Carbon monoxide/hydrogen-based production of hydrocarbons

FIELD: petrochemical processes.

SUBSTANCE: hydrocarbons are produced via contacting synthesis gas with catalytic composition consisting of mixture of iron-containing Fischer-Tropsch synthesis catalyst and acid component at elevated pressures and temperatures and specified iron-containing catalyst reduction conditions. Specifically, said iron component is a mixture of neodymium and cerium silicates at weight ratio between 1:9 and 9:1 and weight ratio of acid component to iron-containing catalyst ranges from 1:1 to 6:1.

EFFECT: increased selectivity and productivity of catalyst and reduced level of aromatic hydrocarbons in product.

3 cl, 1 tbl, 15 ex

 

The technical field

The invention relates to organic chemistry, namely to the petrochemical industry and, 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 in the composition of iron-containing catalysts of the Fischer-Tropsch synthesis with acidic components - crystalline aluminosilicates, silicates of rare earth elements neodymium, cerium, praseodymium. The resulting hydrocarbon fractions used as motor fuel and diesel fuel, are characterized by a lower content of aromatic hydrocarbons in comparison with hydrocarbons, obtained from a mixture of carbon monoxide and hydrogen in the presence of known iron catalysts for Fischer-Tropsch synthesis.

A method of obtaining5+hydrocarbons from the gas containing H2and, by contacting the gas at a temperature of 180-250°C, a pressure of 15-20 ATM and a volume ratio of H2/CO equal to 1.1 to 1.8 with a catalyst containing cobalt and zirconium on the media selected from a silicate or oxide of silicon, aluminum, titanium (EN 1833335, C 07 C 1/04, 1993) [1].

Also known is a method of obtaining cobalt-zirconium catalyst on Al2About3for the synthesis of C5+hydrocarbons from the gas containing H2and CO, and CA is applied at a temperature of 150-350° With the pressure of 10-70 ATM and a volume ratio of H2/CO equal to 1,0-2,3 (EN 1836146, 01 J 37/04, 21/04, 23/74, 1993) [2].

According to the data obtained in the result of a mixture of H2and WITH cobalt catalysts are obtained With5hydrocarbons with selectivity from 68-85 wt.% [1] to 87-91 wt.% [2] and performance 100-108 g/l cat/HR

The main disadvantage of the above methods of obtaining liquid hydrocarbons from synthesis gas in the presence of cobalt catalysts is the low content of hydrocarbons from the structure in the reaction products and the high cost of the catalysts.

Therefore, the developed methods for producing liquid hydrocarbons from synthesis gas in the Fischer-Tropsch process using iron catalysts. Although the selectivity and performance of these catalysts is lower in comparison with cobalt, however, the liquid products obtained in the presence of these catalysts contain a greater amount of hydrocarbons from the structure and, in addition, the cost of these catalysts is much lower than cobalt (EN 2180651 C1 11.01.2001).

Closest to the present invention is a method of producing hydrocarbons from carbon monoxide and hydrogen, comprising contacting in a reactor synthesis gas with a catalytic composition consisting of a mixture of an active iron catalyst synthesis the Fischer-the Ropsha and acid component, at high pressure and temperature and desired conditions restoration of iron-containing active component of the catalytic composition (EN 2204546 C1, 2002). The distinctive feature of which is that as the acid component used crystalline aluminosilicate or silicoaluminate use the circulation gas stream after reactor with a volume ratio of the number of circulating gas to the raw synthesis gas, equal 1-1000, and the process is performed at a pressure of 10-100 ATM, a temperature of 220-400°C, space velocity initial synthesis gas 100-5000 h-1, a molar ratio of H2-CO equal to 1-3, and volumetric content of CO2in the gas stream at the inlet to the reactor is from 0.01 to 40%. As catalysts for the Fischer-Tropsch synthesis using fused iron catalyst in the oxidized or the reduced form, promoted by oxides of aluminum, silicon, magnesium, potassium and calcium. As the acid component of the catalyst used crystalline silicates with the structure of ZSM-5 type, as well as crystalline silicoaluminate with the structure of SAPO-5. Catholic composition comprises 10-90% iron catalyst for Fischer-Tropsch synthesis and 10-90% of the acid component.

According to prototype products conversion of synthesis gas are gasoline fraction (5-C1010-C20hydrocarbons), paraffin waxes With21+and the reaction water containing oxygenated compounds.

However, in the prototype has a major drawback:

When used in the synthesis of hydrocarbons from carbon monoxide and hydrogen catalytic compositions from a number presented in the patent, giving the lowest content of aromatic hydrocarbons in the reaction products and 2.9 wt.% (example 13 prototype), there is a decrease in process efficiency, which is expressed in the reduction of the yield of liquid hydrocarbons to 105 g/nm3the synthesis gas and the utilization of carbon contained in the original monoxide to 50 wt.%, in comparison with indicators of more effective catalysts. However, it should be noted that for a more effective catalytic compositions (example 8 prototype), characterized by a high yield of liquid hydrocarbons - 159 g/nm3and utilization of carbon from the source of carbon monoxide equal to 78 wt.%, the content of aromatic hydrocarbons in the reaction products increases to 22.5 wt.%.

