Fischer-tropsch catalyst regeneration by oxidation and treatment with mixture of ammonium carbonate, ammonium hydroxide and water

FIELD: chemistry.

SUBSTANCE: invention relates to catalysis. Described is a method of regenerating one or more particles of a cobalt-containing Fischer-Tropsch catalyst in situ in a reactor tube, the method comprising steps: (i) oxidising the catalyst particle(s) at temperature of 20-400°C; (ii) treating the catalyst particle(s) for more than 5 min with a solvent; (iii) drying the catalyst particle(s); and (iv) optionally reducing the catalyst with hydrogen or any hydrogen-containing gas.

EFFECT: high catalyst activity.

10 cl, 4 tbl, 4 ex

 

The present invention relates to a method of regenerating the catalyst. More specifically, the invention relates to a method of regenerating the catalyst in situ in the reactor tube. The catalyst is intended for use in the production of gaseous under normal conditions, liquid under normal conditions and, possibly, solid under normal conditions of hydrocarbons from synthesis gas, usually obtained from coal-hydride materials, for example, using the Fischer-Tropsch process. The invention also relates to a regenerated catalyst and to its use in the Fischer-Tropsch process.

the Fischer-Tropsch process can be used for the conversion of synthesis gas (from different coal-hydride materials in liquid and/or solid hydrocarbons. As a rule, raw materials (e.g. natural gas, associated gas and/or coal bed methane, heavy and/or residual oil fractions, coal, biomass) is converted in the first stage, in a mixture of hydrogen and carbon dioxide (this mixture is commonly referred to as synthesis gas). After that, the synthesis gas is fed into the reactor where it is converted in one or more stages over a suitable catalyst at elevated temperature and pressure into paraffinic compounds and water. The resulting paraffin hydrocarbons ranging from methane to high molecular weight hydrocarbons. The floor is aimie high molecular weight hydrocarbons can contain up to 200 carbon atoms, or under special circumstances, even a greater number of carbon atoms.

For the reaction of the Fischer-Tropsch process have been developed many types of reactors. For example, the reactor system Fischer-Tropsch include reactors, fixed bed, in particular mnogohramie reactors, fixed bed, fluidized bed reactor, such as reactor viable fluidized bed, or a reactor with a fixed fluidized bed, and the reactors with the suspension layer, such as bubble columns with three-phase slurry and the reactor with a fluidized bed of catalyst.

Used in the Fischer-Tropsch synthesis catalysts often contain media-based substrate material and one or more metals from groups 8-10 of the periodic system, in particular from the group of cobalt or iron, possibly in combination with one or more metal oxides and/or metals as promoters selected from zirconium, titanium, chromium, vanadium and manganese, especially manganese. Such catalysts in the technique known and described, for example, in the descriptions of the patents WO 9700231A and US 4595703.

One of the limitations of the way the Fischer-Tropsch process is that the catalyst activity for a number of reasons decrease over time. The catalyst after use in the Fischer-Tropsch process has low activity, sometimes referred to as desanti the new catalyst, although he usually still has activity. This is sometimes called catalyst degraded catalyst. In some cases, this catalyst can be regenerated. This can be accomplished, for example, in one or more stages of oxidation and/or recovery.

The aim of the present invention is to provide a method of regenerating in situ in the reactor tube cobalt containing catalyst Fischer-Tropsch process. The present invention particularly relates to a method, which can be used for regenerating in situ fixed layers of catalysts, such as pellets and extrudates larger 1 mm in one or more of the tubes of the reactor Fischer-Tropsch fixed bed. The present invention also particularly relates to a method, which can be used for regenerating immobilized suspension of catalyst in the reactor tube, mainly suspension immobilized catalyst containing one or more catalyst particles larger than 1 mm Particle size of at least 1 mm are defined as particles having the largest internal straight length of at least 1 mm.

According to one aspect of the present invention, a method of regenerating in situ in the reactor tube of the one or more particles of cobalt containing catalyst F. the Fischer-Tropsch process, after the particle(s) of the catalyst was deactivated as a result of its use in the Fischer-Tropsch process, and this method of regenerating includes stages:

(i) oxidation of the particles (particles) of the catalyst at a temperature of from 20 to 400°C, mainly from 100 to 400°C and, more preferably, from 200 to 400°C;

(ii) processing of particles (particles) of the catalyst for more than 5 min solvent;

(iii) drying and optionally heating the particles (particles) of the catalyst; and

(iv) optionally recovering the particles (particles) of the catalyst with hydrogen or any hydrogen-rich recycle gas.

All stages of the method of the invention are performed in the order listed. The method may include additional stages. All stages of the method of the invention carried out in situ in the reactor tube. The particle(s) of the catalyst is mainly deactivated as a result of its use in the Fischer-Tropsch process in the reactor tube in situ and all stages of this aspect of the method of the invention are carried out in situ in the same reactor tube. This is advantageous because it eliminates the need for unloading and reloading of the deactivated catalyst.

When using the method according to the invention, the activity of the deactivated cobalt containing catalyst Fischer-Tropsch process can be significantly is isana.

The method of the present invention is suitable for catalysts in a fixed bed, slurry catalysts, i.e. powdered catalysts, suspension and immobilized catalyst, for example a wire structures coated with catalyst material. The method of the present invention is particularly suitable for catalysts in a fixed bed and suspension immobilized catalysts.

Examples of suitable catalysts in a fixed bed are pellets and extrudates larger than 1 mm, which contain cobalt as the material carrier of any heat-resistant metal oxide.

Examples of suitable suspension immobilized catalysts in respect of whom may be applied the method of the present invention are catalysts larger than 1 mm, which contain a substrate and a catalyst material.

Immobilized catalyst suspension may, for example, be in the form of a fixed structure (or ordered packings, such as wire mesh, corrugated sheet material which may be perforated or may not be perforated, woven or non-woven structure, cell structure, the foam or sponge structure, mesh, rib structure, foil design, woven Mat, wire, ball, cylinder, cube, sphere, eizabeth the I form, monolith or any combination thereof.

The substrate acts as a catalyst carrier material, which it is. The substrate includes mostly inert material capable of withstanding the conditions inside the reactor. The substrate may, for example, contain a heat-resistant metal oxide and/or metal. Mostly the substrate contains a metal, such as stainless steel, iron or copper.

The material of the catalyst includes a carrier and a catalytically active metal. Suitable carriers are heat-resistant metal oxide such as aluminum oxide, silicon oxide and titanium oxide, preferably titanium oxide. In the present invention the catalytically active metal is cobalt.

Containing cobalt catalyst to be regenerated after decontamination in use in the Fischer-Tropsch process. The activity of the deactivated catalyst mainly of at least 10% below its initial activity when it was freshly prepared. The catalyst can be completely deactivated, i.e. lost more than 90% of its initial activity. In some cases it may be useful to regenerate the catalyst when the decrease of its activity has reached at least 50% and, more preferably, at least 60%. In some cases, can the t to be useful to regenerate the catalyst by reduction of activity of not more than 90%, mostly not more than 85% and, most preferably, not more than 80%.

The catalyst mainly contains cobalt and material media for cobalt. The material of the carrier mainly contains heat-resistant metal oxide such as aluminum oxide, silicon oxide and titanium oxide and mixtures thereof, more preferably titanium oxide.

In the case where the catalyst material contains as a carrier for the cobalt titanium oxide, the amount of cobalt metal is mostly in the range from 10 to 35 wt.% and, more preferably, in the range from 15 to 30 wt.% on the total weight of titanium oxide and cobalt metal.

In one embodiment of the method according to the invention the catalyst particle can be recovered hydrogen or hydrogen-rich recycle gas after stage (i) oxidation and before stage (ii) processing. As a result of such recovery can be obtained partially or completely recovered catalyst particle. During this recovery stage (i) a certain amount of cobalt in the catalyst particle, which is present in the form of cobalt oxide (II, III) (CO3O4), is transformed into the cobalt oxide (II) (CoO) and/or metal cobalt (Co).

Stage (ii) processing is carried out mainly with the removal of the catalyst, oxygen is a, for example, using an inert gas, preferably using nitrogen.

Used in stage (ii) of the method, the solvent is predominantly contains one or more chemical compounds selected from the group consisting of nitric acid, a weak organic acids, ammonium salts and alkylammonium salts. These solvents may be used in combination with ammonia and/or ammonium hydroxide, and/or Ethylenediamine, and/or urea. Used in stage (ii) the solvent may also contain water.

