The composition of the sorbent, the method of obtaining the composition of the sorbent and the use of a composition of the sorbent

 

(57) Abstract:

The invention relates to sorbent to remove sulfur. The composition of the sorbent includes: zinc-containing component, the component colloidal oxide component is a metal oxide. The mixture components thermoablative at 50-800C and treated with steam, which improves its ability to absorb sulfur. 2 C. and 14 C.p. f-crystals, 2 tab.

The invention relates to the composition of the sorbent, the method of obtaining the composition of the sorbent and the use of a composition of the sorbent.

The necessity of selection and removal of sulfur from streams of liquid or gas existed for a long time. For example, if sulfur-containing stream of liquid or gas is a waste product, the removal of sulfur from such a stream is necessary to protect the environment from pollution, and if containing sulfur stream of liquid or gas should be used in the catalytic process, the removal of sulfur necessary to prevent contamination of the catalyst.

The sorbents used in the processes of removing sulfur from sulfur-containing flow of liquid or gas, with time dirty grey that their sorption capacity is significantly reduced. Therefore, to restore the sorption capacity of their water vapor, which can significantly reduce the effectiveness of such sorbents for removal of sulfur.

Brief description of the invention

The subject of this invention is the composition of the sorbent.

Another object of this invention is the composition of the sorbent, which is treated with water vapor.

Another object of this invention is a method of obtaining a composition of the sorbent.

The subject of this invention is also a method of using the composition of the sorbent.

The sorbent composition in accordance with this invention includes: (a) zinc-containing component; (b) the colloidal oxide; and (C) component is a metal oxide.

The sorbent composition in accordance with this invention includes: (a) zinc-containing component; (b) the colloidal oxide; and (c) component is a metal oxide, the composition of the sorbent is subjected to the steam treatment.

In accordance with this invention is a method of obtaining includes the following stages: (a) a zinc-containing compound of the component, the component colloidal oxide component and a metal oxide; (b) steam treatment compositions obtained in stage (a), when the temperature is the invention of a method of removing sulfur from sulfur-containing flow of liquid or gas includes contacting the specified sulfur-containing flow of liquid or gas with composition includes zinc-containing component, the component colloidal oxide component and a metal oxide.

Detailed description of the invention.

The sorbent composition of this invention include (or optionally consists essentially of, or consist of) a zinc-containing component, the component colloidal oxide component and a metal oxide.

In General, the zinc component is zinc oxide. However, it can be a compound which is capable of being converted to zinc oxide under the conditions of obtaining compositions described next. Examples of such compounds include, but are not limited to this list, zinc sulfide, zinc sulfate, zinc hydroxide, zinc carbonate, zinc acetate and zinc nitrate. The amount of zinc-containing component in the composition of the sorbent of this invention is in the range of from about 10 to about 90 weight. % based on the total weight of the composition of the sorbent. The preferred amount is from about 25 to about 75 wt.%, most preferably a number in the range from about 40 to about 60 wt.%.

In the General case, the colloidal oxide is a liquid the x particles is in the range from about 10 to about 10000 angstroms. Typically, the concentration of solid particles in such components of the colloidal oxide may be in the range from about 1 to about 30 wt.% based on the total weight of the component. the pH component of the colloidal oxide may be from about 2 to about 11, depending on the method of obtaining a colloidal oxide. In another embodiment of the colloidal oxide may be a solid material containing particles of a metal oxide. For example, the colloidal oxide may be a powder containing particles of metal oxide. However, in the case where the colloidal oxide is a solid substance containing particles of metal oxide, it must have the ability to easily dispergirujutsja in a liquid medium. In other words, if a component of the colloidal metal oxide is a solid substance containing particles of metal oxide, then the conditions for obtaining a composition described below, the colloidal oxide must possess the ability to form the dispersion, the particle size of which corresponds to the size of colloidal particles. In the preferred embodiment the metal oxide is chosen from the group comprising alumina, silica, cerium oxide, yttrium oxide, copper oxide, iron oxide, ecocidal. In the General case in a more preferred embodiment the component colloidal oxide comprises colloidal alumina, colloidal silica or a mixture thereof. In the composition of the sorbent, the amount of metal oxide from the colloidal oxide is from about 1 to about 30 wt.% based on the total weight of the sorbent composition, but preferably a number in the range from about 1 to about 20 wt.% and most preferably a number in the range from about 5 to about 15 weight. %.

