Method of water cleaning at stage of hydrocarbons synthesis during gtl process, and method of its use
FIELD: oil and gas industry.
SUBSTANCE: invention can be used during HCs production from natural or associated petroleum gas. Method of oxygenates cleaning from reaction water generated at stage of HCs synthesis from syngas during GTL process includes conversion of even part of the contained oxygenates under conditions of syngas chilling by even part of the reaction water at temperature over 500°C upon contact with catalyst of the oxygenates steam conversion. Further syngas cooling temperature below 400°C is performed by the cleaned water injection in the syngas flow. Method of use of the reaction water generated at stage of HCs synthesis from syngas during GTL process includes its cleaning of the oxygenates under conditions of the syngas chilling at temperature over 500°C upon contact with catalyst of the oxygenates steam conversion, cleaned water degassing. The cleaned degassed water is used to cool the syngas to temperature below 400°C and produce the water steam.
EFFECT: invention ensures effective cleaning of the reaction water of the oxygenates, and use of the produced cleaned water as feed water for boilers and water steam production.
The invention relates to the preparation of hydrocarbons from natural or associated petroleum gas processes using Fischer-Tropsch or MTG process (conversion of methanol to gasoline) or TIGAS (conversion of a mixture of dimethyl ether/methanol to gasoline), in particular, ways of using the water produced at the stage of synthesis of hydrocarbons from synthesis gas, methanol or dimethyl ether.
In recent decades, the attention of researchers and investors are attracted to the process of producing liquid hydrocarbons from natural gas and associated gas, the so-called GTL processes, as an alternative source of liquid fuels, oils and raw materials for organic synthesis. These processes include the step of producing synthesis gas and the stage of synthesis of hydrocarbons from synthesis gas in the Fischer-Tropsch process or from methanol or dimethyl ether in the processes of firms MobilOil and Haldor Topsoe. Tight integration stages of the GTL process, the use of new catalysts and technologies allow to improve economic indicators of production of liquid hydrocarbons from gaseous hydrocarbons and to use the GTL processes on remote oil and gas fields with the aim of rational use of natural raw materials.
The most promising method of producing synthesis gas is partial oxidation of hydrocarbons in Pris�accordance free oxygen and water vapor. Receive at least partially balanced by the warmth of the process, since the oxidation by free oxygen - the process is exothermic and steam reforming of hydrocarbons is an endothermic process. In addition, the combination of these oxidation methods control the composition of the resulting synthesis gas, the ratio of its main components CO and H2. As the source of molecular oxygen using the air, including enriched with oxygen, or pure oxygen.
As for the second stage of the GTL process, the stage of synthesis of liquid hydrocarbons, the expediency of application of the option depends on many factors. In any case on 1 mol of CO converted to hydrocarbons, to produce 1 mol of water and a minor amount of by-products - oxygenates (oxygen-containing hydrocarbons). After cooling and condensation of liquid products the stage of synthesis of hydrocarbons produced water separation is separated from the hydrocarbon products. Received side water contains dissolved hydrocarbons and oxygenates. For example, depending on the conditions of the Fischer-Tropsch process and the used catalyst side process water contains 0.02 wt%. hydrocarbons, 0,09-1,41% wt. acidic oxygenates and 1-4,47 wt%. non-acid oxygenates (patent US7147775). Especially large, up to several percent contained�C oxygenates may be water in the reaction processes of MTG and TIGAS in the conversion of methanol and dimethyl ether to hydrocarbons, because it includes part unturned components of raw materials. The use of the reaction water is associated with its purification from mechanical impurities, dissolved gases, hydrocarbons and oxygenates, and in some cases, and with the cleaning of metal ions.
A method of producing hydrocarbons using steam reforming of hydrocarbons and the reaction of the Fischer-Tropsch process according to the patent US 7323497, from which water formed in the reaction of Fischer-Tropsch as a by-product, get steam for steam reforming of oxygenates and depleted water: water is heated by the reaction and in the saturator raw gas saturated with water vapor and oxygenates contained in the water and forming with it the low-boiling azeotropic mixture. Depleted water impurities is less expensive to clean. In this way, preferably purified all the water formed during the synthesis of hydrocarbons.
A known method of disposal of water side stage production of synthesis gas and/or the stage of synthesis of hydrocarbons by Fischer-Tropsch process according to the patent RU 2433085, which is carried out in the processing side of the water, her and received a deaeration water is used for boiler feed, and at the processing stage side water oxygenates removed at least one way: biological treatment, adsorption, membrane separation.
Most Blimber�cue to the present invention a method of cleaning and use water reaction described in the application WO 99/15483 to a method of producing liquid hydrocarbons from a hydrocarbon feedstock. One of the variants of the prototype method includes obtaining synthesis gas in the process of partial oxidation of the feedstock in the presence of oxygen-containing gas and water vapor and/or water quenching of the produced synthesis gas by injecting water into hot stream of synthesis gas to reduce its temperature to 100-500°C, preferably up to 300-400°C, further cooled in the apparatus of indirect heat exchange to a temperature of 40-130°C, preferably 50-100°C, and the condensation of water vapor, separation from synthesis gas water condensation, catalytic conversion of synthesis gas to the Fischer-Tropsch process in a gaseous, liquid hydrocarbons and water, which is used in the process of partial oxidation of the raw material and quenching the synthesis gas, and electricity using the obtained gaseous hydrocarbons and water after quenching the synthesis gas. Electricity is used to produce oxygen.
