Method for preparing hydrocarbon and catalyst for its realization

FIELD: petroleum chemistry, organic chemistry, chemical technology.

SUBSTANCE: method involves contacting a mixture of carbon monoxide and hydrogen at increased temperature and pressure with a catalyst comprising manganese and cobalt on a carrier wherein cobalt, at least partially, presents as metal and catalyst comprises also inorganic phosphate in the amount at least 0.05 wt.-% as measure for elementary phosphorus relatively to the catalyst weight. Also, catalyst can comprise vanadium, zirconium, rhenium or ruthenium additionally. Method provides selectivity in formation (C5+)-hydrocarbons and decrease in formation of CO2.

EFFECT: improved preparing method.

7 cl, 1 tbl, 2 ex

 

The present invention relates to a method for producing hydrocarbons from synthesis gas and the catalyst, which can be used in this way.

Catalytic preparation of hydrocarbons from synthesis gas, i.e. a mixture of carbon monoxide and hydrogen is well known and is commonly referred to as Fischer-Tropsch synthesis.

The catalysts on a carrier suitable for use in the method of synthesis by the Fischer-Tropsch usually contain a catalytically active metal of group VIII of the Periodic table of the elements (Handbook of Chemistry and Physics, 68thedition, CRC Press, 1987-1988). In particular, it is well known that iron, Nickel, cobalt and ruthenium are catalytically active metals for such catalysts. You can refer to EP-A-398420, EP-A-178008, EP-A-167215, EP-A-168894, EP-A-363537, EP-A-498976 and EP-A-71770.

There is a continuous interest in the development of catalysts for enhanced selectivity in the conversion of carbon monoxide in the target hydrocarbons, particularly hydrocarbons with 5 or more carbon atoms (here, "C5+ hydrocarbons"), which reduces to a minimum the formation of carbon dioxide, which is a low-value carbon-containing by-product.

It has been unexpectedly discovered that when used in the Fischer-Tropsch synthesis catalyst containing inorganic phosphate, the hydrocarbon on ucaut more in particular, more With5+hydrocarbons, and to a lesser extent carbon dioxide. In addition, there is less reduction in the activity of the catalyst, therefore, the catalysts can be used over a prolonged period of time without replacement or reactivation.

Accordingly, the claimed invention provides a method of producing hydrocarbons, which involves contacting a mixture of carbon monoxide and hydrogen at elevated temperature and pressure with a catalyst containing a metal of group VIII on a carrier, and the metal of group VIII, at least partially present in the form of metal, and the catalyst additionally contains inorganic phosphate in the amount of at least 0,05 wt.% in the calculation of the elemental phosphorus relative to the weight of the catalyst.

As the metal of group VIII is preferably selects one or more metals from the group comprising iron, Nickel, cobalt and ruthenium. More preferably, when the metal of group VIII choose cobalt or ruthenium, because the catalysts based on cobalt and ruthenium provide a relatively high output With5+hydrocarbons. As the metal of group VIII of the most preferred cobalt.

Additional metal may be present to improve the catalyst activity or the CE is aktivnosti conversion of synthesis gas into hydrocarbons. Suitable for this additional metals can be selected from manganese, vanadium, zirconium, rhenium and ruthenium. Preferred additional metal may be manganese or vanadium, and especially manganese.

Catalysts that contain supported on a carrier metal of group VIII selected from Nickel, cobalt, iron and ruthenium, and an additional metal selected from manganese, vanadium, zirconium and rhenium, as well as inorganic phosphate in the amount of at least 0,05 wt.%, in the calculation of the elemental phosphorus relative to the weight of the catalyst, are new. On the other hand, the present invention also provides these new catalysts.

The amount of metal of group VIII contained in the catalyst can vary widely. Typically, the catalyst contains from 1 to 50 wt.% metal of group VIII in the calculation of the total amount of metal relative to the weight of catalyst, preferably from 3 to 40 wt.%, more preferably 5-30 wt.% based on the same conditions.

The number of additional metal, if present, is usually from 0.05 to 60 wt.%, more often from 0.1 to 25 wt.% based on the weight of the metal relative to the weight of the catalyst.

The atomic ratio of the metal of group VIII and an additional metal, in case of its presence in the catalyst, is typically at least 5:1 and, as a rule, with the hat at most 200: 1.

