Method of regeneration of a copper-chromium catalyst

 

(57) Abstract:

The invention relates to the production of higher fatty alcohols (WGS) method for the hydrogenation of fatty acids and their esters, in particular to a technology for copper-chromium catalysts from spent catalyst sludge process of hydrogenation. The regenerated catalyst can be used at the stage of hydrogenation of fatty acids and their esters in the synthesis VGS alone or in mixture with fresh catalyst. In the regeneration process of the copper-chromium catalysts for the hydrogenation of fatty acids and their esters to alcohols from spent catalyst sludge by treating them with oxygen-containing gas at elevated temperature before processing oxygen-containing gas from the slurry is distilled alcohols by heating the product up to 300-400oC at a pressure of 5-20 mm RT.article (665-2660 PA) or in a current of superheated steam at a pressure of 50-300 mm RT. Art. (6650-3990 PA) without mechanical mixing, and the resulting catalyst mass is treated with oxygen-containing gas at 350-450oC to stop the absorption of oxygen, with subsequent cooling and grinding until the particle size of the fresh catalyst.

The invention relates to the production Ÿ copper-chromium catalysts from spent catalyst sludge process of hydrogenation. The regenerated catalyst can be used at the stage of hydrogenation of fatty acids and their esters in the synthesis VGS alone or in mixture with fresh catalyst.

Current production VIS, based on the direct hydrogenation of fatty acids or the hydrogenation of the methyl esters of the acids include stage:

the preparation of suspensions of powdered copper-chromium-barium catalyst VIS or methyl esters;

hydrogenation of the mixture of fatty acids (esters) with catalyst suspension;

separation of unreacted hydrogen and return it in the hydrogenation process;

separation from the hydrogenated feed is cut (VGS) the main part of the catalyst on the centrifuge;

final separation of the catalyst from the hydrogenated feed is cut (VGS) filters;

distillation of the hydrogenated feed is cut (VGS).

The drawback of the current technology is the high consumption of expensive copper-chromium-barium catalyst (14-20 kg/t VGS) and a noticeable loss of VIS with sludge. High consumption of fresh catalyst due to the fact that the return separated in centrifuges and filters, catalyst in the hydrogenation process due to the deactivation of its organic compounds is possible only partially, Bolo 30% VIS. Only Shebekino chemical plant emit up to 150 tons of sludge per year, including up to 50 tons VGS, clogging the water bodies and the atmosphere of toxic compounds of copper, chromium, barium and organic substances.

Known methods of isolation of the waste, the deactivated catalyst (slurry) is contained in fats, or alcohols or other organic substances by treating them with volatile solvents (such as methanol, isopropanol) [1] solutions of detergents [2] or dispersant [3]

These methods do not provide complete removal of organic substances, and fat-free catalysts are not fully restore its activity. In addition, methods or fire and explosive or environmentally hazardous due to the formation of a large stream of waste water containing detergents, dispersing agents and other contamination.

Known methods of regenerating exhausted deactivated catalysts by the method of oxidation of organic substances adsorbed on the catalyst [4]

The closest in technical essence is a method for the regeneration of spent copper-chromium-barium catalyst for the hydrogenation of methyl esters of fatty kiram NaOH [5] which allows the use of the regenerated catalyst in the hydrogenation process and to reduce the consumption of fresh catalyst.

This method has not found application in production due to the inherent drawbacks:

during combustion of the sludge without extraction costly VIS are not, are not used and useless burn;

when burning a large number of alcohols stands out a lot of heat, removal of solid product is technically complex, resulting in separate zones develops a high fever (up to 1000-1200oC) at which the particles are sintered catalyst, its activity decreases;

when removing VGS extraction with methyl alcohol or other solvent process is technologically complicated, requires more equipment, high energy consumption and goes into the category of increased fire and explosion;

the annealing at 600-700oC results in a catalyst with low activity.