The value of this drawback significantly. Taking into account modern requirements to motor fuels aimed at reducing their composition content of aromatic hydrocarbons, and the main primeneniye in the specified way hydrocarbons - it is their use as motor fuels, high content of aromatic hydrocarbons is undesirable.

The present invention is the development and establishment of a method of producing hydrocarbons from carbon monoxide and hydrogen, with improved performance.

The solution of this task is possible obtain a technical result consists in increasing the selectivity and productivity of the catalyst in the liquid hydrocarbon with a simultaneous decrease in the liquid products and polynuclear aromatic hydrocarbons.

These technical results are achieved by the fact that in the method of producing hydrocarbons from carbon monoxide and hydrogen, comprising contacting in a reactor synthesis gas with a catalytic composition consisting of a mixture of iron catalyst for Fischer-Tropsch synthesis and acid component at elevated pressures and temperatures and desired conditions restoration of iron-containing catalyst, as an acid component, a mixture of silicates of neodymium and cerium in a weight ratio of iron-containing catalyst and an acid component of from 1 to 6 and the ratio of the silicates of neodymium and cerium, wt.%:

silicate neodymium10-90
the silicate Church is I 10-90

In addition, apply the circulation of the gas stream after reactor with a volume ratio of the number of circulating gas to the source gas is equal to 1-1000, and the process is performed at a pressure of 10-100 ATM, a temperature of 220-400°C, 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 gas stream at the inlet to the reactor is from 0.01 to 40%.

Distinctive features of the invention are:

for the catalytic conversion of synthesis gas into hydrocarbonaceous products as catalyst a mixture of iron catalysts for Fischer-Tropsch synthesis in oxidized or reduced form, promoted by oxides of aluminum, silicon, alkaline or alkaline-earth metals, with the acid component - silicates of rare earth elements neodymium and cerium mass ratio of iron-containing catalyst/acid component, equal 50/50 - 85/15.

The weight ratio of neodymium and cerium, forming part of the acid component of the catalyst ranges (wt.%):

silicate of neodymium - 10-90,

silicate of cerium - 10-90.

The choice of catalyst for the conversion of synthesis gas to hydrocarbon products based on the fact that all of the catalysts of the Fischer-Tropsch synthesis most of the producer is generated in the temperature range 220-400° With are fused iron catalysts. The combination of fused iron catalysts with acidic components leads to enhanced synthesis of hydrocarbons from H2, CO and CO2due to more rapid reactions of conversion of the intermediate products of the Fischer-Tropsch synthesis (alcohols, olefins) on the acid component in the target hydrocarbon products.

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 (220° (C) determined by the minimum activity of the catalyst, the excess of the upper temperature (400° (C) 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, with fixed values of pressure and temperature. The claimed value of the flow rate is optimal for obtaining the gasoline and diesel fractions. The ratio between H2and FROM, and between CO and CO2is determined by the stoichiometry of the course of chemical reactions synthesis of hydrocarbons. For education group "CH2" paraffin hydrocarbons at one and the ω carbon requires two hydrogen atoms, and the amount of bound "On" in the feedstock determines the consumption of hydrogen for the formation of molecules N2O. Based on theoretical assumptions, experiments were conducted under conditions sufficiently close to the stoichiometric ratio between the atoms of carbon, oxygen and hydrogen. Terms of recovery of the catalyst was determined experimentally.

An important role in achieving high selectivity and productivity of the catalytic composition on the synthesis of liquid hydrocarbons belongs circulation of the gas stream after separation of the liquid products. Permanent removal of water and liquid hydrocarbons from the contact of the gas prevents the poisoning of the surface of the iron catalyst with water vapor, substantially suppresses the reaction of formation of carbon dioxide passive component in the reaction of the Fischer-Tropsch and reduces cracking of the formed liquid hydrocarbons in the acid component. When recycling light olefins and the intermediate oxygen-containing products are repeatedly in contact with the catalyst and are converted into desired products.

Examples of implementation of the method

Examples of implementation of the method of producing hydrocarbons from carbon monoxide and hydrogen are presented in table 1 (examples 3-15).

In examples 3-8 were used catalytic composition consisting of fused glands the second catalyst and the acid component is a mixture of silicates of neodymium and cerium with weight ratio (wt.%) 50/50 and content of the acid component (wt.%) 15-50.

In examples 9-11 were used catalytic composition with the content of the acid component (wt.%) - 30, the weight ratio of silicate neodymium and cerium, forming part of the acid component was varied in the range (wt.%):

silicate of neodymium - 10-90,

silicate of cerium - 10-90.

In examples 12-15 acid component in Agrocomplex was (wt.%) - 30, and the ratio of the silicates of neodymium and cerium 50/50.

Example 1 (the prototype).