Inorganic phosphate can be present in the catalyst in any amount, at least 0.5 wt.%, in the calculation of the elemental phosphorus relative to the weight of the catalyst. Inorganic phosphate is usually present in amounts of < 5 wt.%, the preferred amount is within the range from 0.1 to 2.5 wt.%, for example, 0.5 wt.%, based on the same conditions.

Usually porous inorganic carrier may be considered suitable for use in the present invention. As a preferred carrier is a refractory (refractory) oxide carrier. Examples of such refractory oxide carriers are aluminum oxide, silicon dioxide, titanium dioxide, zirconium dioxide and mixtures thereof, such as a mixed oxide of silicon, aluminum, or obtained by physical mixing of the mixture of silica and titanium. Preferably the carrier comprises titanium dioxide, aluminum oxide, zirconium dioxide or mixtures thereof, especially titanium dioxide or aluminum oxide.

Media containing titanium dioxide, aluminum oxide, zirconium dioxide or mixtures thereof, may also optionally contain up to 50 wt.% another refractory oxide, typically silicon dioxide, calculated on the total weight of the carrier. More preferably, when the additional refractory oxide, in case of its presence, Staritsa amount up to 20 wt.% and most preferably up to 10 wt.%, based on the same conditions.

Most preferably, when the medium contains titanium dioxide, particularly titanium dioxide, which was obtained in the absence of sulfur-containing compounds. An example of such a method of obtaining includes the hydrolysis of titanium tetrachloride in a flame. It should be noted that powdered titanium dioxide obtained by this method may not be the desired size and shape. Then, as a rule, conduct phase shape (particles) media. Methods the shape is well known in the art and include granulation, extrusion, methods, spray drying and dropping in the hot oil.

The catalyst may be suitably prepared by methods well known in the art, for example, by deposition of the catalytically active components or precursors on the substrate, irrigation with the formation of the coating, mixing, heating, and/or impregnation of the carrier of the catalytically active components or precursors, and/or extruding one or more catalytically active components or precursors together with the material of the carrier in order to obtain extrudates of catalyst. The term "catalytically active components" includes the metal of group VIII, some additional metal and inorganic phosphate, in St. the zi with his presence in the catalyst. It is not excluded, however, that, in addition to the catalytically active component and the carrier, the catalyst may contain other components.

It should be noted that the method of obtaining can change (vary) depending on, for example, the desired size of the catalyst particles. The choice of the most suitable way in the most various circumstances and requirements depends on specialist training.

The preferred method of preparation of the catalyst involves the preparation of a mixture of media, the catalytically active components and/or precursors and liquid, for example, by mixing or dispersion, shaping and drying the thus obtained mixture, followed by calcination, as described in WO 99/34917.

A suitable liquid is water, ammonia, alcohols, such as methanol and ethanol, ketones such as acetone, aldehydes, for example, propanal and aromatic solvents such as toluene. Preferred is water.

The metal of group VIII and an additional metal can be applied in the form of the metal itself, and in the form of oxide, hydroxide or salt, such as nitrate or acetate, or a mixture thereof.

Suitable for use predecessors phosphate, if they are contained in the catalyst are, for example, connect the deposits of phosphorus, includes phosphorus-containing acid, such as metaphosphoric acid, pyrophosphoryl acid, phosphorous acid, but preferably orthophosphoric acid (H3PO4), or predecessors fosforsoderzhashchie acid, which are phosphorus-containing compounds, capable of forming a compound containing at least one acidic hydrogen atom in the presence of water or under conditions, which are used in the preparation of the catalyst and/or activation of the catalyst, as will be stated below. Predecessor fosforsoderzhashchie acid is, for example, phosphorous pentoxide, pentachloride phosphorus or ammonium phosphates.

The calcination is usually carried out at a temperature between 200 and 900°C, preferably between 250 and 600°C. the duration of the calcination is usually from 0.5 to 24 hours, preferably from 1 to 4 hours. Convenient to carry out stage of annealing in oxygen-containing atmosphere, preferably in air. It should be noted that the average temperature during annealing is usually higher than the average temperature during drying.

This catalyst is usually used in catalytic method of producing hydrocarbons from synthesis gas. Usually when you use it in this way, at least part of the metal of group VIII is present in the form of metal. Pre is respectfully from 50 to 100 wt.% metal of group VIII is contained in the form of metal, preferably from 60 to 98 wt.%.