In the described method obtained at the stage of synthesis of hydrocarbons water (reaction water) is used at the stage of generation of synthesis gas to partial oxidation of hydrocarbon raw materials and hardening of the produced synthesis gas. Cleaning parts obtained at the stage of synthesis of hydrocarbons, the reaction water is used in the process of partial oxidation of the raw materials and organic impurities present in the water are converted into oxides coal�ode and hydrogen under conditions of high-temperature partial oxidation process. Part of the reaction water after use for quenching the synthesis gas contains oxygenates, and for further recycling requires special water treatment, however, this fact, the authors described method of producing hydrocarbons do not attach importance to, using it to generate electricity.
The use of water condensate to produce process steam is possible only in accordance with the requirements for nutrient or water boiler. The use of the reaction GTL process water for steam production, for example, when using the heat generated in the process of synthesis of hydrocarbons from synthesis gas (upon cooling of the reaction zone of synthesis of hydrocarbons), requires purification from organic impurities and special training which is not provided in the method of producing liquid hydrocarbons by the prototype.
The technical problem of the invention is the purification of water from the reaction of oxygenates and the use of the reaction water to produce steam - the present invention is solved by converting the oxygenates contained in the reaction water, mainly oxides of carbon and hydrogen in the conditions of quenching the synthesis gas reaction with water at a temperature above 500°C in contact with a catalyst for steam reforming of oxygenates, followed by degassing of the water. Purified in such way water at �neobhodimosti sent for water treatment, associated with the cleaning of metal ions, dissolved gases, and is used to produce steam.
The technical result achieved the claimed invention is to reduce hardware costs for the preparation of purified water and operating costs of GTL plants in General due to the absence of external sources of purified water and use in the synthesis of the entire purified water reaction. The reaction using the purified water to produce steam GTL process makes installation independent from external water sources (stand-alone), which is especially important when placing the installation in the steppe, desert or Arctic regions. Additionally, the reaction using the purified water to produce steam in the GTL process can significantly reduce the consumption of reagents at the stage of water treatment for steam generating, since the reaction water does not contain salts (ions of calcium and magnesium) and reduce the amount of exhaust salt-containing effluent.
Said technical result is achieved by a method of purification from the reaction of oxygenates water formed at the stage of synthesis of hydrocarbons from synthesis gas in the GTL process comprising the step of producing synthesis gas from gaseous hydrocarbons under conditions of partial oxidation or steam reforming at least part of these carbohydrate�birth and the stage of synthesis of hydrocarbons from syngas, characterized by conversion of at least part of the oxygenates with the formation of mainly carbon monoxide and hydrogen at the stage of producing synthesis gas, wherein the conversion of at least part of the oxygenates at the stage of obtaining the synthesis gas is carried out in conditions of quenching the synthesis gas reaction with water at a temperature above 500°C in contact with a catalyst for steam reforming of oxygenates.
Said technical result is achieved by a method of using the reaction water formed at the stage of synthesis of hydrocarbons from synthesis gas in the GTL process comprising the step of producing synthesis gas by partial oxidation of hydrocarbon raw materials in the conditions of steam reforming at least part of these hydrocarbons and the stage of synthesis of hydrocarbons from synthesis gas, comprises feeding at least part of the reaction water to the stage of producing synthesis gas for the implementation of hydrocarbon steam conversion of raw materials and for quenching the synthesis gas, at the same time carry out the purification from the reaction of oxygenates water in the conversion of at least part of the oxygenates with the formation of mainly carbon monoxide and hydrogen in the conditions of quenching the synthesis gas reaction with water at a temperature above 500°C in contact with a catalyst for steam reforming of oxygenates, purified from oxygenates reaction water Tegaserod and used to produce steam.
Offer FPIC�b purification of oxygenates from the reaction water of Fischer-Tropsch process is based on pyrolysis and catalytic steam reforming at temperatures above 500°C alcohols, esters, aldehydes, ketones and acids upon contact with a catalyst comprising at least one of the transition metals.
The reaction water of the process of synthesis of hydrocarbons from synthesis gas typically contains 2-5 wt%. oxygenates: acids, mainly formic and acetic acid; alcohols (C1-C5mainly methanol and ethanol; aldehydes, primarily formaldehyde, acetaldehyde and propionic aldehyde, esters, mainly dimethyl. Most rich on the composition of the reaction water of Fischer-Tropsch process. The composition of oxygenates in the reaction water of Fischer-Tropsch process depends on the catalyst and process conditions for the synthesis of hydrocarbons. For example, when using a cobalt catalyst as impurities are formed mainly alcohols. The process of synthesis of hydrocarbons from synthesis gas using an acid catalyst, comprising the further intermediate step of obtaining from synthesis gas to dimethyl ether and/or methanol, contain mostly methanol.
