Wear-resultant copper-containing catalyst for low-temperature methanol synthesis at median-pressure
FIELD: industrial organic synthesis catalysts.
SUBSTANCE: invention relates to copper-containing catalysts for low-temperature synthesis of methanol in fluidized bed at median pressure and provides catalyst, whose preparation involves impregnation and which contains oxides of copper, zinc, chromium, magnesium, aluminum, boron, and barium and has following molar ratio: CuO:ZnO:Cr2O3, MgO:Al2O3:B2O3:BaO = 1:0.3:(0.014-0.038):(0.047-0.119):(0.05-0.1):(0.007-0.014):(0.0292-0.054).
EFFECT: increased mechanical strength and wear resistance of catalyst.
The invention relates to copper-containing catalysts for low-temperature methanol synthesis in a fluidized bed at an average pressure.
There are many catalysts for low-temperature methanol synthesis under medium pressure. The most common form of such catalysts is an industrial catalyst SNM-3 (Karavaev M.M., Leonov V.E., Popov I.G., Shepelev ET Technology of synthetic methanol. Under. editor Prof. Karavaeva M.M.-M.: Chemistry, 1984. - 240 C., Il.). As analogue accept received GIAP catalyst mole of CuO•(0,2-0,4)ZnO•(0,2-0,4)Cr2O3•(0.1 to 0.3)MnO•(0,1-0,3)MgO•(0,05-0,1)Al2O3labeled DS-8-1 (Materials of scientific-technical conference of NIRTO. The development marked the methanol synthesis catalyst of high and medium pressure. Kurylev, A., Barkovsky A.I. Novomoskovsk, 9-13 December 1996, Part 1, 49-50. Dept. in VINITI. 5.02.98, No. 331-98 In /1/). Analog /1/ is suitable for methanol synthesis at 220-280°C and 10 MPa. Its activity exceeds the activity of the catalyst SNM-3, and the selectivity reaches 93 to 95 wt.%. The difference of the catalyst from the catalyst described in the closest analogue is the method of its production and the ratio of catalyst components.
The proposed catalyst designed to increase mechanical firmly the tees and wear resistance to abrasion of the existing catalysts.
To achieve this goal in the composition of the analogue /1/ injected additive In2About3and examine its influence on the mechanical strength and wear resistance of the obtained catalyst (preparation of all samples of the analog /1/ produced by the method of mixing - deposition and catalyst with the additive - impregnated).
The introduction of boron oxide in the catalyst in an amount up to 25 weight% shows a significant increase in mechanical strength and wear resistance of the obtained catalyst. The marked increase in the pore volume and the operating temperature of the catalyst.
In addition, this goal is achieved by obtaining the catalyst by impregnation wear-resistant base, which consists of oxides of boron, aluminum and chromium. The introduction of aluminum oxide in the catalyst stabilizes it, increases its strength properties when abrasion and crushing, and provides a high internal surface, moderately good thermal stability of the catalyst. The introduction of chromium oxide in the catalyst shows a significant increase in the pore size and improving the durability of the catalyst.
The introduction of additives barium oxide in the catalyst contributes to the increase in its activity and selectivity.
Based on the results of testing the most active samples was selected composition of the catalyst for further optimization, mole D. what if:
Analysis of the results of experiments on the optimization showed that the activity and stability of catalyst increases with decreasing content of additives Cr2About3, MnO and MgO from the main level.
Whereas studies of catalysts of the type DS to work under pressure of 10 MPa, offer a catalyst of the following chemical composition, mole fraction:
An example of the preparation of the catalyst.
Separately receive the solution of the basic aluminum chloride Al2(OH)5Cl.
To do this, first of 1000 grams of pure aluminum metal by the electrolytic deposition (I=10-25 A, U=40-80) get the aluminum hydroxide (electrolysis hold up until the weight of the aluminium plate is reduced by 100 g). In the resulting mass is added 70 ml of concentrated hydrochloric acid to pH 3-4. Get 220 ml thixotropic colloidal solution of basic aluminum chloride, which is left to ripen at room temperature.