Component metal oxide may be a metal silicate, a silicate of a metal or a mixture. The metal component of the metal oxide can be selected from the group comprising beryllium, magnesium, calcium, strontium, barium, radium, zinc, cadmium, mercury and mixtures thereof. However, the preferred magnesium, calcium, zinc and mixtures thereof, the most preferred zinc. Examples of such components include, but are not limited to this list, magnesium silicate, calcium silicate, secondary acidic calcium silicate, zinc silicate, calcium aluminate and zinc aluminate. The quantity of the component metal oxide present in the sorbent composition is from about 5 to about 90 wt.% IDO about 75 wt.%, most preferably the content is in the range from about 15 to about 60 wt.%. In another embodiment of the component metal oxide can be formed in the process of obtaining the composition of the sorbent. For example, zinc oxide and silica can be connected in the process of sorbent and subjected to thermal or hydrothermal treatment, in which the component is formed of metal oxide, which is a silicate of zinc.

The above three components can be connected by any known method. In addition, they can be added in any sequence. Components after the initial connection can be agglomerated by any known method. Such agglomeration may include phase separation, which can be obtained particles of a certain size. Additionally, the operation of the sieving can be carried out after any drying or calcination.

Usually after agglomeration of the components they pass the stage of drying. This stage is used to remove the liquid medium component of the colloidal oxide. Stage drying can be carried out at any temperature suitable to remove essentially all of the liquid environment. These temperatures are usually zaklyucha region from approximately 100 to approximately 200oC. the drying Time depends on the type of liquid medium and drying temperature, but in the General case, the time average of from about 0.5 hour to about 4 hours is preferred.

The dried composition can then be calcinate to obtain a calcined composition. The calcination may be conducted under any suitable conditions, under which is the removal of residual water, the oxidation of any combustible materials and/or education component containing a metal oxide. The dried composition can be calcinate in oxygen. In General, the temperature at which the calcination is in the range of from about 300 to about 1300oC, more preferably when the temperature is from about 450 to about 1100oC. the Calcination should be carried out for from about 0.5 hours to about 24 hours. In General, any component, in which zinc is present not in the form of oxide, may be converted at this stage of the process of obtaining a composition in zinc oxide. Therefore, under these conditions, the zinc oxide and silica can be connected with the formation of silicate of zinc.

Sometimes is necessary to improve the physical and chemical properties of the sorbent composition. For example, such promoters, representing the oxides of metals of group VIII, can increase the ability of the composition of the sorbent to gidrirovanii oxide sulfur in the sulfide. Therefore, these promoters can increase the ability of the composition of the sorbent to be regenerated after a failover in the process of removing sulfur. Examples of suitable oxides of metals of group VIII, which can be used as promoters include, but are not limited to this list, iron oxide, cobalt oxide, Nickel oxide, ruthenium oxide, palladium oxide, osmium oxide, nitric oxide iridia and platinum oxide. The amount of promoter in the composition of the sorbent is in the range of from about 0.1 to about 20 wt.% based on the weight of the sorbent composition. However, more preferably a number in the range from about 1 to about 15 wt.%, most preferably from about 5 to about 10 wt.%.

The promoter can be added to the sorbent composition in the form of metal, metal oxide and/or metal containing compounds, which can turn into metal oxides in terms illnerova described above. Some examples of such metal - containing compounds include acetates, metals, Carbo is dinani.