Partial oxidation purified from the impurities of sulfur and nitrogen-containing compounds hydrocarbons, preferably hydrocarbons (C1-C4natural or associated gas, carried out by known methods by atmospheric oxygen and water vapor in the presence of a catalyst (EP 101765, WO 2012084135), usually at a temperature of 800-1200°C. synthetic�-gas at the outlet of the catalyst bed has a temperature of not lower than 800°C, typically 800-1100°C. the Cooled synthesis gas (quenching) is carried out in a quenching zone by spraying the reaction of water with the stage of synthesis of hydrocarbons from synthesis gas. At the stage of synthesis of hydrocarbons the reaction water condensed during cooling of the product stream containing synthesized hydrocarbons, and produce in the separator at a temperature of 30-40°C. as a carrier gas during the injection of water into the quenching zone may be used or exhaust recycled gas from the stage of synthesis of hydrocarbons.
The quenching zone, the synthesis gas may be located in the lower part of the generator synthesis gas (EN 2465194, WO 2001024922) or may be a separate apparatus. The catalyst in the oxide layer (transition metal media Al2O3, SiO2industrial catalysts for steam reforming of gasoline) may be deposited on the heat-resistant metal mesh or the contact elements placed in the quenching zone.
The reaction water in an amount required for cooling the synthesis gas to a predetermined temperature above 500°C, using spray nozzles is injected into the stream exiting the reaction zone a hydrocarbon feedstock containing carbon oxides, hydrogen, water vapor and methane. The quench zone by contact with synthesis gas reaction water is vaporized and heated to a predetermined temperature above 500°C. In these conditions, proisxodit.eslib oxygenates, moreover, the esters are decomposed with formation of corresponding acids and hydrocarbons, alcohols and acids at temperatures above 700°C with the formation of carbon oxides, hydrogen, methane, ethane, ethylene, formaldehyde. The most stable light components: formaldehyde, methanol, ethanol, acetic acid. At lower temperatures produces acetone, acetaldehyde, formaldehyde, at 700°C in the pyrolysis products is dominated by hydrocarbons, oxides of carbon and hydrogen, and with high speed pyrolysis is at a temperature above 800°C. the deeper the conversion of oxygenates occurs when steam reforming on the catalyst. The processes of steam reforming of methanol, ethanol, acetone and acetic acid in the presence of different catalysts have been extensively studied in connection with the problem of obtaining biofuel from organic materials.
It is known that in the presence of transition metals (Pt, Pd, Rh, Ni, Co, Cu) on oxide carriers occurs steam reforming of oxygenates with the formation of mainly carbon monoxide and hydrogen (A. S. Basagiannis, X. E. Verykios. CatalyticSteamReformingofAceticAsidforhydrogenproduction. International Journal of Hydrogen Energy, 2007, 32 (15), p.3343-3355; M. Marquevichetal. Hydrogen from Biomass: Steam Reforming of Model Compounds of Fast-Oil Hydrolysis. Energy Fuels, 1999, 13 (6), p.1160-1166). At temperatures above 500°C methanol, ethanol, aldehydes and acetic acid upon contact with the catalyst are decomposed almost completely to oxy�s of carbon and hydrogen, and at 650°C and above - even with a small contact time.
In a preferred case, the cooling of the synthesis gas in the quenching zone is carried out to a temperature below 500°C, preferably 300-350°C. After cooling, the synthesis gas reaction water and chemical transformations contained oxygenates further cooling the flow is carried out with purified water. This purified water is sprayed through a pneumatic or other suitable design of the nozzles in the quench zone below the catalyst for steam reforming of oxygenates.
The output from the generator synthesis gas prepared stream at a temperature below 500°C, preferably at a temperature of 300-350°C, containing products of partial oxidation of hydrocarbons in the presence of free oxygen and water vapor, and purified from the reaction of oxygenates water, used in the first stage of hardening, and water, used in the second stage of tempering. The stream is cooled in recuperative heat exchangers and air cooling devices, condense water and produce condensate in the gas-liquid separator. Condensate Tegaserod, that is, removing dissolved gases - carbon dioxide, light hydrocarbons, ammonia, etc. the Degree of degassing must meet the requirements of the water with its further use in to�quality boiler feed water and treated water for quenching the synthesis gas. Next, the water prepared by conventional methods for use as feed water for boilers and steam generation.
The proposed method of purification and use of the reaction water may be carried out as follows.