Examples of suitable weak organic acids are carboxylic acids having the General formula R-(COOH)nin which n is 1-3 and R is a cyclic or aliphatic, saturated or unsaturated fragment, which may be substituted by one or more of the groups nitro, amino, hydroxy or alkoxy. Specific examples of suitable acids include formic acid, acetic acid, citric acid, succinic acid, malonic acid, propionic acid, butyric acid, Valerian acid, Caproic acid, glutaric acid, adipic acid, lactic acid, benzoic acid, phthalic acid, salicylic acid, ascorbic acid, oxalic acid, carbonic acid, glycine, aminopropionic acid, aminobutanol acid, iminodiethanol is islote and mixtures thereof. Preferred weak organic acids are acetic acid, citric acid, carbonic acid, glycine and iminodiacetate acid and their mixtures, in particular glycine.

Examples of suitable ammonium salts are ammonium salts of weak organic acids and mixtures thereof, in particular ammonium salts of the above weak organic acids and mixtures thereof. Examples of particularly preferred ammonium salts are ammonium acetate, ammonium carbonate and mixtures thereof, in particular ammonium carbonate.

Examples of suitable alkylammonium salts are mono-, di-, tri - and tetraalkylammonium salts and mixtures thereof, particularly mono - and dialkylammonium salt of the above weak organic acids and mixtures thereof.

In a highly preferred embodiment, used in stage (ii) of the method, the solvent contains glycine, ammonium carbonate, a mixture of glycine with Ethylenediamine, a mixture of glycine with ammonium hydroxide or a mixture of ammonium carbonate with ammonium hydroxide, most preferably a mixture of ammonium carbonate with ammonium hydroxide. Even more preferably used in stage (ii) of the method of solvent containing water and optionally water glycine, ammonium carbonate, a mixture of glycine with Ethylenediamine, a mixture of glycine with ammonium hydroxide or a mixture of carbonate Ammon is I with ammonium hydroxide, most preferably a mixture of ammonium carbonate with ammonium hydroxide.

In the case of use on stage (ii) a mixture of water, ammonium carbonate and ammonium hydroxide are preferred the following weight ratio. The weight ratio of ammonium hydroxide to ammonium carbonate is preferably from 1:0.25 to 1:2, more preferably from 1:0.5 to 1:1. The weight ratio of ammonium carbonate to water is preferably from 1:0.5 to 1:4, more preferably from 1:1 to 1:2. The weight ratio of ammonium hydroxide to water is preferably from 1:0.25 to 1:4, more preferably from 1:05 to 1:2.

Mostly at least 10 wt.%, more preferably more than 20 wt.% cobalt processed in stage (ii) the catalyst particle is present in the form of Co3O4. Mainly to 99 wt.%, more preferably less than 95 wt.% cobalt processed in stage (ii) the catalyst particle is present in the form of Co3O4. Mostly less than 50 wt.%, more preferably not more than 40 wt.% cobalt in the catalyst particle are cobalt (II), for example present in the form of a divalent oxide or divalent hydroxide.

This catalyst particle can be obtained under normal conditions, when the catalyst particle Fischer-Tropsch process, which was deactivated in the Fischer-Tropsch process, an oxide is Aut on stage (i) as a result of processing the catalyst particles within about 12 hours of oxygen-containing gas at a temperature of from 20 to 600°C, mainly from 100 to 450°C and, more preferably, from 200 to 450°C. the Oxygen-containing gas may be pure oxygen, oxygen-enriched air (mainly containing from 25 to 70 vol.% oxygen), air (containing about 21 vol.% oxygen or air diluted with an inert gas, for example, N2. Oxygen-containing gas contains oxygen mainly in the amount of from 0.1 to 10 vol.% O2and, more preferably, from 0.3 to 5% vol. O2. In one embodiment, the implementation of the catalyst particle is subjected to an operation (partial) recovery phase (i) oxidation and before stage (ii) processing.

Without intending to be bound by any theory, I believe that used in stage (ii) the solvent dissolves a portion of the possibly present Co and CoO, as well as a small portion is present in the catalyst particle Co3O4.

Stage (ii) is carried out mainly at a temperature of from 5 to 90°C, more preferably at a temperature of from 40 to 70°C and, more preferably, at a temperature of from 50 to 60°C. In some applications it may be useful to increase the temperature during processing. The duration of the treatment stage (ii) can be adjusted in accordance with the temperature at which it is held. When the stage (ii) is carried out at relatively low the first temperature, for example from 35 to 40°C, the processing may be performed within a few days to several weeks. When the stage (ii) is carried out at a temperature from 50 to 60°C, for processing, you may need only about 4 hours. When the stage (ii) is carried out at relatively high temperatures, for example from 70 to 80°C, the solvent may begin to evaporate, which is less preferable.

Stage (i) oxidation stage (ii) processing stage (iii) drying and stage (iv) recovery carried out in situ in a tube reactor Fischer-Tropsch process. In one of the preferred embodiments the entire catalyst particle or all of the catalyst particles in the reactor tube are subjected to operations (i) oxidation and operations (iv) recovery.

All catalyst particle or all of the catalyst particles in the reactor tube may be subjected to operations (ii) processing. In an alternate operation, (ii) processing may be exposed portion of the catalyst particles (particles).

Substantially all of the catalyst particles in the reactor tube is subjected to an operation (ii) processing in the case where the reactor tube is a suspension catalyst, at least 90% of particles which have a size less than 1 mm, mostly less than 0.5 mm, Particularly preferably, when in the reactor tube is a suspension catalyst is, 100% of the particles had a size less than 1 mm, mostly less than 0.5 mm.

In the case when the reactor tube is one or more particles fixed catalyst layer or one or more particle suspension immobilized catalyst, mainly part of the catalyst particles (particles) in the reactor tube is subjected to an operation (ii) processing. This is particularly preferred when the particle or at least 30% of the particles have a size greater than 1 mm, Mostly 90% or less particles (particles) stationary layer or suspension immobilized catalyst is treated for more than 5 min the solvent, more preferably 85% or less, even more preferably 80% or less, even more preferably 65% or less and, most preferably 55% or less. Mainly 20% or more of particles (particles) stationary layer or suspension immobilized catalyst is treated for more than 5 min the solvent, more preferably 35% or more and, more preferably 45% or more.

In the case when the reactor tube is one or more catalyst particles fixed layer or one or more particles immobilized suspension of the catalyst, and part of the catalyst particles (particles) are subjected to an operation (ii) processing the portion of the catalyst particles (h is STIC) in the reactor tube, which is subjected to operations (ii) processing, is located on the output end of the pipe. The "input" or "output" is defined in the application in relation to the supplied stream of synthesis gas, i.e. the flow of the mixture of hydrogen and carbon monoxide in the reactor Fischer-Tropsch process. Mentioned here the input end of the catalyst particles (particles) is, thus, by the end of the particle (particles) of the catalyst during the reaction of the Fischer-Tropsch serves synthesis gas. Mentioned here the output end of the catalyst particles (particles) refers to the opposite end.

In one of the preferred embodiments is treated with 85% or less of the catalyst particles (particles), mostly 65% or less and, more preferably 55% or less, resulting in a portion of the catalyst particles (particles that are on the input end, is not subjected to operations (ii) processing or difficult is processed. Along with this, or alternatively, preferably, at least 20%, mostly at least 35%, even more preferably at least 45% of the catalyst particles (particles) were processed, resulting in a portion of the catalyst particles (particles that are in the output end, is subjected to an operation (ii) processing. In a particularly preferred embodiment, from 35 to 85% and, more preferably, from 45 to 65% ka is alistore particles (particles) is processed, resulting in part of the catalyst particles at the input end, is not subjected to operations (ii) processing or difficult it is treated as part of the catalyst particles (particles), located at the output end, is subjected to an operation (ii) processing.

In the case when the reactor tube are one or more particles fixed catalyst layer, stage (ii) processing is performed with the use of the method of filling the pores. The pores of the catalyst carrier particles (particles) are filled with solvent. The solvent can be filled in the pores of the whole particle or all of the particles in the pipe. In the case when any portion of catalyst particles (particles) are subjected to an operation (ii) processing, the pores of the part being treated, filled with solvent using the method of filling the pores.