Separately receive the chromium hydroxide in two ways: heterogeneous (from the dilute salt solution chromium nitrate 33 g with a solution of ammonia water to pH 8, followed by washing the precipitate fine chromium hydroxide is distilled water) and homogeneous (by heating the salt solution chromium nitrate 33 g with the addition of 15 g of urea for 1-1,5 hours to fall a voluminous precipitate followed by washing on the filter).
In Mature psevdosily Al2(OH)5Cl enter svezheosazhdennoi the chromium hydroxide and 14 g of boric acid and mix thoroughly. The resulting suspension is left for 1-2 days to complete peptization the hydroxide precipitate chroma education of the molding material.
To obtain spherical granules using the method of hydrocarbon moulding. Spheroidal drops is carried out in a layer of kerosene thickness of 2-3 cm and volume structuring Zola 15% ammonia water.
In the first stage of the pellets is maintained at a temperature of 313 K in 2-3 days to visually observe the full shrinkage. Then on the second, high temperature, stage of raising temperature at a rate of 10 deg/hour up to 423 K and kept at this temperature for 4 hours.
Temperature calcination of the pellets in the small regulating heat tracing is as follows:
- temperature rise from 423 K To 473 K - 20 deg/h;
- rise of temperature from 473 K To 773 K - 50 deg/h;
- rise of temperature from 773 K To 1373 K - 100 deg/h;
- excerpt at 1373 K for 4 hours.
Separately receive 60% (based on crystalline) impregnating a solution of a density of 1.56 g/cm3of the salts of copper nitrate [Cu(NO3)2] 1250 g of zinc nitrate [Zn(NO3)2] 375 g of magnesium nitrate [Mg(NO3)2] 104 g of barium nitrate [BA(NO3)2] 53 g and nitrate XP is mA [Cr(NO 3)3] 7 g with the addition of oxalic acid [H2With2O4•2H2About] 964,
Impregnation of the granules impregnating solution is carried out at 60-80°within hours.
Calcined catalyst for two hours at 500-550°C. the Number of cycles "impregnation-calcination for all samples is equal to three. The result is 680 g of the catalyst composition is shown in table 1.
|The molar fraction||1||0,3||0,026||0,083||0,08||0,011||0,042|
|The mass fraction||64,3||19,5||3,2||2,7||6,6||2.4||1,3|
From the obtained weight of the finished catalyst choose a sample of 100 g, grain size of 0.6-1.5 mm and subjected to the test for abrasion (by the mass loss of granules during tests in a fluidized bed).
Industrial tests of the obtained low-temperature catalyst medium pressure is carried out in the synthesis of methanol, chetyrekhsektornoi installation. For the organization of the fluidized bed without leakage of gas bubbles and the use of gas distribution grid with holes of 0.5 mm, and the apparatus is placed vertical plane lattice with holes 10 mm
Test conditions: the composition of the synthesis gas (vol.%): CO20,4; 2,6; N272,8; N224,2; a pressure of 10 MPa; the temperature of 220-260°; space velocity of the synthesis gas 10000 h-1. As pseudoviruses agent use the air. The number of fluidization is equal to 1.5. The test time of 720 hours.
Abrasion of the catalyst after 240, 480 and 720 hours of testing, equal respectively to 1.3; 1.9 and 2.25 g, which is 1.3; 1.9 to 2.25 wt.%.
During the test, the catalyst support the following composition of the source gas, vol.%: hydrogen 74-77, oxide of 2-4 carbon, carbon dioxide of 0.3-0.4, inert impurities 15-20. When 220-260°and 10 MPa carbon monoxide is almost completely converted into methanol.
As shown by industrial tests, this low-temperature catalyst substantially wear-resistant (< 5 wt.%), what makes possible its use in industry for carrying out the process in a fluidized bed.
Wear-resistant copper-containing catalyst for low-temperature methanol synthesis at an average pressure obtained by impregnation, comprising the oxides of copper, zinc, chromium, magnesium, aluminum, characterized in that the catalyst additionally contains oxides of boron and barium, and has the following molar ratio:
FIELD: industrial organic synthesis.