The objective of the invention is to develop such technology for the reprocessing of irradiated copper-chromium catalyst, which will provide:

obtaining catalyst, its activity is not inferior to fresh;

the maximum recovery VGS of sludge;

improving the environment.

The essence of the technical solution mentioned is uume at a pressure of 50-300 mm RT.article (6650-39900 PA) with an additive superheated water vapor, followed by processing the resulting solid porous mass, fat-free catalyst with air at 350-450oFor oxidation of the remaining organic substances. The desired temperature interval in the processed mass support, changing the pressure, the flow rate of air, steam and steam condensate.

The catalyst mass is then cooled to 100oC with a mixture of cold air and condensation of water vapor, and then to the 40oC cold air, loosen mixer with retractable blades and auger unload in a sealed mill, in which the agglomerates are crushed to particles having a particle size original (fresh) catalyst. The crushed catalyst is loaded into a suitable container and used in the production VIS. Earlier in the reactor or in the mill, the catalyst may be blended with alcohols or methyl esters of fatty acids for easy application. Achievable technical result is characterized by a high activity of the regenerated catalyst, which is 97-99%

The regenerated catalyst activity is not inferior to the fresh catalyst. This is achieved by strictly controler.

The degree of distillation VGS is 95-98% Distilled VIS used in production for commodity VIS that allows to reduce losses VIS slurry 20-50 times.

The activity of the catalysts is determined by the hydrogenation of the standard sample distilled methyl esters of synthetic fatty acids WITH10-C18in the presence of 5% of the catalyst. Hydronaut a mixture of 200 g of methyl ester and 10 g of a catalyst in an autoclave at a hydrogen pressure of 300 at (3107PA) and a temperature of 300oC for 60 minutes In the obtained hydrogenation product after filtration the purpose of separation of the catalyst, determine the number of saponification according to standard procedures.

The activity of the catalyst is determined by the formula

,

where h O.met.EF.the number of saponification of the methyl esters;

H. O.hydrogenes.the saponification number of the hydrogenated feed is cut.

Example 1. 265,6 g catalyst sludge from the centrifuge in the production VIS by direct hydrogenation of fatty acids in Shebekino the chemical plant workshop PHC-2), loaded into a 0.5-liter glass flask, placed in an electric bath. The flask report with condenser, receiver distillate and a vacuum pump. Sludge in addition to the catalyst contains by 110.6 g of alcohols and 33.0 gut and 31.7 g of water. Then connect the vacuum pump and at a pressure of 20 mm RT.article (2660 PA) of the slurry is distilled off and condensed alcohols. The temperature of the slurry evenly over 2.5 hours increase from 150 to 395oC. the Last 0.5 h, the pressure in the flask is maintained at the level of 5-6 mm RT.article (665-798 PA). After that, the product is cooled to 40oC, the vacuum pump is shut off. From the receiver extracts 107,3 g alcohols (degree of distillation 97%), and from a flask 123,3 g catalyst comprising a after opening easily crushing the lumps. Lumps of catalyst is placed in a porcelain Cup on the electric stove and calcined in air at stirring with a spatula, with lumps of pounded into powder. The temperature of the powdered mass is maintained within the range of 380-400oC. Oxidation over 30 min, after which the temperature of the catalyst decreases. The sample obtained regenerated thus the catalyst is a powder dark gray, almost black color with a bulk weight of 1310 g/DM3. Test it with the hydrogenation of standard methyl esters of fatty acids WITH10-C18on the pilot plant showed activity of 98.5% is equal to the activity of fresh catalyst.