Under the method of filling the pores imply the operation, in which the most part of the pores of the material of the carrier on the surface of one or more catalyst particles are filled with solvent, while the particle(s) in the solvent is not immersed.

The filling of the pores can be made by filling the solvent of the reactor tube in which the catalyst particle(s), up to a certain level with removal at a later stage of excess fluid. Excess liquid may, for example, methoden drain it from the bottom of the reactor tube. To accelerate the removal of excess fluid in the reactor tube mainly let the gas, preferably an inert gas, such as nitrogen. After removal of excess liquid solvent still remains in the pores of the catalyst particles.

In the case when the reactor tube are one or more immobilized suspension of particles, stage (ii) processing can be carried out using the method of filling the pores. Alternatively, during the operation (ii) processing all or part of the catalyst particles (particles) are fully immersed in the solvent. In this case the reactor tube in which is immobilized particle suspension (particles), filled up to a certain level of solvent and designed to handle part of the catalyst particles (particles) stand on stage (ii) processing immersed in the solvent.

In case of application of the method of pore filling stage (ii) processing may include two stages. At stage (ii)a pore catalyst particles (particles) are filled using the method of filling the pores. At stage (ii) (b solvent left in the pores for more than 5 minutes

At stage (ii)a filling of the pores can be produced, as described above, by filling the solvent of the reactor tube in which the catalyst particle(s), up to a certain level with deletion is observed at a later stage of excess fluid. The pores are filled at the stage (ii)a predominately at temperatures in the range from 5 to 40°C and, more preferably, at a temperature in the range from 15 to 30°C.

Stage (ii)b is carried out mainly at a temperature of from 5 to 90°C, more preferably at a temperature of from 40 to 70°C and, more preferably, from 50 to 60°C.

Stage (ii) processing is carried out mainly with the simultaneous removal of oxygen from the exposed processing catalyst particles (particles) or part thereof. Subjected to the processing of the catalyst particle(s) or part thereof is not in contact during the operation (ii) treatment with any containing oxidant gas.

In the case when the reactor tube are one or more immobilized suspension of particles, the reactor tube, in which the particle(s) suspension immobilized catalyst can be filled with solvent to a certain level and intended for treatment of the part may then be immersed in the solvent during the operation (ii) processing. Particle(s) of catalyst (or part of it), which is immersed in the solvent, isolated during the operation (ii) processing of oxygen. Particle(s) of catalyst (or part of it), which is immersed in the solvent, insulate well as during the operation (ii) processing of any containing oxidant gas.

In the case of application of the method of filling the pores of the one or more catalyst particles fixed layer or to one or more immobilized suspension of particles (or parts thereof) stage (ii) processing is carried out mainly by filling solvent reactor tube in which the catalyst particle(s), up to a certain level with removal at a later stage of excess fluid. The access of oxygen to the treated particle(s) of the catalyst or its (their) part can, for example, be removed by the flow in the reactor tube of inert gas, preferably nitrogen, when particles (particles) of the catalyst is performed to remove excess liquid. Inert gas, preferably nitrogen, is used primarily to remove excess fluid from the particles (particles) of the catalyst.

Stage (iii) drying can, for example, be performed with air or inert gas, preferably an inert gas. Drying can occur at room temperature or at elevated temperature. Along with this, or alternatively, the catalyst particle can be heated before, during and/or after drying. During the operation, (iii) drying the catalyst mainly subjected to the action of air or inert gas having a temperature of from 70 to 300°C, more preferably from 80 to 120°C and, even more predpochtitel is but from 85 to 95°C. During or after the operation (iii) drying the catalyst may be subjected to calcination.

According to another aspect of the present invention the method of the present invention is preceded by a stage in which the particles removes the product of the Fischer-Tropsch synthesis. In this case provides a method of regenerating one or more cobalt containing catalyst particles Fischer-Tropsch reactor Fischer-Tropsch, and this catalyst particle(s)was deactivated when using the Fischer-Tropsch process. The specified regeneration method involves the following stages:

(0) removing the product of the Fischer-Tropsch synthesis;

(i) oxidation catalyst particles (particles) at a temperature of from 20 to 400°C, mainly from 100 to 400°C and, more preferably, from 200 to 400°C;

(ii) treating the catalyst particle (particles) for more than 5 min with a solvent selected from the group consisting of: ethanol, acetic acid, Ethylenediamine, nitric acid, glycine, iminodiacetic acid, urea, sodium hydroxide, ammonium hydroxide, ammonium carbonate and mixtures thereof;

(iii) drying the particles (particles) of the catalyst; and

(iv) optionally recovering the particles (particles) of the catalyst with hydrogen or a hydrogen-containing gas.

All stages of this aspect of the invention is performed in the order listed. The method can include all the I additional stages. All stages of the method of the invention carried out in situ in the reactor tube. All stages of the method of the invention mainly carried out in situ in the same reactor tube in which the catalyst particle(s) have been deactivated as a result of use in the Fischer-Tropsch process.

The catalyst particle is treated with hydrogen gas or hydrogen-containing gas mixture, it is possible, after removal of the product of the Fischer-Tropsch synthesis stage (0). Such processing may be performed for several hours at elevated temperatures, for example within 15-30 hours at a temperature in the range from 220 to 300°C.

All stages and symptoms, including preferred and possible stages and characteristics described for the method of the present invention can be combined with the specified initial removal of particles (particles) of the catalyst product of the Fischer-Tropsch synthesis.

Stage (0), this aspect of the invention the product of the Fischer-Tropsch synthesis are removed in situ from the deactivated catalyst mainly in the reactor. This can be done by washing the catalyst with any hydrocarbon easier compared with the product of the Fischer-Tropsch synthesis. For example, heavy paraffin wax, Fischer-Tropsch process can be removed by washing the oil; the oil may be oil gas oil or, preferably, synthetic oil, is for example a gas oil, produced using the Fischer-Tropsch synthesis. After this stage (0) removal in the reactor tube is less than 30 grams of hydrocarbons per 100 g of the catalyst particles, preferably less than 10 g of hydrocarbons per 100 g of the catalyst particles and, most preferably, less than 5 grams of hydrocarbons per 100 g of the catalyst particles.

The present invention also proposed a regenerated catalyst, which can be obtained by the regeneration method of the present invention. In the present invention a method, including the use of the catalyst according to the invention in the process of the Fischer-Tropsch synthesis.

In the present work it was found that by using the method of the present invention the activity of the deactivated (spent) catalyst can be significantly increased.

Stage (stage) oxidation can be accomplished by treatment of the catalyst oxygen-containing gas at the above temperatures. Stage of recovery can be done by introducing the catalyst into contact with hydrogen or a hydrogen-containing gas, usually at temperatures of from about 200 to 350°C.

The catalyst for the Fischer-Tropsch or catalyst precursor contains a catalytically active metal or its predecessor, and possibly promoters supported on a carrier catalysis is ora. Catalyst carrier in this case mainly contains heat-resistant metal oxide, preferably aluminum oxide, silicon oxide, titanium oxide or mixtures thereof, most preferably the porous titanium oxide. Mostly, more than 70 wt.% the material of the carrier consists of a heat-resistant metal oxide, more preferably more than 80 wt.% and, most preferably more than 90 wt.% calculated on the total weight of the material medium. As an example of a suitable material of the carrier may be mentioned the sales of Titanium Dioxide P25 ex Evonik Industries.

The media may contain titanium oxide or any other heat-resistant oxide or a metal silicate, or combinations thereof. Examples of suitable materials of the carrier, which may be present in the catalyst along with the titanium oxide include silicon oxide, aluminum oxide, zirconium oxide, gallium oxide and mixtures thereof, in particular silicon oxide and aluminum oxide.

The catalytically active metal in the catalyst is cobalt. Cobalt can be added to the carrier in the form of, for example, cobalt hydroxide, CoOOH, cobalt oxide, precipitated together hydroxides of cobalt and manganese, nitrite cobalt or ammonium complex of cobalt, such as cobalt carbonate-ammonium. The catalyst may also include one or more additional components, such as promoters and/or the catalysts.

Suitable socializaton include one or more metals, such as iron and Nickel or one or more noble metals of groups 8-10 of the periodic table of elements. Preferred noble metals are platinum, palladium, rhodium, ruthenium, iridium and osmium. Such socializaton usually present in small amounts.

