US20150151237A1 - Use of iron ore agglomerates for acid gas removal - Google Patents
Use of iron ore agglomerates for acid gas removal Download PDFInfo
- Publication number
- US20150151237A1 US20150151237A1 US14/614,487 US201514614487A US2015151237A1 US 20150151237 A1 US20150151237 A1 US 20150151237A1 US 201514614487 A US201514614487 A US 201514614487A US 2015151237 A1 US2015151237 A1 US 2015151237A1
- Authority
- US
- United States
- Prior art keywords
- pellets
- sorbent
- acid gas
- fluid stream
- starch
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/0005—Degasification of liquids with one or more auxiliary substances
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/0407—Constructional details of adsorbing systems
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28085—Pore diameter being more than 50 nm, i.e. macropores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
- B01D2253/11—Clays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
- B01D2253/1124—Metal oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/30—Physical properties of adsorbents
- B01D2253/302—Dimensions
- B01D2253/304—Linear dimensions, e.g. particle shape, diameter
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/304—Hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/306—Organic sulfur compounds, e.g. mercaptans
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/40—Further details for adsorption processes and devices
- B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
- B01J2220/56—Use in the form of a bed
Definitions
- This invention relates to a composition for fluid treatment and processes for making and using the composition.
- the invention relates to a regenerable sorbent for the removal of hydrogen sulfide from production fluid streams and processes for making and using the sorbent.
- Hydrogen sulfide can be present in various fluid streams and is often found in fluid streams associated with petroleum and gas production. The removal of the hydrogen sulfide from these fluid streams is desirable because of its toxicity, corrosive properties, and unpleasant odor.
- the sorbent for the removal of hydrogen sulfide employed in the current application is not only cost effective through its ability to be easily renewed, the process also exhibits high single pass performance in its ability to remove hydrogen sulfide from a production fluid stream.
- the primary object of the present invention is to provide a renewable sorbent for the removal of acid gas from a fluid stream.
- composition for the removal of acid gas from a fluid stream comprising iron mineral, vermiculite and starch.
- a process for the removal of acid gas from a fluid stream comprising the steps of: crushing a composition comprising vermiculite and an iron mineral; sifting the crushed vermiculite and iron mineral composition; calcinating the vermiculite and iron mineral composition; and contacting the calcinated vermiculite and iron mineral composition with the fluid stream.
- FIG. 1 illustratively depicts a non limiting process for the manufacture of the renewable sorbent.
- FIG. 2 graphically depicts the H2S adsorption of differing concentrations and compositions of the renewable sorbent.
- FIG. 3 graphically depicts the drop in H2S pressure in the system after regenerization.
- FIG. 4 graphically depicts the trend for the H2S absorption values and regeneration stages.
- FIG. 5 graphically depicts the percentage of sulfur accumulated on the pellets according to the reutilization/regeneration cycle.
- FIG. 6 graphically depicts the H2S adsorption of the renewable sorbent at differing calcinating temperatures.
- FIG. 7 graphically depicts the H2S adsorption of the renewable sorbent at differing experimental conditions.
- the invention relates to a cost effective system and process for the removal of acid gas from fluid streams.
- fluid includes but is not limited to matter in gaseous and/or liquid state.
- the term “fluid” may refer to any one or all of the following terms: oil, gas, water, liquids in an oil well, gases in an oil well, air and the like.
- step 1 the general steps for manufacturing the renewable sorbent of the present invention.
- Raw materials are obtained in step 1, for example from a national market such as Venezuela, where raw material, such as iron mineral and an expansive clay, may be easily obtained.
- the raw materials are then dried at 100° C. for about 24 hours. After drying the raw materials are then mixed together into a composition before they are crushed and sifted in a milling process 2.
- the milling may be carried out under any procedure that is well known within the art.
- the dried raw material may be milled by a planetary ball mill.
- the raw material is milled to obtain a desired particle size of between about 50 microns to about 200 microns.
- the milled material may then be sifted through a 100 mesh sieve 3. In order to facilitate pelletization of the iron ore, the milled material is sifted to remove particles or materials that are above about 150 microns.
- the raw material composition may be pelletized 4.
- the pelletization of the composition may be carried out under any procedure that is well known within the art, such as a tilted rotary disk, the pelletizing drum, the pelletizing disk and/or the pelletizing cone.