The metal, metal oxide and/or metal-containing compound can be added to the sorbent composition by any known method. One such method is the impregnation of the composition of the sorbent solution in water or in an organic solvent containing a metal, metal oxide and/or metal-containing compound. After adding in the composition of the sorbent of metal, metal oxide and/or metal-containing compounds promoted composition is dried and calicivirus, as described above.

The metal, metal oxide and/or metal-containing compound can be added to the composition of the sorbent in the form of components of the original mixture or after the drying and calcination of the sorbent composition. In that case, when the metal oxide as a promoter is added to the sorbent composition after drying and calcination, promoted thus the composition is dried and calicivirus again. Drying is conducted preferably at a temperature of from approximately 50 to approximately 300oC, more preferably at a temperature of from approximately 100 to approximately 250oC. the Drying is conducted for from about 0.5 to about 5 hours, Bo is ositio then calicivirus in the presence of oxygen or oxygen-containing gas at a temperature of from about 300 to about 800oC, more preferably at a temperature of from about 450 to about 750oC until volatile matter is removed and until at least part of the metal, which is contained in its pure form, is not converted into a metal oxide. The time required for the on-going therefore the calcination will generally be from about 0.5 to about 4 hours, preferably from about 1 to about 3 hours.

In another embodiment of the present invention the composition of the sorbent is treated with steam. This steam treatment comprises contacting the sorbent composition with a gaseous mixture of air and water vapor. If necessary, this mixture may also contain other gases such as nitrogen, helium and argon. The flow of gaseous mixture should contain from about 5 to about 90 volume percent water, and the rest must be the air. Preferably the mixture of steam should contain from about 10 to 80 vol.% water, and the rest must be the air. Steam treatment should be carried out at a temperature in the range from approximately 100 to approximately 1100oC, preferably at temperatures from approx the temperature dependent where is the steam treatment. Typically, the contact time steam mixture with the composition of the sorbent is from about 1 to about 24 hours, preferably from about 2 to about 8 hours. The steam treatment can be performed before and after the introduction of the promoter is a metal oxide of group VIII. Additionally you can carry out one or more treatments of steam to obtain a desired composition of the sorbent. Therefore, the composition of the sorbent, which is then subjected to the steam treatment can be a dry powder that comes into contact with steam mixture or composition can be a water-containing composition, which is subjected to the action of the above high temperature.

The sorbent composition of this invention can be used in the methods of sulfur removal, in which there is a contact (contact) composition of the sorbent with serosoderjaschei gaseous stream, and then contact the sorbent composition with oxygen or oxygen-containing gas, which is used for regeneration of the sorbent. Method of removing sulfur is not limited to use of any particular equipment. This process can be carried out using HDMI is gushima layer. Examples of such processes are described in U.S. patents NN 4990318; 5077261; 5102854; 5108975; 5130288; 5174919; 5177050; 5219542; 5244641; 5248481 and 5281445; which is entered in the reference list of this invention. The sorbent composition of the present invention is particularly useful when implementing such methods of sulfur removal, which is carried out at temperatures from about 300 to about 800oC. in Addition, they are particularly useful in the processes of removing sulfur, which is carried out at temperatures from about 430 to about 650oC. Thus, the sorbent composition is particularly useful in processes carried out at temperatures in the range from about 475 to about 625oC.

EXAMPLES

These examples are given to illustrate the invention. Specific reagents, conditions etc. are given only to illustrate the invention and do not limit the scope of the present invention.