Mentioned in the application groups of the periodic table belong to the new IUPAC version of the periodic table of elements, which are described in the ' 89 edition of the Handbook of Chemistry and Physics (CRC Press).

Typically, the number contained in the catalyst is catalytically active metal can be from 1 to 100 parts per 100 parts of material media, mainly from 3 to 50 parts per 100 parts of the material medium.

The catalyst may also contain one or more promoters. As the promoters may be present one or more metals or metal oxides, more specifically one or more d-metals or oxides of d-metals. Suitable metal promoters can be selected from groups 2 to 7 of the periodic table of the elements or of the actinides and lanthanides. In particular, the most suitable promoters include oxides of magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, cerium, titanium, zirconium, hafnium, thorium, uranium, vanadium, chromium and manganese. Suitable metal is practical promoters can be selected from the group 7-10 of the periodic table of elements.

Particularly suitable as promoters are manganese, iron, rhenium and the noble metal of groups 8-10, which is primarily used in the form of a salt or hydroxide.

The promoter (if present in the catalyst) is usually contained in an amount of from 0.001 to 100 parts per 100 parts of material media, mainly from 0.05 to 20 and, more preferably, from 0.1 to 15 parts Should, however, be borne in mind that the optimum amount of promoter may vary for an individual acting in the capacity of promoter elements.

One of the particularly preferred catalysts for the Fischer-Tropsch contains manganese or vanadium promoter.

Being freshly prepared, the catalyst may be formed using spray drying, granulation, (wheel) pressing, extrusion or coating on a metal substrate (type of metal wire). The catalytically active metal and/or promoter can be added to the material of the carrier before or after molding.

In the case of particles fixed layer, for example, any cobalt compound, preferably cobalt hydroxide, CoOOH, cobalt oxide or co-precipitated hydroxides of cobalt and manganese, can be mixed with any refractory metal oxide with subsequent extrusion. Or heat-resistant metal oxide may be extruded, and the extrudates at a later stage can be impregnated with a compound of cobalt, mainly cobalt salt which is soluble in water and/or ethanol.

When the material of the carrier is subjected to molding, it may be useful to add a binder material, for example, to increase the mechanical strength of the catalyst or catalyst precursor. Along with this, or alternatively, before or during the molding of the material of the carrier may be added to any liquid. Such fluid may be any known in the art suitable liquid, such as water, ammonia, alcohols, such as methanol, ethanol and propanol; ketones, such as acetone; aldehydes, such as propanol; aromatic solvents such as toluene; and mixtures of the above liquids. The most convenient and preferred liquid is water. The liquid may contain improving the viscosity substances such as polyvinyl alcohol.

In the case of extrusion may be a desire to improve the characteristics of the yield strength of the material of the carrier. In this case, it is preferable to add one or more improves the fluidity agents, and/or extrusion additives prior to the extrusion process. In a number of suitable additives include fatty amines, Quaternary ammonium compounds, polyvinylpyridine, sulfoxonium, sulfonamide, postname and itaniemi compounds, alkylated aromatic compounds, acyclic is monocarbonate acid, fatty acids, sulfonated aromatic compounds, sulfates of alcohols, sulfates of atherosperma, sulfated fats and oils, salts of phosphonic acids, polyoxyethylene-alkyl phenols, polyoxyethylene-alcohols, polyoxyethylene-bonds alkylamines, polyoxyethylene-alkylamine, polyacrylamides, polyols and acetylene glycols. Preferred additives are sold under the factory trademarks of Nalco and Superfloc.

To obtain a solid extrudate prior to extrusion, it is preferable to add at least one compound acting as peptizyme agent for heat-resistant metal oxide. For example, before extrusion can be added peptizyme agent for titanium oxide. Suitable patiserie agents well known in the art and include basic and acidic compounds. Examples of basic compounds include ammonia, produce ammonia compounds, ammonium compounds and organic amines. In the event of a stage of annealing after forming such basic compounds during combustion are removed and the extrudates are not saved. This is desirable because such basic compounds may reduce the catalytic characteristics of the final product. Preferred basic compounds are organic amines or ammonium compounds. The most suitable organic the min is ethanolamine. Suitable acid patiserie agents include weak acids, for example formic acid, acetic acid, citric acid, oxalic acid and propionic acid.

In some cases, to create in the resulting extrudates macropores, before extrusion can be added consumable materials. Suitable consumable materials are widely known in the technique.

The total number of improving fluidity agents/extrusion additives, peptizyme agents and consumable materials in the extrudable material carrier, is mostly in the range from 0.1 to 20 wt.%, more preferably from 0.5 to 10 wt.% calculated on the total weight of the mixture.

After the molding material of the carrier, which may include additional components, can be hardened by annealing known in the art by the way. The temperature of annealing depends on the material used media. The titanium oxide mainly calcined at a temperature of from 350 to 700°C, more preferably from 400 to 650°C and even more preferably from 450 to 600°C. the stage of calcination is not, however, mandatory, especially in the case of the preparation of the catalyst Fischer-Tropsch containing titanium oxide and cobalt.

Activating a freshly prepared catalyst regardless of whether he Poroskov asnam suspension catalyst, the fixed catalyst layer or suspension immobilized catalyst, can be carried out by any known method and in any practice environment. For example, the catalyst can be activated by the introduction of it into contact with hydrogen or a hydrogen-containing gas, usually at temperatures of from about 200 to 350°C.

The catalyst, which was implemented method of the present invention has been deactivated as a result of its use in the Fischer-Tropsch process.

the Fischer-Tropsch process is well known to specialists in this field and includes the synthesis of hydrocarbons from synthesis gas by introducing the synthesis gas into contact with a catalyst for Fischer-Tropsch under the reaction conditions.

Synthesis gas can be obtained using any suitable means, method or device. For this purpose, the technique used partial oxidation and/or reforming coal-hydride materials. To regulate the relationship of H2/CO in the synthesis gas in a partial oxidation process you can enter the carbon dioxide and/or water vapor. A suitable ratio of H2/CO in the synthesis gas is from 1.5 to 2.3, mostly from 1.6 to 2.0.

Synthesis gas containing mainly hydrogen, carbon monoxide and possibly nitrogen, carbon dioxide and/or water vapor is introduced into contact with a suitable catalyst at a stage of catalytic is oversee, which are formed hydrocarbons. It is considered normal if the catalyst is in contact at least 70 vol.% synthesis gas, preferably at least 80%, more preferably at least 90% and, most preferably, the whole amount of the synthesis gas.

Sustainable process for catalytic synthesis of hydrocarbons can be carried out in known in the art, the traditional synthesis. Typically, the catalytic conversion can be performed at a temperature in the range from 100 to 600°C, mostly from 150 to 350°C, more preferably from 175 to 275°C and most preferably, from 200 to 260°C. Typical total pressure in the catalytic conversion process is in the range from 5 to 150 bar (abs) and, more preferably, from 5 to 80 bar (abs). In the process of catalytic conversion are formed mainlyC5+-hydrocarbons.

Appropriate mode for carrying out the Fischer-Tropsch process with a catalyst containing particles size of at least 1 mm is fixed layer, in particular an ink jet mode. The most suitable reactor is Novotrubny reactor with a fixed bed.

Experimental part

Method of measurement. Activity

Catalytic activity you can measure the e l e C for example, in the model reactor Fischer-Tropsch process. The measured catalytic activity can be expressed in volumetric time yield (STY) or by using factor activity, where the activity coefficient is equal to 1, corresponds to a volumetric temporary yield (STY)of 100 g/l·h at 200°C.

Sample preparation

Particles fixed layer were prepared as follows. Preparing a mixture containing a powder of titanium oxide, cobalt hydroxide, manganese hydroxide, water and a few extrusion additives. The mixture is kneaded and molded using an extrusion. The extrudates are dried and calcined. The catalyst (precursor) contains about 20 wt.% cobalt and about 1 wt.% manganese.

The catalyst used in the Fischer-Tropsch process for a number of years. Then the product of the Fischer-Tropsch removed from the deactivated (spent) catalyst using gasoil obtained in the Fischer-Tropsch process. In the next stage of the deactivated catalyst was processed within a few hours the hydrogen-containing gas at elevated temperature. The deactivated catalyst was oxidized in a single day in situ in the reactor at a temperature of 270°C. thereafter, the reactor was unloaded, receiving samples of the deactivated catalyst particles.