Therefore, usually considered useful to activate the catalyst prior to use with the help of recovery in the presence of hydrogen at elevated temperature. Usually the recovery procedure includes treatment of the catalyst at a temperature of from 100 to 450°at high pressure and usually 1-200 bar, often within 1-200 hours. At the stage of recovery can be used pure hydrogen, but usually prefer to use a mixture of hydrogen and inert gas, e.g. nitrogen. The relative content of hydrogen in the mixture may be in the range from 0.1 to 100 vol.%.

In accordance with a preferred embodiment of the invention the catalyst is introduced at the desired level of temperature and pressure in a nitrogen atmosphere. Subsequently, the catalyst is in contact with a gas mixture containing only a small amount of hydrogen, the rest is nitrogen. In the process of recovering the relative amount of gaseous hydrogen in the gas mixture gradually rises to 50% vol. or even up to 100%vol.

You can activate the catalyst in situ, i.e. inside the reactor for the production of hydrocarbons from synthesis gas. In WO 97/17137 described method of activating the catalyst in situ, which includes the contacting of the catalyst in the presence of a liquid hydrocarbon with a hydrogen-containing gas is m at a partial pressure of hydrogen, equal to at least 30 bar abs. Usually in this process, the partial pressure of hydrogen is almost 200 bar abs.

A method of producing hydrocarbons from synthesis gas is usually carried out at a temperature in the range from 125 to 350°C, preferably from 175 to 275°C. the Pressure is typically from 5 to 150 bar abs., preferably from 5 to 80 bar abs., particularly preferably from 5 to 60 bar abs.

Hydrogen and carbon monoxide is usually served at a molar ratio in the range from 1 to 2.5. Low molar ratio of hydrogen and carbon monoxide will increase With5+selectivity, i.e. the selectivity of the formation of C5+hydrocarbons. With5+selectivity of the method is preferably at least 90 wt.% in the calculation of the total number of received hydrocarbons, preferably 95 wt.%.

However, in the version of the present invention, in which the metal of group VIII is cobalt, and the additional metal is manganese and/or vanadium, which are contained in the atomic ratio of cobalt/manganese+vanadium), at least 12:1, p5+ selectivity of the catalyst is very high, even if you are using a synthesis gas with a high atomic ratio of hydrogen and carbon monoxide. In this embodiment, the molar ratio of hydrogen and carbon monoxide is in the range from 1.5 to 2.5.

Hourly space velocity of gas GHSV may vary within a wide range and is usually in the range from 400 to 10000 nl/l/h, for example, from 400 to 4000 nl/l/h

The term "GHSV" is well known in the art and refers to the flow rate of gas per hour, i.e. describes the amount of synthesis gas in the IO (i.e. at normal temperature 0°and a standard pressure of 1 bar (100,000 PA)), which is in contact within 1 hour on a single liter of catalyst particles, i.e. excluding the empty space between particles. In the case of a stationary layer of catalyst GHSV is usually expressed per liter of catalyst layer, i.e. including unoccupied areas of space between particles. In this case, GHSV equal to 1600 nl/l/h for the catalyst in the form of particles, corresponding to approximately 1000 nl/l/h for the catalyst layer.

A method of producing hydrocarbons can be carried out using reactors of various types and in different reaction modes, for example, the mode with the stationary layer, the mode with the suspension phase or in the fluidized bed. It should be noted that the size of the catalyst particles may vary markedly depending on the reaction regime, for which they are intended. It specialist - to choose the most suitable size of the catalyst particles to a specific mode of action.

Moreover, it should be clear that an experienced specialist will be able to choose the most suitable conditions in parts of the special shape of the reactor, the modes of reaction and the workload. Example is, preferred hourly space velocity of the gas may depend on the type of mode of response. In that case, if you want to regulate the synthesis of hydrocarbons in the mode with the stationary layer, the hourly space velocity of the gas is preferably chosen in the range from 500 to 2500 nl/l/h If you want to perform the process of synthesis of hydrocarbons in the suspension phase, the hourly space velocity of the gas is preferably chosen in the range from 1500 to 7500 nl/l/h

The invention is illustrated using the following examples.

Example 1.

