A method of producing hydrocarbons from carbon oxides and hydrogen

 

(57) Abstract:

Usage: petrochemistry. Essence: as a catalyst used iron ore or composition with silicates or alumophosphate mass ratio of 20/80-80/20, and the process is carried out at 10-100 ATM, 220-360oC, space velocity initial synthesis gas 100-5000 h-1, a molar ratio of N2/WITH original synthesis gas, is equal to 1-3, in flowing or circulating mode, and volumetric content of CO2in the gas stream at the inlet to the reactor is from 0.01 to 30.0 per cent; the recovery of the catalyst is carried out the synthesis gas at 220-360oWith 10-100 ATM and a space velocity of the synthesis gas 100-5000 h-1. Effect: increase the output of gasoline and diesel fractions of hydrocarbons and performance of the catalyst. 2 C.p. f-crystals, 1 table.

The invention relates to organic chemistry, namely to the petrochemical industry, in particular to a method for producing hydrocarbons from a mixture of CO, H2and CO2(hereinafter referred to as synthesis gas). As the catalyst used iron ore or composition with the acidic components - crystalline aluminosilicates and alumophosphate. The resulting Ugledar nimi environmental quality indicators due to the low content of benzene and aromatic hydrocarbons and correspondingly high content of paraffins.

A method of obtaining hydrocarbon gasoline fractions from the gas containing H2and CO2or H2, CO2and, by contacting the gas with 320-440oC, 40-100 ATM and the volume ratio of N2/(CO+CO2), is 1-3 with a catalyst containing zeolite ZSM-5 or ZSM-11 and metal oxide component consisting of oxides of zinc, copper and/or chromium (patent 2089533 RF, CL C 07 C 1/12, 10 G 2/00, 1997, [1]).

According to this method, the main hydrocarbon products of the transformation mixture of N2, CO2and are liquid gasoline fraction hydrocarbons with high (40 to 84 wt.%) the content of aromatic hydrocarbons; by-products are gaseous hydrocarbons and the formation of C11-C17paraffin hydrocarbons (components diesel fraction) is not observed.

Closest to the invention in its technical essence is a method of obtaining a linear hydrocarbons (patent 1295995 the USSR, CL 01 J 23/78, C 07 C 1/04, 1987, [2]) with an average mol. mass 725-840 from synthesis gas when it contacts with a catalyst containing the oxides of iron, copper, potassium and silica and titanium in the following ratio, wt.h.: iron oxide (in terms of n the IPA). Linear hydrocarbons with an average mol. mass 725-840 from synthesis gas is obtained as follows. Before the synthesis of the catalyst is subjected to reduction with hydrogen under the following conditions: the duration of 1 h; temperature 240oC; feed rate of the hydrogen - 650 h-1. After recovery of the catalyst is cooled down to 160-170oWith and served under hydrogen pressure of 20 bar. Then carry out the circulation gas: begin feeding CO and H2and the catalyst is slowly brought to a temperature of synthesis. The resulting liquid product is processed by distillation.

In the end, according to the prototype of the main hydrocarbon products of the transformation mixture of N2and are linear hydrocarbons with an average mol. mass 725-840, having a density of 0,912-0.96 g/cm3the melting point 94-117oAnd other characteristics, described in the prototype.

The present invention is to obtain hydrocarbon gasoline and diesel fractions with high yield and high productivity of the catalyst.

The problem is solved in that for the catalytic conversion of synthesis gas into hydrocarbonaceous products as the catalyst used iron ore or at 10-100 ATM, 220-360oC, space velocity initial synthesis gas 100-5000 h-1, a molar ratio of N2/WITH original synthesis gas, is equal to 1-3, and volumetric concentration of CO2in the contacting gas from 0.01 to about 30.0%, and the recovery of the catalyst to carry out the synthesis gas at 220-360oWith 10-1000 MPa and space velocity of the synthesis gas 100-5000 h-1.