During unloading were collected portions from various areas in the reactor tubes. Some of these samples have not been processed in accordance with the present invention (comparative examples). Several samples were taken from the far end of the reactor tubes and processed according to the invention (examples 1 and 2). In examples 3 and 4 were used samples from different sites in the reactor tubes.

For each series of examples (comparative experiments and experiences with treatment) samples were collected from the same party.

Comparative example 1

The raw sample is described under the heading "sample preparation".

The treated sample 1

Prepared as described above, the sample deactivated particles fixed layer were processed using the method of filling the pores. Particles in the solution were not loaded.

The sample was treated with a mixture of ammonium carbonate, ammonium hydroxide and water using the method of filling the pores. Particles filled then left overnight at room temperature. At the next stage, the temperature was raised to about 50°C and left at this temperature for about 4 hours. After this stage the temperature was raised in a stream of air to about 300°C and left at this temperature for 2 hours.

Measurement of activity.

Example 1 and comparative example 1

The sample of comparative example 1 and the sample of example 1 with the processing of recovered Bogorodsk is containing a series of gas and then measured the activity of the samples. Measurement of the activity was performed using the reaction of the Fischer-Tropsch process at a temperature of 225°C and total pressure of 60 bar (abs). The measurement results are shown in table 1.

Table 1
The temperature oxidation stage (i)Processing stage (ii)Relative activity
Example 1270°CAmmonium carbonate and ammonium hydroxide250%
Comparative example 1270°C-100%

The results clearly indicate that the catalyst is treated with a mixture of ammonium carbonate, ammonium hydroxide and water, shows a higher activity in the Fischer-Tropsch process than the untreated catalyst.

Comparative example 2

The raw sample is described under the heading "sample preparation".

The treated sample 2

To a solution of ammonium carbonate in water solution was added ammonia. Made of different mixtures with different concentrations. Samples deactivated particles fixed layer handling the Ali these mixtures using the method of filling the pores. Particles in the solution were not loaded.

Measurement activity. Example 2 and comparative example 2

The sample of comparative example 2 and a few samples from example 2 with the processing of recovered hydrogen-rich recycle gas and then measured the activity of the samples. Measurement of the activity was performed using the reaction of the Fischer-Tropsch process at a temperature of 225°C and total pressure of 60 bar (abs). The measurement results are shown in table 2.

Table 2
The temperature oxidation stage (i)The composition of the mixture at the stage of processing (ii)Relative activity
NH4OH(NH4)2CO3H2O
Example 2a270 C211529%
Example 2b270 C112522%
Example 2c 270 C1,435497%
Example 2d270 C0,512,5460%
Comparative example 2270 C-100%

Measurement of solubility of cobalt. Example 2

Tests were conducted to determine the amount of cobalt, which is soluble in obrabotannykh solutions at 20°C.

Samples deactivated particles fixed layer, described under the heading "preparation of the sample, were tested for solubility of cobalt. 0.5 g of the deactivated particles of the fixed layer of each sample was added to 1 ml of a solution of ammonium hydroxide, ammonium carbonate and water. Particles are kept in solution at 20°C. Samples of these solutions were taken after 4 or 6 hours and diluted with 1 M solution of nitric acid.

The amount of dissolved cobalt was determined using the induced plasma (ICP) coupled with atomic emission spectroscopy (AES).

The amount of dissolved cobalt in the calculation of the total number present in the particles of cobalt is provided in table 3.

Table 3
The temperature oxidation stage (i)The composition of the mixture in the test for solubility of cobaltThe amount of dissolved Co (wt.%)
NH4OH(NH4)2CO3H2O
Example 2e270°C21121 (6 hours)
Example 2f270°C1125 (4 hours)
Example 2g270°C1,4350,9 (4 hours)
Example 2h270°C0,512.52 (4 hours)

The conclusions. Example 2

From the above in that the faces 2 and 3 result clear, that treatment leads to high activity in the Fischer-Tropsch process. In addition, it was found that the processing solution containing a small amount of ammonium hydroxide, as compared with ammonium carbonate and water, leads to a relatively small amount of dissolved cobalt at 20°C.

In the process of the invention, the filling of pores can be achieved in situ by filling the solvent of the reactor tube, in which the particle(s) of the catalyst, to a certain extent with the destruction, at a subsequent stage of excess fluid. The number of removed from the reactor cobalt when removing excess fluid should be minimal.

Thus, when implementing the method of the invention using a solution containing ammonium hydroxide, ammonium carbonate and water, for some embodiments it is preferable to fill the pores in situ in the reactor at a relatively low temperature using a solution containing a small amount of ammonium hydroxide in comparison with ammonium carbonate and water, resulting in a number of cobalt, washed out at the stage of filling of the pores is minimal. After filling the pores and remove excess fluid temperature can be raised.

Example 3

The samples taken from different sites in the reactor tubes (see "Preparation of which were acquired"), were used to load the test tubes. Deactivated particles fixed layer, which were taken from the top of the reactor, were placed in the tops of these test tubes. Deactivated particles fixed layer, which were taken from the bottom of the reactor, were placed in the bottom of these test tubes.

Comparative example 3

Some of the test tubes were left untreated.

Example 3 processing

Some of the test tubes were subjected to treatment. Was processed by the lower half of the catalyst layer in the test tube.

Catalyst layer filled within one hour from the lower end until the middle of the mixture of ammonium carbonate, ammonium hydroxide and water (2:1:1) at room temperature. The excess fluid is drained, after which the layer for two minutes, rinsed with nitrogen. This reach by filling the pores.

After 2 hours, raise the temperature to 50°C and can withstand the catalyst filled pores at 50°C for 4 h.

Further, the catalyst layer is dried, pass a stream of nitrogen, increase the temperature to 90°C and leave the layer at 90°C during the night.

In a subsequent step, the temperature increase in air flow to about 300°C and maintain this temperature for 6 hours.

Measurement activity. Example 3 and comparative example 3

Test tubes of the comparative example 3 and the test tube of example 3 with the processing of recovered hydrogen-rich recycle gas and then determined the activity. Measurement of the activity was performed using the reaction of the Fischer-Tropsch when the total pressure of approximately 60 bar (abs). The measurement results are shown in table 4.

Table 4
Relative activityC5+(wt.%)CO2(%)
Example 3184%of 87.81,5
Comparative example 3100%84,3the 3.8

From the obtained results it is clear that the treatment of the deactivated particles of the lower half of the fixed catalyst layer with a mixture of ammonium carbonate, ammonium hydroxide and water in the reactor tube leads to higher activity in the Fischer-Tropsch process compared with untreated deactivated particles fixed catalyst layer. In addition, increased selectivity forC5+and snigees the selectivity for CO 2.

Example 4

Samples from different sites in the reactor are treated the same way as described under Example 1 with the treatment." After that, the samples recover the hydrogen-rich recycle gas and determine the activity in the reaction of the Fischer-Tropsch process at a temperature of 225°C and total pressure of 60 bar (abs).

Samples from the input side of the reactor, in particular the samples taken near the input of the synthesis gas, found no increased activity after treatment according to the invention.

The samples taken in the middle of the reactor tube, found increased activity.

Samples from the output part was found strongly increased activity in the processing according to the invention.

From the series of these experiments it is concluded that treatment of the particles fixed layer in situ according to the present invention is very effective when applied on the particles of the output end, which in this example is the lower end of the particle at a height corresponding to approximately 85% of the height of the fixed layer.

Another possibility is to conduct processing on the particles at the output end to the middle of the fixed layer. This requires less solvent and the result, however, is the strong increase in the activity of the catalyst layer.

1. Method of regenerating one or more particles of cobalt containing cat who lyst Fischer-Tropsch in situin the reactor tube after deaktivirovana particles of the catalyst used in the Fischer-Tropsch process, which includes stages:
(i) oxidation of the particle(s) of the catalyst at a temperature of from 20 to 400°C;
(ii) processing of the particle(s) catalyst for more than 5 min solvent that contains one or more chemical compounds selected from the group consisting of nitric acid, a weak organic acids, ammonium salts and alkylammonium salts;
(iii) drying and optionally heating the particle(s) of the catalyst;
moreover, the processing stage (ii) includes the following operations on them:
(ii)a pore catalyst particles (particles) are filled with solvent at a temperature in the range from 15 to 30°C using the method of pore filling by filling solvent reactor tube in which the catalyst particle(s), up to a certain level with removal at a later stage of excess fluid;
(ii)b solvent left in the pores for more than 5 minutes at a temperature of from 40 to 70°C;
and all the stages of this method are executed in the order they are listed.