SUBSTANCE: invention relates to improved process of producing methanol from purge gas produced in basic methanol or ammonia synthesis. Process comprises dispensing compressed carbon dioxide into basic synthesis purge gas, heating resultant gas mixture to starting synthesis temperature, passing thus heated gas through methanol synthesis catalyst, cooling reacted gas, recovering condensed crude methanol, and separating non-condensed gas stream into return stream and purge stream, the former being designed for mixing with basic synthesis purge gas stream and passed to one or two circulation jet compressors. Circulation is effected by energy provide either by (i) pressure of basic synthesis purge gas, which is supplied to jet compressor and further dispensed into compressed carbon dioxide stream, or by (ii) pressure of compressed carbon dioxide, which is dispensed into jet compressor and then introduced into basic synthesis purge gas stream, or by (iii) pressure of basic synthesis purge gas and pressure of indicated compressed carbon dioxide, both being supplied to one or two jet compressors. Ammonia or methanol production purge gas is successfully used for production of methanol without utilizing additional hydrogen-containing streams.
EFFECT: reduced methanol production cost.
4 cl, 5 dwg, 1 tbl, 4 ex
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to a new method for preparing methanol and other aliphatic alcohols by gas-phase interaction of hydrocarbon gases with water vapor under effect of ultraviolet radiation. Methanol and other aliphatic alcohols are prepared by direct hydroxylation of hydrocarbon gas or mixture of hydrocarbon gases with water vapor. For this aim hydrocarbon gas and vapor or mixture of gases and vapor are fed into reactor wherein the reaction mass is subjected for effect of ultraviolet radiation in wavelength range 240-450 nm at temperature lower vapor formation point. The end product is isolated from vapor-gaseous mixture by condensation and unreacted gas or mixture of gases removed from the reaction zone is purified from the end product by bubbling through water layer and recovered into reactor by adding the parent gaseous component in the amount equal to consumed one. The process is carried out for a single stage and can be realized under atmosphere pressure. Invention can be used in chemical, petroleum chemical, petroleum processing and petroleum and gas extracting industry.
EFFECT: improved preparing method.
2 cl, 1 tbl, 8 ex
FIELD: organic chemistry, chemical technology.
SUBSTANCE: method for synthesis of methanol involves the following stages: removing hydrocarbon gas to be processed, sulfur elimination, catalytic steam conversion to obtain converted gas, heat utilization with separation of water, synthesis of methanol and separation of condensed methanol. Hydrocarbon gas with unstable composition is removed under pressure 0.001 MPa, not less, and sulfur elimination of hydrocarbon gas with unstable composition is combined with stage of step-by-step stabilization of pressure to form steam-gaseous mixture. Methanol synthesis is carried out for at least two successive flow steps with reducing volume of catalyst under pressure 1.5 MPA, not less, and separation of methanol between successive stages. Method provides significant reducing cost of gas processing and service of devices and allows carrying out the processing in mobile traveling devices in field conditions. Invention can be used in processing gas with unstable composition, for example, casing-head petroleum gas in petroleum-extracting holes, in field conditions in small traveling devices.
EFFECT: improved preparing method.
2 cl, 2 dwg
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to the improved method for preparing methanol. Method involves the successive feeding hydrocarbon-containing gas, injection of chemically purified water, carrying out the preliminary steam reforming for preparing synthesis gas and carrying out the final reforming if formed gas with addition of oxygen under pressure for carrying out synthesis of methanol, heating reactor for preliminary reforming by flow of obtained synthesis gas going out from reactor for the final reforming that is fed to intertubular space of reactor for preliminary reforming followed by cooling synthesis gas obtained as result of reforming by vapor-gas mixture and carrying out synthesis of methanol in 2-step reactor. Cooling the reaction mixture for carrying out isothermal reaction for synthesis of methanol in intermediate external heat exchanger of two-step reactor is carried out with vapor-gas mixture and cooling flow going out from reactor for synthesis of methanol is carried out with vapor-gas mixture and chemically purified water. Also, invention relates to unit for preparing methanol including the source of hydrocarbon-containing gas and unit for complex preparing gas, reactor for preliminary vapor reforming heated with flow going out from reactor for final reforming, two-step reactor for synthesis of methanol, heat exchangers for cooling synthesis gas, heat exchangers for cooling flow going out from reactor for synthesis of methanol, separator for separation of reaction products and exhausting gases and crude methanol. The unit for preparing methanol is assembled with unit for complex gas preparing including block for preparing chemically purified water, block for preparing raw, additional manufacture involving torch making, cleansing constructions, sources of electric energy, air of control and measuring instruments and automatic equipment, chemical laboratory and operating block. Two-step reactor for synthesis of methanol joined with heat exchanger for cooling synthesis gas with vapor-gas mixture, intermediate external heat exchanger for cooling the reaction mixture with vapor-gas mixture is joined in-line with heat exchanger for cooling flow obtained in reactor with vapor gas mixture, heat exchanger for cooling of chemically purified water and separator for separation of reaction products. Ignition device is assembled in reactor for final reforming that promotes to carry out the start of unit without trigger furnace. Water is injected in flow hydrocarbon gas directly before heat exchanger for the reaction mixture that provides excluding boiler-utilizer and trigger boiler from schedule and to solve the problem for cooling the reaction mixture in reactor for synthesis of methanol also. Based on integration of the device for preparing methanol in technological schedule with unit for complex preparing gas and significant change of the conventional schedule for preparing methanol method provides 3-fold reducing capital investment.