- organic or inorganic binders such as clays, cassava starch, potato starch and/or corn starch; admixtures, such as organic or inorganic binders in altering proportions; and water may be added to the ground raw material in order to control the binding strength of the pellets, to improve the mechanical properties of the pellets, to diminish thermal shock cracking of the pellets and to increase the strength of the pellets once they are burned.
- the particle size of the raw material may be less than 75 microns (200 mesh).
- Pelletization process factors include the fineness of the ground raw material, input flow of the ground raw material, the humidity content of the ground raw material and the mineralogy of the ground raw material.
- Process formation of the pellets by pelletizing disk is characterized by the formation of a flow pattern that ranks particles among three classes: Input fineness, the ground raw material entering the disk; Primary agglomerates, the initial pellet core; and Final pellets. Pellets are formed inside the disk due to the disks rotation, inclination and the homogenization of the mixture.
- the pelletizing disk is continuously and steadily fed with the ground raw material as a liquid, such as water, is sprayed over the ground raw material inside the rotating pelletizing disk.
- the liquid drops collect rotating particles forming a primary agglomerate seed with increased density.
- the seed becomes denser as the liquid disturbed on its surface continues to collect ground raw material.
- the newly formed fresh or green pellet is extracted from the pelletizing disk once the desired pellet size is reached.
- the pelletization process preferably results in iron ore agglomerate pellets of approximately 1 centimeter in size.
- the composition is calcined 5.
- the calcination process may be carried out by any procedure that is well known within the art. In order to prevent evaporation of the liquid and a violent breakage of the green iron ore agglomerate pellets, the temperature of the green pellets is gradually increased at a rate of 10° C. per minute until they are calcined at a temperature of about 500° C. to about 600° C.
- the raw material used in this regenerable sorbent may include iron mineral, expansive clays and starch.
- the iron mineral may be an iron oxide obtained from Planta de Pellas Ferrominera del Orinoco (FMO) in Bolivar State.
- Other iron minerals that may be employed in the present invention include and are not limited to hematite, magnetite, maghemite and mixtures thereof.
- the expansive clay may be any expansive clay, such as vermiculite, bentonite, montmorillonite, blends of chlorite, kaolinite and mixtures thereof.
- the starch may be potato starch, corn starch, cassava, waxy corn and mixtures thereof.
- the resultant sorbent may then be exposed to a fluid stream containing acid gases. Due to a chemical reaction between the molecules of the acid gases in the fluid stream and the sorbent, gaseous particles are attracted to the sorbent. The acid gas particles in the fluid stream react with the molecules of the sorbent and are thus removed from the fluid stream.
- H2S acid gas hydrogen sulfide
- the pelletization step 4 of FIG. 1 may be skipped or altered.
- the pelletization step is employed as a preferred shape for the inventive sorbent; however, the resultant shape of the sorbent may be any shape or design that is suitable for use in the removal of acid gas from a fluid stream. These shapes and designs include pellets, fine particles, shavings, calcined chips and muds.
- the absorption of the commercial sorbents is compared to a pelletized sorbent containing raw material comprising iron oxide and 2.5% w/w (by weight) vermiculite VPE 2.5, a sorbent containing raw material comprising iron oxide and 5% w/w vermiculite VPE 5, a sorbent containing raw material comprising iron oxide, 2.5% w/w vermiculite, 2.5% w/w starch MPE 2.5, a sorbent containing raw material comprising iron oxide, 5% w/w vermiculite and 5% w/w starch MPE 5 and a sorbent containing raw material comprising iron oxide and 2.5% w/w starch APE 2.5.
- FIG. 2 shows the H2S adsorption capacity of pellets with 5% vermiculite to be 0.21 lb H2S/lb sorbent VPE 5 and pellets prepared with 5% vermiculite and 5% starch have an increased adsorption capacity of 0.23 lb H2S/lb sorbent MPE 5.
- These adsorption capacities place the raw material composition of iron mineral, vermiculite and starch within the efficiency range of the adsorption capacities of commercial sorbents.
- the sorbent may be removed and regenerated.
- the sorbent is regenerated by treating the reacted sorbent with hydrogen peroxide.