2. The method according to claim 1, characterized in that the catalyst particles(a) are particles of the stationary layer is larger than 1 mm or particles immobilized suspension larger than 1 mm, and 85% or less of the catalyst particle(s)processed, and part of the catalyst particle(s)located at the input end, is not subjected to operations (ii) processing or subjected to operations (ii) processing in a small degree.

3. The method according to claim 1, characterized in that the processing is subjected to at least 20% of the particle(s) of the catalyst and operations (ii) processing is subjected particles(at) catalyst located at the output end.

4. The method according to claim 1, characterized in that the particle(s) of the catalyst at least partially restore the hydrogen or hydrogen-rich recycle gas after stage (i) oxidation and before stage (ii) processing.

5. The method according to claim 1, characterized in that stage (i) is preceded by a stage in which the product of the Fischer-Tropsch synthesis are removed from the particle(s) catalyst for Fischer-Tropsch by washing of the particle(s) of the catalyst oil gas oil or a synthetic oil.

6. The method according to claim 1, characterized in that is used in stage (ii) a solvent containing one or more chemical compounds selected from the group consisting of nitric acid, a weak organic acids, ammonium salts and alkylammonium salts, further comprises ammonia and/or ammonium hydroxide, and/or Ethylenediamine, and/or urea.

7. The method according to claim 1, characterized in that is used in stage (ii) the solvent contains glycine, ammonium carbonate, a mixture of glycine with ethylendiamine is, a mixture of glycine with ammonium hydroxide or a mixture of ammonium carbonate with ammonium hydroxide.

8. The method according to claim 1, characterized in that is used in stage (ii) the solvent further comprises water.

9. The method according to claim 1, characterized in that is used in stage (ii) the solvent comprises a mixture of ammonium carbonate, ammonium hydroxide and water.

10. The method according to claim 1, characterized in that is used in stage (ii) the solvent comprises a mixture of ammonium carbonate, ammonium hydroxide and water
when the weight ratio of ammonium hydroxide to ammonium carbonate in the range from 1:0.25 to 1:2,
when the weight ratio of ammonium carbonate to water in the range from 1:0.5 to 1:4, and
when the weight ratio of ammonium hydroxide to water in the range from 1:0.25 to 1:4.



 

Same patents:

Catalysts // 2517700

FIELD: chemistry.

SUBSTANCE: invention relates to catalysis. Described are methods of preparing a catalyst precursor, the first preparation step of which involves impregnating catalyst support particles with an organic cobalt compound in an impregnating liquid to form an impregnated intermediate product, calcining the impregnated intermediate product at calcination temperature not higher than 400°C to obtain a calcined intermediate product; and the second preparation step of which involves impregnating the calcined intermediate product from the first step with an inorganic cobalt salt in an impregnating liquid to form an impregnated support and calcining the impregnated support to obtain a catalyst precursor, wherein neither of the inorganic cobalt salts used at the second preparation step is used at the first preparation step. Described is synthesis of hydrocarbons in the presence of catalysts obtained using said method.

EFFECT: high catalyst activity.

20 cl, 5 tbl, 11 ex

FIELD: process engineering.

SUBSTANCE: invention relates to moulded catalyst blocks, method of their production and method of catalyst loading into reactor. Catalyst block to be loaded in tube comprises multiple catalyst Fischer-Tropsh particles containing one or several reducible metals selected from Co or Fe in oxide or reduced form located in removal female die from wax or polymer. Said block features elongated shape wherein particles are filled so that volumetric shrinkage after female die removal makes ≤20%.

EFFECT: homogeneous catalyst block, higher packing density.

16 cl, 3 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing hydrocarbon gasoline fractions from synthesis gas, having volume ratio H2/(CO+CO2) of 1-3, by contacting, at temperature of 360-440°C and pressure of 100 atm, with a bifunctioanal catalyst containing a ZSM-5 or ZSM-11 zeolite which contains 0.1-1 wt % iron, and a metal oxide component consisting of Zn, Cr and W oxides, wherein content of N2 in the synthesis gas ranges from more than 10 to 20 vol. % and content of CO2 ranges from 1 to 15 vol. %. Wherein total content of N2 and CO2 in the synthesis gas is not more than 30 vol. %, and the volume ratio of components (H2-CO2)/(CO+CO2) is in the range of 1.7-2.3, and the process of converting synthesis gas is carried out with not less than 15 circulations. The invention also relates to a method where a stream of synthesis gas, having volume ratio of components (H2-CO2)/(CO+CO2) less than 1.7, with content of N2 from 20 to 30 vol. % and content of CO2 from 1 to 15 vol. %, is divided into two streams, followed by separating H2 from the first stream and adding to the second stream in an amount which enables to lower content of N2 in the second stream to concentration lower than 20 vol. % and increase volume ratio of components (H2-CO2)/(CO+CO2) in the second stream to 1.7-2.3, which is then fed for contacting with the bifunctional catalyst with not less than 15 circulations, wherein the first stream is taken for burning after separating H2.

EFFECT: obtaining gasoline fractions with low concentration of benzene, high selectivity on C5 hydrocarbons and methane.

3 cl, 1 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: described is a Fischer-Tropsch synthesis method where: raw gas containing CO and H2, obtained from coal gasification, is desulphurised and then fed as starting gas into a Fischer-Tropsch synthesis apparatus (3) in which hydrocarbons are formed via catalytic reactions from carbon monoxide and hydrogen, wherein the hydrocarbons are removed in form of liquid products (4), a gas stream containing CO and CO2, coming out of the Fischer-Tropsch synthesis apparatus (3) is compressed and fed into a conversion area (6) in which CO is converted with steam to H2 and CO2 and gas coming out of the conversion area (6) after purification (9, 14), from which CO2 and/or other components except H2 are removed, is fed back as gas with high content of H2 together with the desulphurised starting gas into the Fischer-Tropsch synthesis apparatus (3), characterised by that a partial stream (8) of the desulphurised starting gas is removed and fed before a compressor (5) into a loop with a circulation gas stream and that in the gas stream fed into the Fischer-Tropsch synthesis apparatus (3), molar ratio of H2 to CO is set at least equal to 1.5:1. Also described is an installation for carrying out said method, said installation comprising: a Fischer-Tropsch synthesis apparatus (3) with a reactor and an apparatus for separating liquid products, a pre-switched on apparatus (2) for desulphuration of raw gas containing CO and H2, which is formed during coal gasification (1), an apparatus for returning the gas stream coming from the Fischer-Tropsch synthesis apparatus (3) into the desulphurised starting gas, fed into the Fischer-Tropsch synthesis apparatus (3), wherein the apparatus for returning the gas stream has a compressor (5) which operates on steam from a converter (6) for converting CO to H2 and CO2 and an apparatus (9, 14) for removing CO2 from the circulating gas stream, characterised by that the apparatus for returning the gas stream is linked to with a main line for feeding desulphurised starting gas through a branching line (8), wherein the branching line (8) is connected before the compressor (5) in the direction of flow with the returning apparatus, and that in the gas stream fed into the Fischer-Tropsch synthesis apparatus (3), molar ratio of H2 to CO can be at least 1.5:1.

EFFECT: high output of the product without considerably increasing the cost of the equipment.

10 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to methods of obtaining catalyst precursor, catalyst of Fischer-Tropsch synthesis and to method of Fischer-Tropsch synthesis itself. Method of obtaining precursor of catalyst of Fischer-Tropsch synthesis includes stages at which: (i) Fe (II) carboxilate solution is used, (ii) if molar ratio of carboxyl and carboxylate groups, which come into reaction or are capable of coming into reaction with iron, and Fe (II) in solution, used at stage (i), does not constitute, at least, 3:1, source of carboxyl or carboxilate group is added into the solution, for said molar ratio to constitute, at least, 3:1, until Fe (II) carboxylate oxidation is over at the following stage (iii), (iii) Fe (II) carboxylate is processed by oxidant to convert it into Fe (III) carboxilate solution in conditions, which exclude such oxidation simultaneously with dissolution of Fe(0), (iv) hydrolysis of Fe(III) carboxylate, obtained at stage (iii) and precipitation of one or several products of F(III) hydrolysis are carried out, (v) one or several products of hydrolysis, obtained at stage (iv) are reduced, and (vi) source of activator in form of soluble salt of transition metal and chemical activator in form of soluble salt of alkaline metal or alkaline-earth metal are added in the process pr after realisation of any of preceding stages to obtain precursor of catalyst of Fischer-Tropsch synthesis.