The problem is solved also by the fact that the catalyst contains 20-80 wt.% ore and 20-80 wt.% aluminosilicate.

The problem is solved also by the fact that the catalyst contains 20-80 wt.% ore and 20-80 wt.% alumophosphate.

Distinctive features of the invention are:

a) for the catalytic conversion of synthesis gas into hydrocarbonaceous products as the catalyst used iron ore or composition with silicates or alumophosphate mass ratio of 20/80-80/20;

b) the process is carried out at 10-100 ATM, 220-360oC, space velocity initial synthesis gas 100-5000 h-1, a molar ratio of H2/CO in the original synthesis gas, is equal to 1-3, and volumetric concentration of CO2in the contacting gas from 0.01 to 30.0 per cent;

C) recovering the catalyst to carry out the synthesis gas at 220-360oWith 10-100 ATM and volume RMSE is adnie products based on many iron ores contain a complete set of the oxides of the elements necessary for the chemical reactions for the synthesis of hydrocarbons. The main component of iron ore, used as catalysts in the proposed method, are iron oxides (F and/or Fe2ABOUT3), whose content in the catalyst can be 10 to 90% (depending on the field and the extent of the ore). The combination of iron ores with acid components in a weight ratio of 20/80-80/20 leads to increased activity of the metal oxides in the synthesis of hydrocarbons from H2, Co and CO2.

The choice of process conditions for the synthesis of gasoline and diesel fractions from a gas containing H2, Co and CO2due to the following factors. High blood pressure is necessary for deeper conversion of synthesis gas. Lower limit of temperature range (220oC) determined by the minimum activity of the catalyst, the excess of the upper temperature limit (360oC) leads to a rapid superusuario the catalyst surface. The volumetric feed rate of the original synthesis gas is determined by the activity of the used catalyst in fixed the value of gasoline and diesel fractions. The ratio of H2and FROM, and between CO and CO2is determined by the stoichiometry of chemical reactions synthesis of hydrocarbons. For example, for the formation of a group of CH2paraffin hydrocarbons on one carbon atom requires two atoms of hydrogen, and the amount of bound About in the feedstock determines the consumption of hydrogen in the formation of molecules N2O. Based on theoretical assumptions, experiments were conducted under conditions sufficiently close to the stoichiometric ratio between S, O and N. The process of recovery of the catalyst necessary for the formation of the active catalytic centers of inactive metal oxides. Terms of recovery was determined experimentally. Found the conditions of recovery allow to achieve the objectives of the process of synthesis of hydrocarbons below.

Industrial applicability of the invention is illustrated by examples 2-10.

Example 2. In isothermal reactor load 30 cm3fractions of 0.25-1.0 mm iron rich ore - magnetite (base ore - Fe(FeO2)2or, in another form, Fe2O3Fe). The original synthesis gas is fed in the reactor block to mix with the circulating gas block. Reactor unit with the full collection of liquid products and an electromagnetic pump for circulating the gas. Before the synthesis of the catalyst is subjected to restore the synthesis gas under the following conditions: a pressure of 30 ATM, a temperature of 260oWith the duration of 10 hours, the temperature is 280oWith the duration of 4 h the synthesis of hydrocarbons are under pressure of 30 ATM and at a temperature in the catalyst bed 300oC. To prevent accumulation in the reactor block non-condensable products from the block after the high pressure separator continually remove part of the circulating gas. Liquid products (condensed hydrocarbons, water, methanol), the output from the reactor building gas and allocated by throttling gaseous hydrocarbons analyzed separately by gas chromatography. Conditions and key indicators of the experience shown in the table.

Example 3. Analogous to example 2. Characterized in that the catalyst used iron ore - hematite (base ore - Fe2ABOUT3). Conditions and key indicators of the experience shown in the table.

Example 4. Analogous to example 2. Characterized in that the catalyst used bifunctional catalyst consisting of 50 wt.% magnetite and 50 wt. % crystalline aluminosilicate with structure is s 5-7. Analogous to example 2. Differ in that the catalyst used bifunctional catalyst consisting of 50 wt.% magnetite and 50 wt.% crystal alumophosphate with the structure of SAPO-5. Conditions and the main results of the experiments are shown in the table.