The GTL process includes a step of producing synthesis gas by partial oxidation of petroleum gas in the generator synthesis gas in the presence of atmospheric oxygen and water vapor and the step of producing hydrocarbons in the Fischer-Tropsch process on the cobalt catalyst. The synthetic gas generator is an apparatus in which the reaction zone and the quenching zone, the synthesis gas are connected by the flow of products of partial oxidation of the raw material. From the reaction zone of the generator synthesis gas product stream is withdrawn partial oxidation of the raw material at a temperature of 800°C and a pressure of 0.5 MPa, comprising, in kg/h, methane - 3,06; carbon monoxide - 1922,57; hydrogen - 260,01; carbon dioxide - 506,11; nitrogen - 4827,74; water vapor - 885,61. For cooling a flow of 350°C is required 2225 kg/h of water at 40°C. For cooling the synthesis gas to 600°C in the quenching zone serves 929,29 kg/h of reaction water at a temperature of 40°C and a pressure of 1.8 MPa at the stage of obtaining hydrocarbons in the Fischer-Tropsch process after the three-phase separator. The reaction water has a pH=2.0 and contains of 0.812 wt%. alcohols, including 0.33% methanol and 0.22% of ethanol, 0,032% mA�. organic acids, including 0,007 formic and of 0.021% acetic and 0,0027% wt. ketones. After contact of the mixed stream with a catalyst containing 11% NiO oxide on the carrier for cooling the synthesis gas to 350? C at the outlet of the quenching zone to the stream spray 302,43 kg/h of purified water after degassing and filtration. For spraying water in the quenching zone, use 600 nm3/hour of exhaust gas from the process Fischer Tropsch having a composition, in % by vol., CO - 7,18; N2- 12,07; CO2- 4,99; N2- 73,90; CH4- 1,57; hydrocarbons With2-C4-0,29. The stream from the quenching zone is sent to the recuperative heat exchanger where it is cooled to 230°C and further to devices of air cooling to 40°C. allocate the Water condensate in the separator of the cyclone type, Tegaserod receive condensate from pH=7.5 to 8.5 and directed to the water treatment plant, where after mechanical cleaning processes, ultrafiltration, deionization get purified water used for cooling the synthesis gas in the quenching zone to 350°C and to produce steam while cooling the reactor Fischer-Tropsch. Part of the resulting vapor - 1200 nm3/h is directed to the step of producing synthesis gas for mixing with the hydrocarbon raw material, with air and in the reaction zone of the generator synthesis gas.
1. Method of purification from the reaction of oxygenates water formed during the synthesis� of hydrocarbons from synthesis gas in the GTL process, comprising the step of producing synthesis gas by partial oxidation of hydrocarbon raw materials in the conditions of steam reforming at least part of these hydrocarbons and the stage of synthesis of hydrocarbons from syngas, characterized by conversion of at least part of the oxygenates with the formation of mainly carbon monoxide and hydrogen at the stage of producing synthesis gas, characterized in that the conversion of at least part of the oxygenates at the stage of obtaining the synthesis gas is carried out in conditions of quenching the synthesis gas at least part of the reaction water at a temperature above 500°C in contact with a catalyst for steam reforming of oxygenates.
2. Method of purification from the reaction of oxygenates water according to claim 1, characterized in that the reaction do the cleaning water in the quenching of the resulting synthesis gas at temperatures above 500°C and further cooled synthesis gas to a temperature below 400°C reaction injection water purified from oxygenates.
3. Method of use of the reaction water formed at the stage of synthesis of hydrocarbons from synthesis gas in the GTL process comprising the step of producing synthesis gas by partial oxidation of hydrocarbon raw materials in the conditions of steam reforming at least part of these hydrocarbons and the stage of synthesis of hydrocarbons from synthesis gas comprising feeding at least part of the reaction water to the stage of producing synthesis gas used for�the performance of steam reforming of hydrocarbon feedstock and for quenching the synthesis gas, characterized in that carry out the purification from the reaction of oxygenates water in the conversion of at least part of the oxygenates with the formation of mainly carbon monoxide and hydrogen in the conditions of quenching the synthesis gas reaction with water at a temperature above 500°C in contact with a catalyst for steam reforming of oxygenates, purified water reaction Tegaserod and used to produce steam.
4. Method of use of the reaction water according to claim 3, characterized in that carry out the purification from the reaction of oxygenates water in the quenching of the synthesis gas reaction with water at a temperature above 500°C and further cooled synthesis gas to a temperature below 400°C reaction injection water purified from oxygenates.
SUBSTANCE: invention relates to a method of regenerating one or more particle (particles) of the deactivated cobalt-containing Fischer-Tropsch catalyst in situ in the reactor tube, where the said catalyst particle(s) are deactivated by the application in the Fischer-Tropsch process, with the said regeneration method containing the following stages: (i) catalyst particle(s) is/are oxidised at a temperature from 20 to 400°C, preferably from 100 to 400°C, more preferably from 200 to 400°C; (ii) catalyst particle(s) is(are) processed with a solvent, containing ammonium carbonate and methylamine, ethylamine, propylamine and/or butylamine, for the time period longer than 5 minutes; (iii) catalyst particle(s) is/are dried and, optionally, heated; and (iv) catalyst particle(s) is/are reduced with hydrogen or a hydrogen-containing gas. The method of generating one or more particles of the cobalt-containing Fischer-Tropsch catalyst also contains s the following stages: (a) catalyst particle(s) is/are oxidised in the reactor pipe at a temperature from 20 to 400°C, preferably from 100 to 400°C, more preferably from 200 to 400°C; (b) catalyst particle(s) is/are discharged from the reactor pipe; (c) catalyst particle(s) is/are processed with a solvent, containing ammonium carbonate and methylamine, ethylamine, propylamine and/or butylamine, for the time period longer than 5 minutes; (iii) catalyst particle(s) is/are dried and, optionally, heated.