EFFECT: achievement of complete dissolution of Fe(0) in acidic solution, source of activator can be introduced before Fe(III) carboxylate hydrolysis.

15 cl, 7 dwg, 1 tbl, 14 ex

FIELD: chemistry.

SUBSTANCE: method involves: (a) carrying out an endothermic gasification reaction with a biomass reactant at a temperature lower than or equal to about 750 K, to yield synthesis gas, wherein the temperature is optimum for the synthesis gas recycling reaction or for the carbon-carbon forming reaction; (b) carrying out an exothermic synthesis gas recycling reaction or carbon-carbon bond forming reaction with the synthesis gas from step (a) without any intermediate treatment of the synthesis gas from step (a) at a temperature higher than or equal to the temperature of the gasification reaction carried out at step (a), wherein the reaction produces C2-C36 linear or branched hydrocarbons or oxygen-containing hydrocarbons, and heat; and (c) using the heat generated from the synthesis gas recycling reaction or carbon-carbon bond forming reaction of step (b) in the endothermic gasification reaction of step (a).

EFFECT: use of the invention provides an energy-efficient way of producing fuel and chemicals from renewable biomass resources.

17 cl, 19 tbl, 8 ex, 7 dwg

FIELD: chemistry.

SUBSTANCE: in method applied is catalyst of hydrocracking/hydroisomerisation, which contains hydrogenation-dehydrogenation metal, selected from group, formed from metals of VIB group and group VIII of periodic table of elements, and substrate, which contains, at least, one crystalline solid IZM-2. Chemical composition of IZM-2, expressed in moles of oxides, in water-free condition corresponds to general formula: XO2:aY2O3:bM2/nO, where X stands for, at least, one trivalent element, and M is, at least, one alkaline and/or alkaline-earth metal with n valence, and a and b stand for, respectively, number of moles of Y2O3 and M2/nO, and a constitutes from 0 to 0.5, and b constitutes from 0 to 1.

EFFECT: invention makes it possible to increase quantity of available middle distillates.

16 cl, 5 dwg, 3 tbl, 3 ex

Catalysts // 2497590

FIELD: chemistry.

SUBSTANCE: invention relates to catalyst regeneration. Method of regeneration of waste powder-like, paraffin-containing catalyst of Fischer-Tropsch synthesis based on cobalt is described, where claimed method includes the following sequential processing: (i) de-waxing processing, (ii) oxidative processing with regulation of work temperature by discharge of heat from layer of catalyst particles with application of cooling device, which contains device for providing passage of cooling medium and cooling medium, passing through said device of passage providing, which ensure in such way heat conductive surfaces, located in and/or around catalyst layer, with obtaining oxidised particles of catalyst, and (iii) reduction processing. Re-application of regenerative catalyst is described.

EFFECT: increase of process efficiency.

15 cl, 9 dwg, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to production of a liquid hydrocarbon product (1) from a solid biomass (2). According to the invention, the method of producing a liquid hydrocarbon product (1) from a solid biomass (2) involves: gasifying solid biomass (2) in a gasifier (6) to produce raw synthesis gas (3); preparing the raw synthesis gas (3) to purify the raw synthesis gas (3) to obtain purified synthesis gas (4), the preparation involving lowering the temperature of the raw synthesis gas (3) in a cooler (19) to obtain saturated steam (51); subjecting the purified gas (4) to a Fischer-Tropsch synthesis in a Fischer-Tropsch reactor (5) to obtain a liquid hydrocarbon product (1); treatment of the product (32) to separate the liquid hydrocarbon product (1), obtained from Fischer-Tropsch synthesis, also involves superheating the saturated steam (51) produced by the cooler (19) in a superheating boiler (50) for producing superheated steam (52, 53) by feeding saturated steam (51) into the superheating boiler (50) before using said saturated steam (51); the superheating boiler (50) operates almost exclusively with one or more by-products (9, 49, 48, 47) obtained in the method of producing a liquid hydrocarbon product (1) from solid biomass (2). Disclosed also is an apparatus for producing a liquid hydrocarbon product from biomass.

EFFECT: high energy efficiency of the method and apparatus for producing a liquid hydrocarbon product from biomass.

30 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to an integrated method, in which pure iron carbonyl powder is prepared by decomposition of pure iron pentacarbonyl in a plant A, and carbon monoxide (CO) liberated during decomposition of iron pentacarbonyl is used in plant A for further preparation of iron carbonyl powder from iron or is fed into a connected plant B for preparation of synthesis gas or is fed into a connected plant C for preparation of hydrocarbons from synthesis gas. The iron carbonyl powder prepared in plant A is used as catalyst or catalyst component in the connected plant C for preparation of hydrocarbons from synthesis gas from plant B, and spent catalyst obtained in plant C is used as additional iron source for preparation iron carbonyl powder in plant A.

EFFECT: use of the disclosed method enables to avoid wastes such as salts or waste water.

11 cl, 4 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing methanol, dimethyl ether and low-carbon olefin from synthesis gas. The method includes a step of contacting synthesis gas with a catalyst under conditions for converting the synthesis gas into methanol, dimethyl ether, and low-carbon olefins, characterised, wherein the catalyst contains an amorphous alloy consisting of components M-P, M-B or M-B-P, wherein component M represents two or more elements selected from lanthanides and the third, fourth and fifth series of groups IIIA, IVA, VA, IB, IIB, IVB, VB, VIB, VIIB and VIII of the Periodic Table of Elements.

EFFECT: method increases selectivity of the target product by conducting the process in conditions which ensure high conversion of CO and availability of carbon.

16 cl, 3 dwg, 3 tbl, 11 ex

Catalysts // 2517700

FIELD: chemistry.

SUBSTANCE: invention relates to catalysis. Described are methods of preparing a catalyst precursor, the first preparation step of which involves impregnating catalyst support particles with an organic cobalt compound in an impregnating liquid to form an impregnated intermediate product, calcining the impregnated intermediate product at calcination temperature not higher than 400°C to obtain a calcined intermediate product; and the second preparation step of which involves impregnating the calcined intermediate product from the first step with an inorganic cobalt salt in an impregnating liquid to form an impregnated support and calcining the impregnated support to obtain a catalyst precursor, wherein neither of the inorganic cobalt salts used at the second preparation step is used at the first preparation step. Described is synthesis of hydrocarbons in the presence of catalysts obtained using said method.

EFFECT: high catalyst activity.

20 cl, 5 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: claimed invention provides process of production of methanol, dimethyl ether as main products and low-carbon olefin as byproduct from synthesis gas, in which said process contains stage of contact of synthesis-gas with catalyst. Catalyst contains amorphous alloy, consisting of first component A1 and second component, with second component representing one or several elements or their oxides, selected from group IA, IIIA, IVA, VA, IB, IIB, IVB, VB, VIB, VIIB, VIII and a series of lanthanides of periodic table of elements, and said second component is different from first component A1. Conditions for conversion have reaction temperature 200-270°C, reaction pressure 1-6 MPa, volume rate of synthesis-gas supply 1000-10000 ml/g·hour and molar ratio between H2 and CO in synthesis-gas from 1 to 3.

EFFECT: in accordance with said process synthesis-gas can be converted into methanol, dimethyl ether and low-carbon olefin with high degree of CO conversion, high selectivity of target product and high availability of carbon.