Example 2. In laboratory vertical to the catalyst slurry, taken after centrifuges from the shop ytr-2 Shebekino chemical company and containing 198,5 g WIS. Turn up the heat column electric bath and column serves superheated to 350-400oC water vapor. For 65 min, the product temperature is increased from 50 to 340oC. the Residual pressure in the column of 80-300 mm RT.article (10640-39900 PA), the flow of superheated steam at 200 g/h During this period, the trap system condensation accumulates 188 g VGS (95,0% from contained in the sludge). Then turn off the vacuum pump, close steam and open the air supply (3-5 l/min). The oxidation is carried out at atmospheric pressure for 5 hours, keeping the temperature in the reaction zone within 380-400oC. During oxidation spend 1200 liters of air. After cooling to 40oC product loosens, discharged from the column and crushed in a hammer mill. The regenerated catalyst is a powder dark gray, almost black. When the hydrogenation of standard methyl esters of fatty acids he showed activity equal to 98,3% of the activity of fresh catalyst to 98.5%

Example 3. The experience carried out on poster installation, comprising: a horizontal cylindrical reactor of 1 liter of steel 18CR10NITI equipped with elektroobogrevatel smarati the temperature in different zones of the reaction space; the condensing system with condensers and condensate traps; vacuum pump; gas superheater and the steam generator.

With the help of vacuum in the reactor tighten 787 g of the catalyst slurry from the same batch that used in example 2. The sludge contains 239 g of alcohols. The system is connected to a vacuum pump (pressure in the reactor during the experience is 100-160 mm RT.article which corresponds 13300-21280 PA), heated reactor and serves superheated to 340-400oC water vapor. The total steam consumption during the experience is 120, the product Temperature in the reaction zone uniformly raise from the 60oC to 360oC for 2 hours During this period from the reactor Argonauts and condenses 236 g alcohols, i.e. 98,7% of the contained in the sludge. After that, the steam supply is shut off and open the air supply (3-4 l/min). Due to the heat of the oxidation reaction, the temperature rises to 400oWith and supported within 400-420oC due to the injection into the air with a small amount (at the time of the experience consumed 20 g) condensation of water vapor. Due to the high degree of distillation of alcohols (98,7%) oxidation is completed in a short time and after 30 minutes begins to fall temperature. Oxidizes another 50 minutes, stirring the contents of the reactor elektronischen transparent, that indicates the completion of the oxidation process. During the experience spent 150 liters of air. In the condensing system, in distilled alcohols and condensation of water vapor is practically no particles of catalyst, alcohol and condensate have a light color and transparent, which indicate the absence of entrainment of dust catalyst from the reactor. The product is cooled, the reactor is open, loosen the catalyst is unloaded (550 g) and crushed in molotkovoy mill. The obtained regenerated catalyst is a fine powder dark gray, almost black color with a bulk density of 1020 g/DM3. When the hydrogenation pilot plant standard methyl esters of fatty acids he showed activity equal 99,0%

Example 4. Regeneration of the catalyst is carried out at a pilot plant comprising: a reactor with a volume of 100 l frame with a stirrer, a bubbler for the supply of steam and air and a jacket for heating pairs diphenylene mixture; superheater in the form of a heat exchanger, heated pairs diphenylene mixture; a condenser alcohols; steam-ejector vacuum pump; compressor for air supply. Charged to the reactor 61 kg catalyst slurry from the shop ytr-1 Shebekino, taut pair diphenylene mixture in the jacket of the reactor and the steam superheater. The temperature of the superheated steam is 250-270oC. For 4.5 h, the temperature of the slurry rises from 40 to 270oC and maintained for another 5 h at the level 2702oC when the total flow rate of superheated steam at 200 kg per tonne of regenerated catalyst. The pressure in the reactor is 50-70 mm RT.article (6650-9310 PA). During this period Argonauts and condenses 13,3 kg VGS (88,7%).

Stop filing defiling mixture for heating the reactor and the steam superheater, the steam flow into the bubbler and open the air supply (3 m3/h) from the compressor in the bubbler. Due to the heat of reaction increases the temperature in the mass. It is supported in the range of 430-470oserving in the bubbler wet steam. After 10.5 hours, the temperature starts to drop, the product is cooled wet steam, and then the cold air from a compressor with a spray of steam condensate. Cooled to 40oC the product is discharged, get to 32.7 kg (80%) of the regenerated catalyst in the form of a powder in dark gray with particle sizes from a few micrometers to agglomerates with a diameter of 2-3 see a Significant portion of the catalyst in the form of dust (up to 20%) is carried away from the reactor in the condensation system sledstvennogo catalyst is mixed with methyl esters of fatty acids WITH10-C18in the ratio 6:4 by weight.