EFFECT: advantage of the method consists in the fact that during the processing stage only a small amount of cobalt is washed out, with the simultaneous reduction of the dissolved iron amount.
18 cl, 3 tbl, 2 ex
SUBSTANCE: invention relates to a catalyst of the Fischer-Tropsch synthesis, containing from 10 to 30 wt % counted per atomic metal, metal cobalt and/or cobalt oxide, with respect to the weight of the catalyst, supported on a carrier, containing silica, in which the carrier has an average pore diameter from 8 to 25 nm, and metal cobalt and/or cobalt oxide has the average diameter of crystallites not smaller than the average diameter of the carrier pores and smaller than 35 nm, with the catalyst containing from 0.5 to 10 wt % of zirconium in the form of zirconium oxide, counted per the catalyst weight. The invention also relates to a method of the catalyst manufacturing, as well as to methods of obtaining hydrocarbons.
EFFECT: obtaining the catalyst, possessing improved catalytic activity due to the regulation of active metal distribution between the space inside the pores and the space outside the pores of the porous-inorganic carrier.
11 cl, 2 tbl, 9 ex
SUBSTANCE: claimed is method of obtaining catalyst precursor. Method of obtaining catalyst precursor includes: obtaining suspension, which includes liquid carrier, dissoluble metal salt, particles of insoluble inorganic metal salt and particles and/or one or more bodies of preliminarily formed catalyst supporters, with precipitation of metal from insoluble metal salt on supporter particles due to chemisorptions, and with precipitation of metal from soluble metal salt inside and/or on supporter particles due to impregnation, with chemisorptions and impregnation being realised simultaneously, and metals in insoluble inorganic metal salt and in soluble metal salt being the same and representing Co or Ni, with said metal being active catalyst component, with formation of processed catalyst supporter, and removal of liquid carrier from suspension with obtaining dries processed catalyst supporter, which either represents catalyst precursor directly, or optionally is subjected to calcinations to obtain catalyst precursor. Also claimed are: method of catalyst obtaining, method of synthesising hydrocarbons, method of hydration.
EFFECT: method is economical, provides obtaining required dispersion with high load on strong supporter.
14 cl, 1 tbl, 4 dwg, 23 ex
SUBSTANCE: invention relates to a method for manufacturing a regenerated Fischer-Tropsch synthesis catalyst by regenerating a used catalyst which was previously used in a Fischer-Tropsch synthesis reaction. A method comprises a steaming step of bringing the spent catalyst into contact with a mixed gas comprising 1 to 30% by volume of steam and an inert gas at a pressure of atmospheric pressure to 5 MPa and a temperature of 150 to 350°C. The above spent catalyst being a spent catalyst in which cobalt and/or ruthenium is supported on a carrier comprising silica with an average pore diameter measured by a nitrogen adsorption method of 4 to 25 nm, and of which activity represented by an initial carbon monoxide conversion is 40 to 95%, based on the activity of a corresponding unused catalyst. The invention also relates to a method for producing hydrocarbons using a regenerated FT synthesis catalyst produced by the method.
EFFECT: regenerated FT synthesis catalysts having high activity and high chain propagation probability can be obtained.
5 cl, 1 tbl, 14 ex
SUBSTANCE: invention relates to a method of converting synthesis gas into hydrocarbons, which includes Fischer-Tropsch synthesis of hydrocarbons. A method of converting synthesis gas into hydrocarbons includes steps of: (i) passing synthesis gas including hydrogen and carbon monoxide through a cobalt catalyst at high temperature and pressure to produce a first reaction product mixture comprising hydrocarbons, steam, carbon monoxide and hydrogen, (ii) condensing and separating water from the first reaction product mixture to produce a dehydrated first reaction product mixture, (iii) passing the dehydrated first reaction product mixture containing hydrogen and carbon monoxide through a supported ruthenium catalyst at high temperature and pressure to produce a second reaction product mixture containing hydrocarbons, and (iv) recovering the hydrocarbons from the second reaction product mixture, where the first reaction step to obtain the first reaction product mixture is carried out temperature in the range of 210-225°C and pressure in the range of 1.0-3.0 MPa, and the second reaction step to obtain the second reaction product mixture is carried out at temperature in the range of 230-265°C and pressure in the range of 3.5-5.5 MPa.
EFFECT: C5+ hydrocarbon selectivity of 95% or higher, which characterises high output.