EXAMPLE 1

Mix 158,9 g of calcium silicate Micro-Cel T-38 (Celite Corporation, Lopoc, CA) and 198,6 g of powdery zinc oxide for 10 minutes in the mixer receives the sorbent. This song impregnorium spraying solution 197,0 g of alumina brand Nyacol Al-20 140 g of deionized water. The material obtained is stirred for another 35 minutes. Education and the temperature of 635oC for one hour. The dried agglomerates granularit in the granulator equipped with a sieve of 50 mesh (Stokes Pennwalt, Warminster, PA, Model 43 Oranulater). Two hundred and fifty grams of granular material is placed in a rotary mixer and impregnorium solution 74,27 g of Nickel nitrate in 135,3 g of deionized water. The mixture is then dried at a temperature of 150oC for one hour and calicivirus at a temperature of 635oC for one hour. The product is sieved through a sieve of 50 mesh) to remove particles larger than 50 mesh and less than 200 mesh. Two hundred and fifty grams of sifted product again impregnorium, use a solution 24,75 g of Nickel nitrate in of 122.5 g of deionized water. This material is dried at a temperature of 121oC during the night. The dried product is designated as "Sorbent".

Twenty grams of the Sorbent And placed in a quartz tube and passed through a sorbent mixture consisting of deionized water, air and nitrogen with the same content of these components and with such speed that the flow rate of deionized water is 8.0 cm3/h, air, 250 cm3/hour and nitrogen 7500 cm3/hour. The mixture is passed within 24 hours at a temperature of 760oC. the resulting material is designated as the arch Celite placed in the mixer. In the process of mixing the powder impregnorium for 6-8 minutes or 24.4 pounds (9107,1 g) colloidal alumina brand Nyacol Al-20, using a pump and a spray nozzle. To this mixture is added a slight excess of 25.0 pounds (9331 g) of zinc oxide and again stirred for 22-24 minutes. If necessary, can be used scraper mixers with different types of scrapers to obtain a homogeneous mixture. The total time of mixing, including the addition of alumina, does not exceed thirty minutes. The moisture content in the mixture is 26-27%. In such conditions, the mixture has the appearance of wet powder. The mixture is ekstragiruyut in a screw extruder with a water-cooled drum to maintain the temperature at the level of 45-50oC. the Extrudate is dried on a pallet in circulating air at a temperature of 150oC for three hours. The dried extrudate calicivirus at a temperature of 635oC for one hour using a belt furnace for firing. The resulting mixture impregnorium solution 134,7 g of Nickel nitrate uranyl in sufficient water to obtain 85% moisture. After impregnation, the material is dried at a temperature of 150oC for three hours and calicivirus at a temperature of 635oC for which the manual, similar to the processing described for Sorbent A. the resulting material is referred to as the Sorbent D".

Removal of sulfur from gases

In this experience sorbents sequentially come into contact at a temperature 427-649oC with hydrogen sulfide diluted such gases as carbon and nitrogen, and the temperature 593-649oC with air. During contact of the sorbent with a hydrogen sulfide contamination of the sorbent will be complete when the hydrogen sulfide will be present in the output stream in the amount of 100 ppm. At this time, begin the regeneration of the sorbent by the contact with air. The results are shown in table.1.

Comparison of data obtained for sorbents a and b shows that the latter has a higher content of sulfur at temperatures of more than 430oC, but less than 650oC, which shows the beneficial effect of steam treatment. Comparison of these Sorbents C and D shows that the comparative sorbent has a similar behavior when the steam is not present in the regenerating gases. However, when steam is present in the regenerating gas to the Sorbent D, the sulfur content is significantly reduced.

EXAMPLE 2

This example is carried out according to the method of the present invention sorbent of this sobremesa matrix, containing silicate of zinc.

Mix 1584 g of zinc oxide and 216 g of Celite (silica) in the mixer for 5 minutes to get the sorbent. The resulting powder impregnorium by spraying with a solution of 250 g of alumina Vista Dispal in 450 g of deionized water. The obtained wet pasta aglomerados drying at a temperature of 150oC for 3 hours, and calcining in air for one hour at a temperature of 635oC. the Dried material granularit in the granulator mark Stokes Pennwalt, Warminster, PA, Model 43 Granulater, equipped with a strainer (50 mesh). 151 g of fraction 20-140 mesh is placed in a quartz reactor and treated with a mixture of 1.0 cm3/min of deionized water and 336 cm3/min of air at a temperature of 870oC for 20 hours. 125 g otvarennogo material is placed in a rotary mixer and impregnorium solution of 37.1 g of Nickel nitrate on 26.6 g of deionized water. This material is then dried at a temperature of 150oC and calicivirus at a temperature of 635oC for one hour. The resulting material is designated as "Sorbent E". Analysis using x-ray diffraction shows that the composition of the sorbent is present in 22.1 wt.% zinc-silicate together with zinc oxide and Nickel oxide. The analysis also shows that the composition barbentane sulfur from gases like sorbents A-D. The results are shown in table. II.