Preparing a mixture containing 112,5 g of a commercially available powder of titanium dioxide (P25 ex Degussa), a 49.5 g of a commercially available powder of CO(Oh)2, and 8.2 g of Mn(AC)2×4H2O ("Ac" means the acetate), 2.2 g of phosphoric acid and 45 g of water. The mixture was stirred for 30 minutes and gave her a form by extrusion. The extrudate was dried for 2 hours at 120°and progulivali for 2 hours at 500°C. the Catalyst contained 22 wt.% WITH, 1.2 wt.% Mn and 0.7 wt.% R.

The catalyst was tested in the process of obtaining hydrocarbon. The flow-through microreactor containing 10 ml of the catalyst in the form of a stationary layer of the catalyst particles was heated to a temperature of 260°and increased pressure up to 2 bar abs. with a continuous stream of nitrogen. The catalyst was recovered in situ during the course the e 24 hours with a gas mixture of nitrogen and hydrogen. In the process of recovery relative amount of hydrogen in the mixture is continuously increased from 0 to 100%. The water concentration in the exhaust gases is maintained below 3000 parts (vol.) in a million.

After restoring the pressure was increased to 31 bar abs. The preparation of hydrocarbons was carried out using a mixture of hydrogen and carbon monoxide with H2/ CO ratio of 1.1: 1. GHSV was about 930 nl/l/h the reaction Temperature, expressed as a weighted average temperature of the layer was 205°C. Output with respect to time and volume, expressed in grams of hydrocarbon product per liter of catalyst particles (including the voids between particles) was 100 g/l/h Selectivity for CO2expressed in mol.% received CO2in the calculation of the number of moles converted FROM, selectivity for hydrocarbons, expressed in mol.% carbon contained in the received hydrocarbons in the calculation of the number of moles converted and the selectivity to hydrocarbons with 5 or more carbon atoms (C5+selectivity), expressed as a weight percentage of the total hydrocarbon product, was determined after 30 hours after the process. The results are shown in table 1.

Example 2 (comparative).

I repeat almost the entire Example 1 with the only difference that in a mixture of phosphoric acid is present.

Table 1
ExampleIII *)
The selectivity for CO2(mol.%)0,91,3
Selectivity forof 99.198,7
hydrocarbons(mol.%)
With5+selectivity (wt.%)9492
*) the comparative result

It is evident that the catalyst of example 1, i.e. according to the invention, much better than the catalyst of example 2, i.e. the catalyst for comparison.

1. The method of obtaining5+hydrocarbons comprising contacting a mixture of carbon monoxide and hydrogen at elevated temperature and pressure with a catalyst containing cobalt and manganese, the catalyst is located on the carrier, and at least part of the cobalt is in the form of metal, and the catalyst further comprises an inorganic phosphate in the amount of at least 0,05 wt.% in the calculation of the elemental phosphorus relative to the weight of the catalyst.

2. The method according to claim 1, characterized in that it contains an additional metal selected from vanadium, zirconium, rhenium and ruthenium.

3. The method according to claim 1 or 2, characterized in that the inorganic phosphate content is carried out in a number in the range from 0.1 to 2.5 wt.% in the calculation of the elemental phosphorus relative to the weight of the catalyst.

4. The method according to any one of claims 1 to 3, characterized in that the medium contains titanium dioxide or aluminum oxide.

5. The catalyst for the Fischer-Tropsch process, containing cobalt and manganese, found on the media, which are titanium dioxide, the catalyst further comprises an inorganic phosphate in the amount of at least 0,05 wt.% in the calculation of the elemental phosphorus relative to the weight of the catalyst, and at least part of the cobalt is in the form of metal, and cobalt contained in an amount of from 1 to 50 wt.% based on the weight of the metal relative to the weight of the catalyst.

6. The catalyst according to claim 5, in which inorganic phosphate is present in an amount in the range from 0.1 to 2.5 wt.% in the calculation of the elemental phosphorus relative to the weight of the catalyst.

7. The method of preparation of the catalyst described in claim 5, including the stage of preparation of a mixture of cobalt, manganese and inorganic phosphate and/or their precursors, titanium dioxide and liquid, shaping and drying the resulting mixture and calcining and recovery in the presence of hydrogen.



 

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1 dwg, 2 tbl, 6 ex

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< / BR>
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7 cl, 1 tbl, 2 ex

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9 cl, 3 tbl, 19 ex

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7 cl, 2 tbl, 13 ex

FIELD: chemistry.

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23 cl, 3 ex

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