activity of the produced catalytic agents.

EFFECT: the invention ensures the high activity of the produced catalytic agents.

14 cl, 3 tbl, 97 ex

FIELD: petrochemical processes.

SUBSTANCE: feed stream is passed with admixed oxygen and diluent through catalyst bed at 400-500°C and constant flow rate 50 mL/min, said catalyst being catalytic system for heterogeneous reactions and representing geometrically structured system including microfibers of high-silica fibrous carrier, which is characterized by presence in IR absorption band of hydroxyl groups with wave number ν=3620-3650 cm-1 and half-width 65-75 cm-1. The carrier has specific surface as measured according to BET method from heat desorption of argon SAr=0.5-30 m2/g, surface area as measured by alkali titration method SNa=5-150 m2/g at ratio SNa/SAr=5-50, and at least one active element, whose principal portion is composed in the form of charged either metallic, or bimetallic clusters characterized in UV-vis diffuse reflection spectrum by specific bands in the region 34000-42000 cm-1 and ratio of integral intensity of band attributed to charged either metallic, or bimetallic clusters to integral intensity of band belonging to, respectively, either metallic, or bimetallic particles is not less than 1.0.

EFFECT: increased choice of oxidative dehydrogenation catalysts.

4 cl, 5 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: catalyst containing platinum, rhenium, antimony, and chlorine on alumina are prepared by impregnation of carrier with aqueous solution of compounds of indicated elements, antimony being deposited as first or second component. Once antimony or platinum-antimony combination, or rhenium-antimony combination deposited, catalyst is dried at 130°C and then calcined in air flow at 500°C. Reduction of catalyst is performed at 300-600°C and pressure 0.1-4.0 MPa for 4 to 49 h. After deposition of antimony or two elements (platinum-antimony or rhenium-antimony) and drying-calcination procedures, second and third or only third element are deposited followed by drying and calcination. Final reduction of catalyst is accomplished in pilot plant reactor within circulating hydrogen medium at pressure 0.3-4.0 MPa and temperature up to 600°C for a period of time 12 to 48 h.

EFFECT: enhanced aromatization and isomerization activities of catalyst and also its stability.

2 cl, 1 tbl, 8 ex

FIELD: petroleum processing and catalysts.

SUBSTANCE: invention relates to bismuth- and phosphorus-containing catalyst carriers, petroleum reforming catalysts prepared on these carriers, to methods for preparing both carriers and catalysts, and to petroleum reforming process using these catalysts. Described are catalyst carrier containing γ-alumina particles wherein bismuth and phosphorus are distributed essentially uniformly in catalytically efficient concentrations and a method for preparation thereof comprising (a) preparing solution containing bismuth precursor and solution containing phosphorus precursor; (b) preparing γ-alumina/alumina sol mixture; (c) mixing mixture of step (b) with solutions prepared in step (a) to produce carrier precursor containing essentially uniformly distributed phosphorus and bismuth; (d) molding; and (e) drying and calcination. Invention also describes petroleum reforming catalyst containing above-defined carrier and catalytically efficient amount of platinum, chlorine, and optionally rhenium; method of preparation thereof; and petroleum reforming process after hydrofining, which involves contacting petroleum with above-defined catalyst in presence of hydrogen at elevated temperature and pressure.

EFFECT: reduced catalyst coking velocity and achieved high stable activity of catalyst.

25 cl, 6 dwg, 4 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: method for olefine epoxidation is invented which includes the reaction of the raw material containing olefine, oxygen and organic halogenide, in presence of the catalyst containing silver and rhenium precipitated on the carrier where the catalyst contains rhenium at 1.5 mol/kg of the catalyst mass, at maximum, and 0.0015 mmol/m3 of the carrier surface, at maximum, and where the reaction temperature is increased so as to partially reduce the effect of catalyst loss, and the halogenide is presented in relative Q amount which is maintained constant and where the relative amount of Q is the ratio of the effective molar amount of the active halogen compound in the raw material, to the effective molar amount of hydrocarbon, in the raw material. The invention also implies the method for producing the 1,2-diol, the simple ether of the 1,2-diol and/or alkanolamine and the catalyst to be applied in the said method.

EFFECT: stability of catalyst activity is increased.

22 cl, 8 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: described is mass of metal oxides, intended as catalyst for heterogeneously-catalysed partial oxidation and/or ammoxidation of at least one saturated and/or unsaturated hydrocarbon, of general stechiometry I MO1VaM1bM2cM3dOn (I), were M1= stands for Te; M2=stands for Nb; M3= stands for at least one of elements from group, which includes Pb, Ni, Co, Bi and Pd; a = 0.05 to 0.6, b= 0.01 to 0.5, c= 0.01 to 0.5, d = 0.0005 to 0.5 and n= equals the number determined by valence and number of different from oxygen elements in (I), whose X-ray diffractogragm has diffraction reflexes h, i and k , whose peaks are at diffraction angles (2Θ) 22.2±0.5° (h), 27.3±0.5° (i) and 28.2±0.5° (k), and - diffraction reflex h in the range of X-ray diffractogram is the most intensive and has peak half-width maximal value 0.5°, intensity Pi of diffraction reflex i and intensity Pk fulfill ratio 0.65≤R≤0.85, in which R is determined by formula R=Pi/(Pi+Pk) intensity ratio, and - half-width of diffraction reflex i and diffraction reflex k each constitute ≤1°, and at least one mass of metal oxides (I) represents such, X-ray diffractogram of which does not have diffraction reflex with peak position 2Θ=50.0±0.3°. Described is mass of metal oxides, which contains equal or more than 80 wt % of at least one mass of metal oxides, indicated above, and whose X-ray diffractogram has diffraction reflex with peak 2Θ=50.0±0.3°.Also described are methods of heterogeneously catalysed partial gas phase oxidation or ammoxidation of at least one saturated or unsaturated hydrocarbon, using as catalytic active mass at least one mass of metal oxides, described above. Described is method of obtaining metal oxides mass by mixing sources of its elementary components, calcination of dry mixture at 350-700°C and washing by organic and/or inorganic acid solution.