Charged to the reactor 50 cm3fractions of 0.25-0.5 mm fused iron catalyst (Agrocomplex) and granulated (30 wt.% Al2About3) zeolite ZSM-5 in a mass ratio of 33/67. The original synthesis gas is fed in the reactor block to mix with the circulating gas block. Reactor unit consists of a reactor with heating, condenser, separator, high and low pressure, intermediate 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 10 ATM, the temperature is 350°With the duration of 24 hours and Then raise the pressure up to 30 ATM and continue the recovery of the catalyst at a temperature of 350°C for 8 hours. After the restoration is the process of developing a catalyst at a temperature of 300°C for 20 hours. The process of synthesis of hydrocarbons in the children under a pressure of 30 ATM and a temperature of 280° C. To prevent accumulation in the reactor block condensation products from the block after the high pressure separator continually remove part of the circulating gas. Liquid products (hydrocarbons and water), the output from the reactor building gas and allocated by throttling gaseous hydrocarbons are analyzed chromatographically. The process conditions and the main results are given in table 1.

Example 2 (the prototype).

The conditions of the experiment are shown in table 1. Similar to example 1 except that:

- changed the composition of the catalyst, in which the acid component used zeolite type (SiO2/Al2O3=75),

- mass ratio of the fused iron catalyst to the acid component 70/30,

- the multiplicity of circulation increased to 600,

- volumetric rate reduced to 700 h-1.

Presents the results of the experiments were taken from the examples, prototype, characterized by the lowest content of aromatic hydrocarbons in the produced liquid products. The content of aromatic hydrocarbons is to 11.9 wt.% and 2.9 wt.% for example 1 and 2. The yield of liquid hydrocarbons 148 and 105 g/nm3the original synthesis gas, the degree of carbon contained in the carbon monoxide, 72 and 50%, respectively. The achievement of a higher showing the oil yield of liquid hydrocarbons and extent of use "carbon", contained in the carbon monoxide, which characterizes the efficiency of the process according to the data presented in the prototype, lead to an increase in the content of aromatic hydrocarbons in the produced liquid hydrocarbons.

The latter is undesirable, since the resulting liquid hydrocarbons used as motor fuels in accordance with European and international standards should be characterized by a low content of aromatics.

Example 3. Similar to example 2 except that there is used a catalyst consisting of a fused iron catalyst and an acid component composed of a mixture of silicates of neodymium and cerium, in a weight ratio of 50:50.

The results obtained are characterized by a low content of aromatic hydrocarbons in the produced liquid hydrocarbons to 3.0 wt.%. The yield of liquid products exceed the performance achieved in the prototype (28% for example 1 and 71% for example 2).

Example 4. Similar to example 3 except the weight ratio of calcined catalyst and acid catalyst, which is 50/50.

Example 5. Similar to example 4 except the weight ratio of calcined iron catalyst and an acid component, which is 85/15.

Example 6. Similar is Chen example 3 except this experience working process pressure is increased to 50 ATM.

Example 7. Similar primro 3 except that in this experiment increased to 1000 h-1the volumetric rate of the process.

Example 8. Similar to example 3 except that the space velocity of the process is reduced to 500 h-1.

Example 9. Similar to example 3 except that as the acid component was used a mixture of silicates of neodymium and cerium with weight ratio, wt.%:

silicate of neodymium - 10,

silicate of cerium - 90.

Example 10. Similar to example 3 except that as the acid component was used a mixture of silicates of neodymium and cerium with weight ratio, wt.%:

silicate of neodymium - 30,

silicate of cerium - 70.

Example 11. Similar to example 3 except that as the acid component was used a mixture of silicates of neodymium and cerium with weight ratio, wt.%:

silicate of neodymium - 90,

silicate of cerium - 10.

Example 12. Similar to example 3 except that the pressure in the reaction system is 10 ATM.

Example 13. Similar to example 3 except that the process temperature is 400°C.

Example 14. Similar to example 3 except that the space velocity of the process 100 h-1.

Example 15. Similar to example 3 for the drop is observed in that the volumetric content of CO2in the gas stream at the inlet to the reactor is 4.0%.

As seen in the table 1 results, the proposed method allows to obtain liquid hydrocarbons and has advantages compared with prototype:

- low content of aromatic hydrocarbons in the produced liquid products,

- in this case, the yield of liquid hydrocarbons and extent of use "carbon" monoxide exceeds these prototypes.

1. A method of producing hydrocarbons from carbon monoxide and hydrogen, comprising contacting the synthesis gas with a catalytic composition consisting of a mixture of iron catalyst for Fischer-Tropsch synthesis and acid component at elevated pressures and temperatures and desired conditions restoration of iron-containing catalyst, characterized in that the acid component is a mixture of silicates of neodymium and cerium in a weight ratio of the acid component and the iron-containing catalyst is from 1 to 6 and the silicate content of neodymium and cerium, wt.%:

Silicate neodymium10-90
Silicate of cerium10-90

2. The method according to claim 1, characterized in that applied the circulation of the gas stream after reactor with a volume ratio of the number of circulating gas to the source gas, equal 1-1000.

3. The method according to claim 1 or 2, characterized in that the process is performed at a pressure of 10-100 ATM, a temperature of 220-240°C, 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 gas stream at the inlet to the reactor is from 0.01 to 40%.



 

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