27 cl, 1 dwg, 1 tbl, 1 ex
SUBSTANCE: invention relates to producing hydrocarbons and, optionally, oxygenates of hydrocarbons. The process includes contacting a synthesis gas comprising hydrogen, carbon monoxide and N-containing contaminants selected from the group consisting of HCN, NH3, NO, RxNH3-x, where R is an organic group and x is 1, 2 or 3, with R being the same or different when x is 2 or 3, R1-CN, where R1 is an organic group, and heterocyclic compounds containing at least one nitrogen atom as a ring member of a heterocyclic ring of the heterocyclic compound, with the N-containing contaminants constituting, in total, at least 100 vppb but less than 1000000 vppb of the synthesis gas, at a temperature of at least 180°C and a pressure of at least 10 bar(a), with a particulate supported Fischer-Tropsch synthesis catalyst which comprises a catalyst support, Co in catalytically active form supported on the catalyst support, and a dopant selected from the group consisting of platinum (Pt), palladium (Pd), ruthenium (Ru), rhenium (Re) and a mixture of two or more thereof at a dopant level expressed by formula 1: , where w is expressed as g Ru/g Co; and w<0,019 g Ru/g Co; x is expressed as g Pd/g Co; y is expressed as g Pt/g Co; z is expressed as g Re/g Co; and z<0,005 g Re/g Co; and 0<a<1, to obtain hydrocarbons and, optionally, oxygenates of hydrocarbons, by means of Fischer-Tropsch synthesis reaction of the hydrogen with the carbon monoxide. The invention also relates to the use the said catalyst to produce hydrocarbons.
EFFECT: in process for producing hydrocarbons by means of the above method, high levels of nitrogen contaminants can be tolerated while maintaining good catalyst activity and low catalyst CH4 selectivity.
11 cl, 11 tbl, 24 ex
SUBSTANCE: method includes feeding reaction water from a typical hydrocarbon synthesis process into a countercurrent stripping column from the top and feeding a hydrocarbon-containing gas from the bottom into the countercurrent stripping column in a direction opposite to that of the reaction water, removing purified water from the bottom of the countercurrent stripping column; wherein the obtained steam-gas mixture from the output at the top of the countercurrent stripping column is fed to a standard process of producing synthesis gas; wherein the countercurrent stripping column has a nozzle whose fractionation capacity is equivalent to at least two to three equilibrium thermodynamic stages, and the hydrocarbon-containing gas is formed from a mixture of convertible gas and at least part of a hydrogen-containing waste gas generated from hydrocarbon synthesis waste gases. Furthermore, the countercurrent stripping column is fitted with a reboiler which heats the countercurrent stripping column from the bottom. The reaction water and the hydrocarbon-containing gas are fed at pressure of 1-5 MPa, wherein the obtained steam-gas mixture from the output at the top of the countercurrent stripping column is further superheated to eliminate droplets of a liquid carried from the column.
EFFECT: use of the present method improves efficiency of purifying reaction water while simultaneously broadening recycling capabilities for products used in water purification, and recycling reaction water hydrocarbons when producing synthesis gas.
4 cl, 1 ex, 2 dwg
FIELD: oil and gas industry.
SUBSTANCE: invention refers to oil and gas chemistry, in particular to a method of oil-associated and hydrocarbon gas processing. A method for producing liquid hydrocarbons of hydrocarbon gas is accompanied by water production; if necessary, it involves desulphurisation, flue gas heating of a heat-energised instrumentation assembly followed by synthetic gas production by high-temperature reforming by conversion with atmospheric oxygen, to prepare liquid hydrocarbons and water followed by water distillation from residual hydrocarbons. The method is characterised by the fact that before high-temperature reforming, the hydrocarbon gas and air are subject to low-temperature pre-reforming; a reaction gas mix flow supplied from a pre-reforming reactor is separated into two flows; one of the flows is introduced into a pre-reforming converted gas feed line into the reforming reactor; before injection, the second flow is supplied into the reforming reactor for carbon dioxide venting; the gas flows are then combined; liquid hydrocarbons are produced of the synthetic gas using a narrow-fraction catalyst system; the pre-reforming, reforming and liquid hydrocarbon synthesis reactors use the radial filtration of reaction flows; additionally, water is produced of flue gas and pre-reforming gas outflows; water process loss is compensated with water from a collector, wherein the water recovered from the flue gasses, pre-reforming gasses, synthetic liquid hydrocarbons, optionally reforming gasses, flows. What is also declared is a plant for implementing the method.
EFFECT: creating the method and a light plant producing liquid hydrocarbons to be used on remote, low-pressure deposits, for flared gas processing; the method and plant are characterised by a closed internal water supply system enabling avoiding water discharge into the environment that generally leads to economical efficiency of the method and plant.