The resulting mixture was passed through kraskoterke and get a finely dispersed suspension of catalyst in methyl esters. Using this technology there have been several experiments and made the party a suspension containing 500 kg of regenerated catalyst. The activity in the hydrogenation of standard methyl esters of fatty acids WITH10-C18pilot plant hydrogenation was 98,3-99,2% when activity fresh 98.2% of the Party suspension of regenerated catalyst was used instead of the fresh catalyst was used instead of the fresh catalyst in the shop ytr-1 Shebekino chemical plant.

Mileage in the shop ytr-1 showed high activity of the regenerated catalyst (98-99%) equal to activity of fresh copper-chromium-barium catalyst for the production of the Volgodonsk plant (98-99%).

During the mileage was first made ordinary party methyl esters of synthetic fatty acids with generally accepted parameters of the hydrogenation temperature 3005oC; pressure 3005 at (31075105).

Example 5. Regeneration of the catalyst is carried out on a scaled-up pilot plant comprising: a reactor volume is for even distribution of steam and air in the reaction mass, slowly rotating stirrer (8./min) with a retractable from the horizontal shaft to the walls of knives for opening the solid product; electric furnace for heating the digester; electric heaters; condensers for vapour alcohols and water; sinks alcohols and condensate; liquid ring vacuum pumps; tanks; tanks; centrifugal pumps; kraskoterke.

Catalyst slurry separated in the centrifuge in the shop ytr-2 Shebekino chemical plant, in the amount of 1120 kg using vacuum sucked into the reactor from barrels. In catalyst slurry contains 60 kg of water and 320 kg WIS. In bubblers serves superheated to 340-400oC pairs. The reactor is reported with the vacuum pump includes a furnace for heating the reactor. At a pressure of 80-150 mm RT.article (10640-19950 PA), the flow of superheated steam 20 kg/h of reaction product is heated for 12 h from 60 to 320oC. During this period was autogyros and condensed 304 kg of alcohol (95%) and 300 kg of water, including 240 kg due to condensation supplied superheated steam. Then reduce the supply of steam to 5-10 kg/h and open air supply (100-120 m3/h) from the compressor. The temperature of the product rises to 430-480oC. It supports the entire period of oxidation (27 h) within these limits, adding to wonder cooled by blowing cold air which inject the steam condensate, up to 100oC, and then only cold air.

Cooled to 40oC mass loosen mixer, gradually pushing her knives. Product in the form of crumbs mixed with small particles in the reactor is mixed with VGS in the ratio 8:2. The resulting crude powder auger serves to below the reactor kraskoterke, from which the concentrated thin suspension of particles of the catalyst in the alcohol is fed into the machine with an agitator. In this apparatus to mass add this number VIS to the suspension of regenerated catalyst in WGS was mobile and could be pumped by the pump. This experience gained 1200 kg suspension containing 760 kg of catalyst.

The sample of this catalyst batch, taken before mixing with URS, when the hydrogenation of methyl esters of fatty acids WITH10-C18on the pilot plant showed activity 97,2% with the activity fresh and 97.8% Party regenerated catalyst prepared according to example 5, was used in the shop ytr-2 Shebekino chemical plant instead of the fresh catalyst showed good activity (for 98.5-99.5 per cent) equal to activity of fresh catalyst (for 98.5-99.5% pure ).