19 cl, 3 dwg, 3 tbl, 14 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing hydrocarbon gasoline fractions from synthesis gas, having volume ratio H2/(CO+CO2) of 1-3, by contacting, at temperature of 360-440°C and pressure of 100 atm, with a bifunctioanal catalyst containing a ZSM-5 or ZSM-11 zeolite which contains 0.1-1 wt % iron, and a metal oxide component consisting of Zn, Cr and W oxides, wherein content of N2 in the synthesis gas ranges from more than 10 to 20 vol. % and content of CO2 ranges from 1 to 15 vol. %. Wherein total content of N2 and CO2 in the synthesis gas is not more than 30 vol. %, and the volume ratio of components (H2-CO2)/(CO+CO2) is in the range of 1.7-2.3, and the process of converting synthesis gas is carried out with not less than 15 circulations. The invention also relates to a method where a stream of synthesis gas, having volume ratio of components (H2-CO2)/(CO+CO2) less than 1.7, with content of N2 from 20 to 30 vol. % and content of CO2 from 1 to 15 vol. %, is divided into two streams, followed by separating H2 from the first stream and adding to the second stream in an amount which enables to lower content of N2 in the second stream to concentration lower than 20 vol. % and increase volume ratio of components (H2-CO2)/(CO+CO2) in the second stream to 1.7-2.3, which is then fed for contacting with the bifunctional catalyst with not less than 15 circulations, wherein the first stream is taken for burning after separating H2.

EFFECT: obtaining gasoline fractions with low concentration of benzene, high selectivity on C5 hydrocarbons and methane.

3 cl, 1 tbl, 6 ex

FIELD: process engineering.

SUBSTANCE: this invention relates to production of hydrogen-bearing gas and can be used in processing of Fischer-Tropsh process waste products in the presence of porous membrane-catalytic system. Porous catalytic membrane is produced by vibratory compaction of fine mix containing nickel and cobalt at 1:1 ratio and treated in muffle furnace at spontaneous ignition temperature, then cured and cooled. Invention covers also the process of processing Fischer-Tropsh process waste products. Proposed method comprises processing methane, carbonic acid and organic substances diluted in water (methanol, ethanol, methyl ethyl ketone, acetic acid and acetone) by carbonic acid-steam conversion in the presence of said catalytic module at 680-780°C, 1-1.5 atm and the rate of feeding the initial steam-gas mix along with water steam released in the process, 16000-96000 p-1 to obtain conversion products, that is synthesis gas and water cleaned of organic substance impurities.

EFFECT: efficient process, higher yield of valuable hydrocarbons.

4 cl, 1 dwg, 4 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: described is a Fischer-Tropsch synthesis method where: raw gas containing CO and H2, obtained from coal gasification, is desulphurised and then fed as starting gas into a Fischer-Tropsch synthesis apparatus (3) in which hydrocarbons are formed via catalytic reactions from carbon monoxide and hydrogen, wherein the hydrocarbons are removed in form of liquid products (4), a gas stream containing CO and CO2, coming out of the Fischer-Tropsch synthesis apparatus (3) is compressed and fed into a conversion area (6) in which CO is converted with steam to H2 and CO2 and gas coming out of the conversion area (6) after purification (9, 14), from which CO2 and/or other components except H2 are removed, is fed back as gas with high content of H2 together with the desulphurised starting gas into the Fischer-Tropsch synthesis apparatus (3), characterised by that a partial stream (8) of the desulphurised starting gas is removed and fed before a compressor (5) into a loop with a circulation gas stream and that in the gas stream fed into the Fischer-Tropsch synthesis apparatus (3), molar ratio of H2 to CO is set at least equal to 1.5:1. Also described is an installation for carrying out said method, said installation comprising: a Fischer-Tropsch synthesis apparatus (3) with a reactor and an apparatus for separating liquid products, a pre-switched on apparatus (2) for desulphuration of raw gas containing CO and H2, which is formed during coal gasification (1), an apparatus for returning the gas stream coming from the Fischer-Tropsch synthesis apparatus (3) into the desulphurised starting gas, fed into the Fischer-Tropsch synthesis apparatus (3), wherein the apparatus for returning the gas stream has a compressor (5) which operates on steam from a converter (6) for converting CO to H2 and CO2 and an apparatus (9, 14) for removing CO2 from the circulating gas stream, characterised by that the apparatus for returning the gas stream is linked to with a main line for feeding desulphurised starting gas through a branching line (8), wherein the branching line (8) is connected before the compressor (5) in the direction of flow with the returning apparatus, and that in the gas stream fed into the Fischer-Tropsch synthesis apparatus (3), molar ratio of H2 to CO can be at least 1.5:1.

EFFECT: high output of the product without considerably increasing the cost of the equipment.

10 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to methods of obtaining catalyst precursor, catalyst of Fischer-Tropsch synthesis and to method of Fischer-Tropsch synthesis itself. Method of obtaining precursor of catalyst of Fischer-Tropsch synthesis includes stages at which: (i) Fe (II) carboxilate solution is used, (ii) if molar ratio of carboxyl and carboxylate groups, which come into reaction or are capable of coming into reaction with iron, and Fe (II) in solution, used at stage (i), does not constitute, at least, 3:1, source of carboxyl or carboxilate group is added into the solution, for said molar ratio to constitute, at least, 3:1, until Fe (II) carboxylate oxidation is over at the following stage (iii), (iii) Fe (II) carboxylate is processed by oxidant to convert it into Fe (III) carboxilate solution in conditions, which exclude such oxidation simultaneously with dissolution of Fe(0), (iv) hydrolysis of Fe(III) carboxylate, obtained at stage (iii) and precipitation of one or several products of F(III) hydrolysis are carried out, (v) one or several products of hydrolysis, obtained at stage (iv) are reduced, and (vi) source of activator in form of soluble salt of transition metal and chemical activator in form of soluble salt of alkaline metal or alkaline-earth metal are added in the process pr after realisation of any of preceding stages to obtain precursor of catalyst of Fischer-Tropsch synthesis.

EFFECT: achievement of complete dissolution of Fe(0) in acidic solution, source of activator can be introduced before Fe(III) carboxylate hydrolysis.

15 cl, 7 dwg, 1 tbl, 14 ex

FIELD: chemistry.

SUBSTANCE: invention relates to production of Fischer-Tropsh synthesis oxide cobalt-zinc catalyst. Proposed method comprises making of aqueous dispersion of zinc oxide powder in reactor, adding of cobalt salt water solution and deposition of cobalt from said solution to zinc oxide by addition of ammonium carbonate. Besides, this invention relates to catalyst produced by above described method, and to its application.

EFFECT: decreased amount of used nitrate-anions and ammonium, ruled out use of zinc nitrate.

11 cl, 3 ex

Catalysts // 2497590

FIELD: chemistry.

SUBSTANCE: invention relates to catalyst regeneration. Method of regeneration of waste powder-like, paraffin-containing catalyst of Fischer-Tropsch synthesis based on cobalt is described, where claimed method includes the following sequential processing: (i) de-waxing processing, (ii) oxidative processing with regulation of work temperature by discharge of heat from layer of catalyst particles with application of cooling device, which contains device for providing passage of cooling medium and cooling medium, passing through said device of passage providing, which ensure in such way heat conductive surfaces, located in and/or around catalyst layer, with obtaining oxidised particles of catalyst, and (iii) reduction processing. Re-application of regenerative catalyst is described.

EFFECT: increase of process efficiency.

15 cl, 9 dwg, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an integrated method, in which pure iron carbonyl powder is prepared by decomposition of pure iron pentacarbonyl in a plant A, and carbon monoxide (CO) liberated during decomposition of iron pentacarbonyl is used in plant A for further preparation of iron carbonyl powder from iron or is fed into a connected plant B for preparation of synthesis gas or is fed into a connected plant C for preparation of hydrocarbons from synthesis gas. The iron carbonyl powder prepared in plant A is used as catalyst or catalyst component in the connected plant C for preparation of hydrocarbons from synthesis gas from plant B, and spent catalyst obtained in plant C is used as additional iron source for preparation iron carbonyl powder in plant A.

EFFECT: use of the disclosed method enables to avoid wastes such as salts or waste water.

11 cl, 4 dwg

FIELD: chemistry.

SUBSTANCE: described is method of regenerating catalyst of processing waste gases, which contains ash adhering to its surface, including stages of used catalyst crushing, stage of separation of crushed parts, stage of grinding, stage of formation, stage of annealing, stage of suspension application of coating for application on formed surface of base and stage of coating annealing for annealing of base, which has coating from suspension liquid, at temperature, higher than temperature of annealing in the process of obtaining crushed re-obtained catalyst of processing waste gases, with threshold size S at the stage of separation has value not lower than 0.105 mm.

EFFECT: obtaining regenerated catalyst, possessing high strength and wear resistance.

11 cl, 3 dwg, 3 tbl, 3 ex

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