The data in the table.II, show that the Sorbent E is also effective in removing sulfur from gases at high temperatures and in wet conditions. These data differ from the data for sorbent D, tested in wet conditions. It is noted that while the content of active zinc Sorbent E in accordance with the calculations should be 57.5 wt.%, the content of active zinc sorbent E should be at 46.6 wt.%, the increase in the content of 23.4% active zinc sorbent is not enough to improve the sulphur content of more than 400% with the same number of cycles of regeneration with steam (compare cycle 11 Sorbent D cycle 12 Sorbent E after nine cycles of steaming).

1. The composition of the sorbent comprising zinc-containing component, the component colloidal oxide component and a metal oxide, the composition is subjected to temperatures of 50 - 800oWith the removal of almost all of the liquid medium and the composition is then treated with steam at a temperature of 100 - 1100oC.

2. The composition of the sorbent under item 1, characterized in that the steam treatment includes contacting the composition of the sorbent with steam mixture, merit 5 - 90% vol. water.

4. The sorbent composition according to any one of the preceding paragraphs, characterized in that it further comprises a promoter and a metal oxide of group VIII.

5. The composition of the sorbent under item 4, wherein the promoter is an oxide of a metal of group VIII is present in quantities of 1 to 15 wt.% based on the weight of the specified composition of the sorbent.

6. The sorbent composition according to any one of the preceding paragraphs, characterized in that it is subjected to the action of temperatures from 100 to 1100oC.

7. The sorbent composition according to any one of the preceding paragraphs, characterized in that the zinc-containing component is present in the amount of 25 to 75 wt.%, preferably 40 to 60 wt.%.

8. The sorbent composition according to any one of the preceding paragraphs, characterized in that the colloidal oxide comprises a metal oxide selected from the group comprising alumina, silica, titanium oxide, zirconium oxide, tin oxide, antimony oxide, cerium oxide, yttrium oxide, copper oxide, iron oxide, manganese oxide, molybdenum oxide, tungsten oxide, chromium oxide and mixtures thereof.

9. The sorbent composition according to any one of the preceding paragraphs, characterized in that the specified component of the colloidal oxide is used in such Kolobok cases, based on the weight of the specified composition of the sorbent.

10. The sorbent composition according to any one of the preceding paragraphs, characterized in that the specified component metal oxide contains a metal selected from the group comprising magnesium, calcium, zinc and mixtures thereof.

11. The sorbent composition according to any one of the preceding paragraphs, characterized in that the specified component metal oxide is present in an amount of 10 to 75 wt.% based on the weight of the specified composition of the sorbent.

12. The method of obtaining the composition of the sorbent, comprising contacting the zinc-containing component, the component colloidal oxide component and a metal oxide, the impact on contacting a composition temperature of 50 - 800oWith the removal of almost all of the liquid medium and processing the resulting composition ferry, which is carried out at 100 1100oC.

13. The method according to p. 12, characterized in that the steam treatment includes contacting the specified composition of the sorbent with steam mixture containing water and air.

14. The method according to p. 13, characterized in that the steam mixture contains 5 to 90 vol.% water.

15. The method according to any of paragraphs.12 to 14, characterized in that the composition of the sorbent is exposed to 100 - 1100oC.

16. The composition of the sorbent on the Sabbath.

 

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