During ispy-C18and normally accepted mode hydrovane: temperature 305-310oC, pressure 260-265 at (260105-265105PA), the supply of fatty acids 1.6 m3/h, and the catalyst mixture of 0.96 m3/PM

Example 6. The experience carried out with the setup described in example 2. In laboratory vertical column with a capacity of 1 l load 705 l sludge copper-chromium-barium catalyst from the batch used in example 2. The sludge contained 214 g WIS. In the process of heating from 50 to 340oC for 2 h under pressure 85-110 mm RT.article (11305-14630 PA) without additives superheated water vapor from the slurry Argonauts and condenses to 142.1 g VGS (66,4% of the contained in the sludge). At 340oC through the bubbler in mass discharge air (7-8 l/min). After 20 min the temperature of the mass rises to 600oC. the Oxidation is continued for 6 h at 600-700oC. over 6 h spend 2800 liters of air. After oxidation and cooling, the product is ground in a hammer mill until the particle size of the fresh catalyst. Get 495 g of regenerated catalyst in the form of a gray powder with a greenish tint. Test it in the hydrogenation process of standard methyl esters of fatty acids on the pilot plant showed low activity 28% when activity tamimah conditions, except under the conditions of distillation of alcohols and oxidation, shows the importance of maintaining optimal conditions for the distillation of alcohols and treatment of the catalyst with air.

Example 7 (the prototype). 200 g of the catalyst slurry taken from the batch of example 2, containing of 60.8 g of alcohols WITH10-C18have probalily in a porcelain Cup that is placed on an electric tile outdoors in a fume hood. In the catalyst layer placed pocket with a thermocouple. The intensity of heating of the hot plates was controlled by means of laboratory autotransformer so that the temperature of the mass was not issued from within 600-700oC. After annealing for 8 h received commoratae solid mass of gray-green. The mass was treated with 20% NaOH solution in the amount of 920 g, separated settled catalyst, washed it and dried. Received 139 g of regenerated catalyst. Test it in the hydrogenation process of standard methyl esters of fatty acids showed low activity to 30.1% in the activity of fresh catalyst to 98.5%

The proposed method for the regeneration of copper-chromium catalysts from spent catalyst sludge allows to obtain a highly active catalyst, equal acticare instead of freshly prepared, and in mixtures with different ratios.

The proposed method of sludge allocate 95-98% VIS contained in the sludge, which can be easily turned into a commodity VGS required quality.

The proposed method of regeneration of a copper-chromium catalyst for the hydrogenation of fatty acids and their esters simple to perform, has a low fire risk, has good economic (almost complete removal of the sludge and the transformation into marketable products of higher fatty alcohols; a sharp decline in consumption of fresh catalyst due to the return of the regenerated) and environmental (complete utilization of the catalyst slurry and the termination of its discharge into the dumps) indicators.

The advantage of the proposed method is that it eliminates the possibility of formation of the gas flow from the dust of the catalyst in the process of distillation VIS and oxidation. Typically, heat treatment and oxidation of the powdered catalyst are under stirring in a rotary drum furnaces, forming a dust catalyst, carry out the decomposition, steam, air or other gases. Capture fine dust catalyst is technically challenging, inevitably results in the working conditions of staff.

In the proposed method of heat treatment (dry distillation of alcohols and the oxidation carried out without mixing in a stationary layer of a catalyst comprising a porous non-dusting solid mass, through which quite easily blown steam and air. The grinding of the catalyst is carried out or a wet method or dry in an airtight mills without blowing gas.

The method developed at laboratory, pilot-narabotany installations, and experimental batch of regenerated catalyst in the amount of 500 and 1500 kg were successfully tested in production VIS as a substitute for fresh catalyst.