Examples 8-10. Analogous to example 2. Differ in that the catalyst used iron ore is limonite (base ore - Fe2ABOUT3H2About), and experiments are performed without the circulation of the gas stream after the separator. Conditions and the main results of the experiments are shown in the table.

As seen in the results table, using as a catalyst of iron ores or their compositions with silicates or alumophosphate and application for the conversion of synthesis gas pressure of 10-100 ATM, temperature 220-360oC, space velocity initial synthesis gas 100-5000 h-1, molar relationship of H2/WITH original synthesis gas, is equal to 1-3, and the volumetric contents of CO2in the gas stream at the inlet to the reactor is from 0.01 to 30.0 per cent in the conditions of the present invention allow to obtain petrol and diesel hydrocarbon fractions and have advantages compared with prototype:
< 2) total output WITH2+hydrocarbons in the calculation of the original synthesis gas 1.3-2.7 times higher;

3) conversion of synthesis gas into hydrocarbons 1.5-2.9 times higher;

4) the performance of the catalyst, as well as the productivity per unit volume of iron-containing component of the catalyst is much greater than the values calculated from experimental data of the prototype.

1. A method of producing hydrocarbons from carbon oxides and hydrogen, comprising contacting the synthesis gas with iron-containing catalyst at elevated pressure and temperature and recovery of the catalyst in predetermined conditions, wherein the catalyst used iron ore or composition with silicates or alumophosphate, the process is carried out at 10-100 ATM, 220-360oC, space velocity initial synthesis gas 100-5000 h-1, a molar ratio of N2/WITH original synthesis gas, is equal to 1-3, in a flow or circulation mode, the volumetric concentration of CO2in the gas stream at the inlet to the reactor is from 0.01 to 30.0% and the recovery of the catalyst to carry out the synthesis gas at 220-360oWith 10-100 ATM and a space velocity of the synthesis gas 100-5000 h-1.

2. The way to the floor.

3. A method of producing hydrocarbons under item 1, characterized in that the catalyst contains 20-80 wt. % ore and 20-80 wt. % alumophosphate.

 

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FIELD: chemical industry.

SUBSTANCE: the invention is pertinent to the field of chemical industry, in particular to production of a catalysts and processes of oxidation of ammonia in production of a weak nitric acid. The invention offers an ammonia conversion catalyst on the basis of the mixture of oxides of unitized structure and a method oxidation of ammonia in production of weak nitric acid. The catalyst represents a mixture of oxides of the over-all formula (AxByO3Z)k (MmOn)f, (NwPgvOv)r where: A - cation of Ca, Sr, Ba, Mg, Be, Ln or their mixtures; B - cations of Mn, Fe, Ni, Co, Cr, Cu, V, A1 or their mixtures; x=0-2, y=1-2, z=0.8-l.7; M - A1, Si, Zr, Cr, Ln, Mn, Fe, Co, Cu, V, Ca, Sr, Ba, Mg, Be or their mixtures; m=l-3, n=l-2; N - Ti, Al, Si, Zr, Ca, Mg, Ln, W, Mo or their mixtures, P - phosphorus, O - oxygen; w=0-2, g=0-2, v=l-3; k, f and r - mass %, at a ratio (k+f)/r=0-l, f/r=0-l, k/f = 0-100. The catalyst is intended for use in a composition of a two-stage catalytic system generated by different methods, also in a set with the trapping platinoid screens and-or inert nozzles. The technical result ensures activity, selectivity and stability of the catalyst to thermocycles at its use in two-stage catalytic system with a decreased loading of platinoid screens.

EFFECT: the invention ensures high activity, selectivity and stability of the catalyst to thermocycles at its use in two-stage catalytic system with a decreased loading of platinoid screens.

8 cl, 1 tbl, 5 ex

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