EFFECT: increasing target product selectivity.

17 cl, 1 tbl, 16 ex, 17 dwg

FIELD: environmental protection.

SUBSTANCE: catalyst includes metal oxide substrate consisting mainly of cerium and/or zirconium oxide. Noble metal and metal or semimetal oxide (MOx) are attached to metal oxide substrate, where M is selected out of group including iron, gallium, silver, molybdenum, tungsten, thallium and bismuth. Metal or semimetal M has larger electronegativity than that of cerium or zirconium.

EFFECT: enhanced activity of noble metal in catalyst at low temperatures, prevented caking of noble metal.

11 cl, 3 dwg, 9 tbl, 14 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to catalysis, and specifically to methods of preparing catalysts for gas-phase redox reactions. The invention discloses a method of preparing a catalyst for gas-phase redox reactions based on complex oxides, involving formation of a coating on a support of given configuration through layer-by-layer deposition of an aqueous solution which contains metallic components of a complex oxide in form of a mixture of decomposable salts and a water-soluble polymer, and subsequent roasting at 873-1173 K for 0.5-5 hours. The support material is nickel in form of a highly porous permeable cellular material. Before applying the aqueous solution of salts, the support undergoes thermal treatment in an oxygen or air atmosphere at 673-1073 K for 0.1-6 hours. Before thermal treatment, the support is briefly put into an aqueous solution of an oxygen-containing acid which forms thermally decomposable salts, and then briefly washed with water to remove free acid residues.

EFFECT: simple catalyst preparation technology and increased catalyst activity.

1 tbl, 1 ex

FIELD: vinyl acetate production by ethane catalytic acetoxylation with acetic acid obtained as intermediate.

SUBSTANCE: claimed method includes: a) bringing gaseous raw material, containing ethane as a main component, into contact in the first reaction zone with molecular oxygen-containing gas in presence of catalyst to obtain the first product stream including acetic acid and ethylene; b) bringing the said first product stream in second reaction zone with molecular oxygen-containing gas in presence of catalyst to obtain the second product stream including vinyl acetate; c) separation the second product stream from stage b) to recovery of vinyl acetate. In the first reaction zone catalyst of general formula MOaPdbXcYd is used, wherein X is at least one element selected from Ti, V, and W; Y is at least one element selected from Al, Bi, Cu, Ag, Au, K, Rb, Cs, Mg, Ca, Sr, Ba, Nb, Sb, Si, and Sn; a, b, c, and d are gram-atom ratio, and a = 1; b = 0.0001-0.01, preferably 0.0001-0.005; c = 0.4-1, preferably 0.5-0.8; and d = 0.005-1, preferably 0.01-0.3. Gaseous raw material from step a) preferably includes ethane and molecular oxygen-containing gas in volume ratio of ethane/oxygen between 1:1 and 10:1, and 0-50 % of vapor as calculated to total volume of starting raw material. Ratio of selectivity to ethylene and selectivity to acetic acid in the first product stream is 0:95-95:0.

EFFECT: integrated technological cycle with controllable product yield while changing technological parameters of the process.

6 cl, 11 ex, 2 tbl, 1 dwg

FIELD: catalyst carrier materials.

SUBSTANCE: microspherical particles are manufactured by adding specified proportion of fine, preferably reused particles to suspension of silica sol and silica powder, which suspension is then subjected to spray drying to form microspherical particles, which are finally calcined. Thus obtained particles are suitable for use as carrier for catalytically active component when preparing catalyst employed in fluidized-bed form in production of monomers used as vinyl polymer precursors.

EFFECT: increased abrasion resistance of particles.

10 cl, 1 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a layered composite, method of making and method of converting hydrocarbons using said composite. A layered composite is described for catalytic production of alkenyl alkanoates, containing an inner core and an outer layer, which contains heat-resistant inorganic oxide, a fibrous component, inorganic binder and palladium, gold or their mixture as the catalytic component, dispersed in the outer layer. A method is described for production of alkenyl alkanoates, involving bringing a mixture of alkene, alkanecarboxylic acid and oxygen-containing gas into contact with the catalyst described above. A method is also described for making a catalyst for production of alkenylalkanoate, involving coating an inner core with a suspension, containing an outer heat-resistant inorganic oxide, fibrous component, inorganic binder precursor, organic binder and solvent, so as to obtain a core with an outer coating layer, and baking at temperature below 200°C for a period of time sufficient for binding the outer layer to the inner core, so as to obtain a layered composite, which contains a catalytic component containing palladium, rhodium, gold or their combination.

EFFECT: obtaining high-strength catalyst.

28 cl, 5 ex

Up!