4 cl, 2 dwg, 2 ex
SUBSTANCE: method of processing hydrocarbon gas into stable liquid synthetic petroleum products, for instance into synthetic petroleum or synthetic motor fuel, includes preliminary treatment of initial hydrocarbon gas depending on its physical-chemical properties, for instance, purification from hydrogen sulphide compounds, and/or separation and drying, and/or compression, as well as further division of the said preliminarily treated gas into two flows: the main flow, processed into the final product, and the technological flow, used to increase temperature of the main gas flow in the process of the final product obtaining, further processing each of the said separated flows: main flow - by catalytic vapour reforming with obtaining synthesis-gas, its further cooling, processing into stable synthetic petroleum and, if necessary, separation of synthetic petroleum into fractions of synthetic motor fuel, processing the separated technological flow is realised by passing through a gas-turbine installation with obtaining electric energy and combustion products, with excess hydrogen being additionally separated from obtained by vapour reforming cooled synthesis-gas, and combustion products of the technological gas flow, passed through the gas-turbine installation, being first after-burnt together with excess hydrogen and a part of technological flow of preliminarily processed initial hydrogen gas, and then being supplied to heating of the main gas flow in the process of its conversion by vapour reforming. Also claimed is an energy complex for hydrocarbon gas processing.
EFFECT: creation of effective conditions for carrying out the process of obtaining synthetic petroleum in the Fischer-Tropsch reactor due to the stabilisation of the synthesis-gas flow by the removal of excess hydrogen from it, as well as the creation of effective conditions for carrying out the process of obtaining synthesis-gas due to heating the main gas flow in the process of its conversion by vapour reforming by products, obtained from after-burning of combustion products of the technological gas flow, passed through the gas-turbine installation, together with excess hydrogen and a part of the technological flow of preliminarily processed initial hydrogen gas, and provision of the optimally stable process of the main gas flow conversion due to support of its temperature in the synthesis-gas reactor in an automatic mode.
5 cl, 1 dwg
SUBSTANCE: invention relates to field of synthesis of hydrocarbons from synthesis-gas mixture. Invention deals with method for optimisation of functioning of zone of hydrocarbon synthesis from raw material, which contains synthesis-gas, in which catalyst, containing cobalt, is present, with claimed method including the following stages: a) determination of theoretic value of partial pressure of carbon monoxide in reaction zone, b) regulation of partial CO pressure, determined at stage a), to value, higher or equal 4 bars, c) determination of new value of theoretic value of partial CO pressure CO in reaction zone.
EFFECT: optimisation of device operation, improvement of catalyst stability.
21 cl, 2 tbl, 14 ex
FIELD: process engineering.
SUBSTANCE: invention relates to filter to be incorporated with waster filtering assembly. Water filtering assembly comprises filter of, mainly, a flat profile. Water filtering assembly comprises container for filtered water, intake funnel to be fitted in said container and to intake unfiltered water. This filter can be fitted in intake funnel for filtering of water fed therein. The filter makes the exit from intake funnel for filtered water to get into aforesaid container. The filter makes the intake funnel bottom and as a result water filtering goes over the entire intake funnel bottom. The filter comprises case with water intake and filtered water outlet. Note here that filtering medium is arranged between said intake and said outlet. Water filtering medium includes the ply of ion-exchange resin and ply of material filled with activated carbon. Note that said plies are separated in said case.
EFFECT: higher filtering rate.
22 cl, 6 dwg
FIELD: machine building.
SUBSTANCE: desalination multistage adiabatic plant additionally comprises a thermosoftener (52) which serves for the generation of sludge particles in the feed water heated in a steam heater (26) and taken from a pipeline to supply the feed water to the inlet of a multi-stage adiabatic evaporator (4), as well as a two-section feed water receiver (76) to reduce supersaturation in the sea water being evaporated due to the usage of sludge particles as "seed crystals" in the supersaturated solution volume. The thermosoftener (52) comprises a perforated membrane (56) built-in in the casing (53) under the cover, a dome-shaped horizontal partition (61) installed with a gap in respect to the inner casing wall, vertical cylindrical shells, a manifold to withdraw the vapour (62) under the dome-shaped partition, a branch pipe for water withdrawal is united with the sludge particle removal and is mounted in the casing bottom, and the branch pipe for steam supply is built-in in the casing cover.
EFFECT: lower rate of scale formation on working surfaces of the plant elements.
2 cl, 9 dwg
SUBSTANCE: invention relates to a device and a method of detecting the quality of a liquid, which are used in water treatment devices. The detector "renders" the quality of water in the form of visible radiation instead of converting intensity of UV radiation into digital form and comprises a first detection window coated with a first material for converting first received UV radiation emitted by a UV source and transmitted through the liquid into first visible radiation. The device additionally mixes the first visible radiation with second visible radiation to produce third visible radiation. A different colour of the third visible radiation reflects different quality of water.
EFFECT: invention simplifies the device and method owing to absence of UV sensors in water, which detect UV intensity.
14 cl, 6 dwg
FIELD: process engineering.
SUBSTANCE: invention relates to combined magnetic processing of fluids. Proposed device comprises housing 1 connected via fluid feed and discharge pipes and magnetic unit 6 fitted therein and composed of the set of permanent magnets. Fluid flow channel is arranged between said magnetic unit 6 and housing 1 and composed of spiral with pitch ratio equal to six. The length of magnetic unit 6 is comparable with its diameter. Ferromagnetic washers 7 are fitted between three circular magnets of magnetic unit 6. Electromagnets 4 built around Helmholtz coils 5 with reactive power compensators are arranged at fluid feed and discharge pipes 2 and 3.