Method of regeneration of a copper-chromium catalyst for the hydrogenation of fatty acids and their esters to alcohols from spent catalyst slurry comprising the heat treatment of the sludge in the presence of oxygen-containing gas, characterized in that before heat treatment, the sludge is heated to 300 to 400oC at a pressure of 5 to 20 mm RT.article or in a current of superheated steam at a pressure of 50 to 300 mm RT.article and heat treatment is conducted at 350 to 450oTo stop the absorption of oxygen, followed by cooling and grinding the obtained catalyst mass to the particle size of the fresh to the

 

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22 cl, 1 dwg, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of regenerating catalytic activity of a spent hydrogen processing catalyst which does not contain an additive. A method is described for regenerating catalytic activity of a spent hydrogen processing catalyst which does not contain an additive (versions), which involves: bringing a spent non-additive containing hydrogen processing catalyst which contains a metal component and carrier material, which has low catalytic activity with respect to the catalyst in fresh state before its use, which results in the catalyst being spent, with a solution, where the said solution contains a chelating agent chosen from a group of compounds consisting of amino carboxylic acids, and a solvent, and where said contacting takes place in a period of time longer than 10 hours, with provision for regenerated catalytic activity, obtaining old catalyst containing said chelating agent and said solvent, where said spent hydrogen processing catalyst contains amount of said chelating agent in the interval from 0.005 mole of chelating agent per mole of active metal to 1 mole of chelating agent per mole of active metal; keeping said old catalyst in conditions which include drying temperature so as to remove part of said solvent from said old catalyst with removal of not less than 50 wt % of said chelating agent from said old catalyst, obtaining dried old catalyst as a result; and treatment of said dried old catalyst with sulphur, obtaining regenerated catalyst. Also described is a catalyst produced using methods described above and hydrogen processing method, involving bringing hydrocarbon starting material in hydrogen processing conditions with a catalyst produced using methods described above.

EFFECT: higher degree of regenerated catalytic activity of spent hydrogen processing catalyst.

19 cl, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of separating and freeing a catalyst during conversion of oxygen-containing compounds to olefins, involving the following steps: (a) converting oxygen-containing compounds to olefins in a fluidised zone in a reactor in the presence of a molecular sieve type catalyst, having carbon-containing deposits, where said oxygen-containing compounds are selected from a group consisting of methanol, ethanol, dimethyl ether or mixtures thereof; (b) tapping the output stream containing olefins from the reactor, where the output stream surrounds part of the catalyst, having carbon-containing deposits; (c) separation of part of the catalyst from the output stream through contact of the output stream with neutralised liquid slaking medium in a slaking column in order to form a stream which contains the catalyst; where neutralisation of the slaking medium is carried out in a separate section after separating part of the catalyst; and (d) burning in an installation for burning carbon-containing deposits which are in that part of the catalyst which lies in the stream containing the catalyst.

EFFECT: method increases efficiency of the process by preventing accumulation of acids in the recycled slaking water.

10 cl

FIELD: oil and gas production.

SUBSTANCE: here is disclosed procedure for processing gas condensate consisting in its preliminary heating in corresponding process vessels, in contacting in adiabatic reactor at temperature 320-480°C and pressure 0.1-4 MPa with zeolite containing catalyst, in cooling and in separation of reaction products into gaseous and liquid fractions by separation and rectification, and in successive oxidising regeneration of catalyst. Also, prior to process of regeneration heavy resins collected on catalyst are removed by vacuumising of adiabatic reactor during 0.5-6.0 hours. Catalyst is regenerated in a regenerator at temperature 350-620°C and pressure 0.1-0.2 MPa with air with contents of oxygen 21 vol. %. Upon heating an upper or lower layer of catalyst air is supplied from a side opposite to a heated layer.

EFFECT: reduced time for processing gas condensate due to reduced process of regeneration of coked catalyst and reduced expenditures for regeneration process.

3 cl, 1 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to methods of regenerating catalysts. Described is a method of regenerating a catalyst for producing 4,4-dimethyl-1,3-dioxane by firing coke and resin in the presence of water vapour and air or an oxygen-containing mixture in series-connected reactors at temperature 400-500°C and pressure in the first reactor of 0.9-1.4 atm and pressure at the output of the second reactor of 0.5-0.7 atm.

EFFECT: low specific consumption of water vapour and other energy resources.

3 cl, 3 ex

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