EFFECT: improved method for preparing methanol.
2 cl, 1 dwg
FIELD: technology for production of methanol from syngas.
SUBSTANCE: claimed method includes mixing of hydrocarbon raw material with water steam to provide syngas by steam conversion of hydrocarbon raw material and subsequent methanol synthesis therefrom. Conversion of hydrocarbon raw material and methanol synthesis are carried out under the same pressure from 4.0 to 12.0 MPa. In one embodiment hydrocarbon raw material is mixed with water steam and carbon dioxide to provide syngas by steam/carbonic acid conversion of hydrocarbon raw material in radial-helical reactor followed by methanol synthesis therefrom under the same pressure (from 4.0 to 12.0 MPa). In each embodiment methanol synthesis is carried out in isothermal catalytic radial-helical reactor using fine-grained catalyst with grain size of 1-5 mm. Methanol synthesis is preferably carried out in two steps with or without syngas circulation followed by feeding gas from the first or second step into gasmain or power plant.
EFFECT: simplified method due to process optimization.
12 cl, 3 tbl, 3 dwg
FIELD: organic synthesis catalysts.
SUBSTANCE: invention provides improved method for preparing catalyst for synthesis of N-methylaniline from aniline and methanol. Method comprises impregnation of alumina carrier with copper nitrate solution, to which were added nitrates of modifying metals selected from group consisting of manganese, chromium, iron, cobalt, and zinc, after which impregnated carrier is dried at temperature ensuring effective conversion of deposited nitrates into oxides of corresponding metals. When calcined, catalyst is subjected to additional impregnation with copper ammine solution, wherein Cu content (on conversion to oxide) lies within 0.6 to 7.0% based on the weight of catalyst, then dried at 100-120°C, and re-calcined at 230-250°C. After first calcination Cu content is 10.1-13% and after the second it rises by 0.6-5.0%. Lifetime of catalyst increases by a factor of 1.3 to 2.
EFFECT: increased lifetime of catalyst.
1 tbl, 12 ex
FIELD: inorganic synthesis.
SUBSTANCE: iron-chromium-nickel spinels are prepared by homogenization of original oxides of nickel(II), iron(III), and chromium(III) in presence of 0.5-1.5% of potassium halides as mineralizing agent followed by briquetting and heat treatment of oxides at 800-1000°C.
EFFECT: enabled preparation of spinels at lowered temperatures and in shorter time.
2 tbl, 2 ex
FIELD: hydrogenation-dehydrogenation catalysts.
SUBSTANCE: invention relates to catalysts used in isoamylenes-into-isoprene dehydrogenation process and contains, wt %: iron oxide 62-75.4, potassium carbonate 12-21.5, chromium oxide 1-3, potassium hydroxide 0.5-2.5, sulfur 0.1-2.0, ammonium nitrate 0.1-2.0, silicon dioxide 1-5, calcium carbonate 1-5, and cerium nitrate 1-3.
EFFECT: increased mechanical strength, resistance to saturated steam and moisture, and stability during long-time operation.