EFFECT: efficient magnetisation of fluid flow, ruled out permanent magnet effects.
FIELD: process engineering.
SUBSTANCE: invention relates to water crystal cleaning of harmful admixtures including heavy isotopes of deuterium. Proposed device comprises case 11 to house riser 8 with two chambers 4, 1. The latter make inlets for portable water and heat carrier. Portable water chamber 4 is connected with inside of case 11 that has outlet at its bottom. Heat carrier chamber 1 is connected with inside of ribs 7 arranged in case 11 and combined by outlet. Outer surface of ribs 7 is wavy.
EFFECT: continuous formation of deuterium ice in portable water.
FIELD: process engineering.
SUBSTANCE: invention relates to steam fractions separators. Steam separator comprises vessel for boiling fluid with top section provided with circular horizontal ring with inner groove and hole for condensate. Several identical elements consist of vertical tubes with horizontal rings arranged at their lower part and like rings at upper part provided with grooves with holed for condensate draining. Note here that said elements are fitted one on the other while the last one at upper part is plugged.
EFFECT: higher efficiency.
2 cl, 1 dwg
SUBSTANCE: group of inventions relates to technology of processing water with ozone and can be used in systems of water supply of towns and settlements for decontamination of drinking water from surface water sources, in particular, with large seasonal fluctuations of water contamination, requiring up to sixfold change of ozone dose. Ozone-air mixture is supplied by steps with constant consumption at each step and change of ozone concentration in ozone-air mixture. Ratio of maximal consumption of ozone-air mixture at the last step to minimal at the first step is taken equal to not more than 2. Dimensions of ozone-air mixture bubbles is from 0.8 to 1.2 mm. Device for processing water with ozone contains system of preparation of dried and cooled air, providing its supply into ozone and ozone-air mixture generator onto disperser in steps, as well as three separate lines of similar dispersers.
EFFECT: group of inventions provides reduction of loss of ozone produced by generator, efficiency of produced ozone application not lower than 95%, increased accuracy of ozone dosing, increased reliability of installation functioning and its safety.
12 cl, 14 dwg, 6 tbl
SUBSTANCE: method of purifying waste water includes adding a natural zeolite to the water to be treated, mixing, settling and filtering. The natural zeolite used is a natural zeolite containing 50-60% clinoptilolite with particle size of 1.0-1.5 mm. Uniform mixing is carried out at a rate of 1-2 rps for 10-15 s and settling is carried out for 12-48 hours.
EFFECT: low content of heavy metal and ammonium ions when treating waste water below the maximum allowable concentration while enabling use of the treated water for crop irrigation.
1 tbl, 2 ex
FIELD: process engineering.
SUBSTANCE: invention relates to agriculture, particularly to sea water desalination and can be used for purification of sweet water. Sweet water can be produced by evaporation and condensation of water vapours in costal areas and at sea platforms. Sea water desalination includes its evaporation and condensation of water vapour. Sea water is taken separately from top warm and cold bottom layers. Note here that warm water is forced to evaporation while cold water is used for condensation of water vapour resulted from heated sea water and atmospheric air.
EFFECT: lower power and metal input, higher efficiency of desalination.
2 cl, 1 dwg
SUBSTANCE: invention relates to microbiological industry and can be used in biological purification of water and soil from oil and oil products. Claimed is consortium of strains of microorganisms Acinetobacter sp. VKM B-2753D and Ochrobacterium sp. VKM B-2754D, possessing nitrogenase activity.
EFFECT: consortium is capable of atmospheric nitrogen fixation and possesses high utilising ability with respect to oil and oil products with their high content in substrate.
1 tbl, 3 ex
SUBSTANCE: invention refers to a system for hydrogen development and a method for controlled hydrogen development. A method consists in carrying out a reaction of a metal agent selected in alkali metals, alkali earth metals, alloys and mixtures consisting of alkali metals, alkali earth metals, alloys consisting of at least one alkali metal, and at least one alkali earth metal with water for producing hydrogen and a residual product of reaction in the form of metal hydroxide specified in alkali hydroxides and alkali earth hydroxides; the metal agent is condensed by heating in vacuum; the liquid metal agent is supplied into a homogeneous reactor by extrusion by means of feed units, and water is simultaneously supplied to maintain a stoichiometric ratio of water in accordance with an amount of the liquid metal agent; the hydrogen and residual product are transported into the separation units and separated; separated hydrogen is transported into a hydrogen receiver; the residual reaction product is transported into a metal hydroxide receiver; the oxygen ingress into the metal agent feed units, water feed system, reactor, separators and hydrogen receiver by the selective use of vacuum.
EFFECT: developing the method for controlled hydrogen development.
22 cl, 5 dwg, 4 tbl