- Hydrogen peroxide in the presence of an iron catalyst results in an oxidation known as Fenton's reaction. The procedure involves the oxidation of Fe 2+ to Fe 3+ by hydrogen peroxide, yielding hydroxyl radicals:
- pellets After the pellets are exposed to the acid gas stream and/or oil stream they are composed of iron sulfurs. The pellets are regenerated by exposing them to H2O2:
- the black exposed pellets are embedded in hydrogen peroxide (3% m/v) for 24 hours.
- the pellets recover their initial red color as a result of the oxidation of iron to maghemite and hematite, respectively. Traces of sulfur were found in the oxygenated water after washing out the pellets.
- FIG. 3 graphically depicts the pressure drop values for three subsequent uses of the pellets.
- FIG. 3 shows a H2S pressure drop for each stage of reutilization/regeneration of pellets containing 5% of vermiculite.
- the pressure drop is an indicator of the H2O2 regenerative capacity of the 5% VPE pellets.
- FIG. 4 displays the experimental trend for the H2S adsorption capacity values estimated from the H2S pressure drop.
- FIG. 4 shows that while the number of regenerations of the pellets increases, the mass of H2S that can be removed from the system decreases; however, after three regenerations the same pellet is still able to remove acid gas.
- the percentage of sulfur accumulated on the pellets grows according to the reutilization/regeneration cycles. It can be inferred from FIG. 5 that following three cycles of regeneration, the pellets adsorption capacity is affected, diminished or depleted, possibly due to Fenton's reaction, i.e. sulfur obstructs the pellets active collection centers. However, upon further testing, after reacting to H2S and being subject to a bath with hydrogen peroxide for approximately 24 hours, the pellets mechanical strength was higher than the initial mechanical strength.
- Table 2 lists some physical and chemical characteristics of the 5% MPE sample (5MPE) and the 5% VPE sample (5VPE).
- FIG. 6 depicts the adsorption capacity of pellets calcined at about 500° C. to about 600° C.
- the absorption of CVG 12 and the commercial sorbents, Sulfatreat XLP 11, and Sulfatreat STD 10, is compared to a pelletized sorbent containing raw material comprising iron oxide and 5% w/w (by weight) vermiculite calcined at 500° C. VPE 5-500 and 600° C. VPE 5-600, along with a sorbent containing raw material comprising iron oxide, 5% w/w vermiculite and 5% w/w starch calcined at 500° C. MPE 5-500 and 600° C. MPE 5-600.
- FIG. 6 confirms that raw material compositions VPE 5-500, VPE 5-600, MPE 5-500 and MPE 5-600 exhibit an efficiency that is either within the range of the commercial sorbents or comparable to the commercial sorbents.
- the raw material composition comprising iron oxide, 5% w/w vermiculite and 5% w/w starch calcined at 500° C.
- MPE 5-500 exhibits the most efficient adsorption capacity of approximately 0.23 lb H2S/lb sorbent.
- FIG. 7 evaluates the raw material composition comprising iron oxide, 5% w/w vermiculite and 5% w/w starch calcined at 500° C. MPE 5-500 at differing experimental conditions.
- the MPE 5-500 composition was evaluated against CVG 12 and the commercial sorbents, Sulfatreat XLP 11, and Sulfatreat STD 10, for the absorption capacity of pellets with a diameter of 0.5 cm 20, for the effect of 0.6 ml of water on the pellets 21, and for the effect of regeneration after treatment with hydrogen peroxide.
- the MPE 5-500 composition remains effective at a pellet diameter of 0.5 cm. Additional tests have shown that as the diameter of the pellet diminishes in the fluid stream the adsorption capacity can increase. FIG. 7 also shows that after the MPE 5-500 composition has been exposed to the fluid stream, the composition may be reacted with hydrogen peroxide to again obtain a H2S removal efficiency of 0.20 lb H2S/lb sorbent.
- the regenerable sorbent of the present invention is used within a cost effective process for the removal of hydrogen sulfide from production fluid streams.
- the regenerable sorbent for the removal of acid gas employed in the current application is not only cost effective through its ability to be easily renewed through a reaction with hydrogen peroxide, the process also exhibits high single pass performance in its ability to remove up to 0.23 lb H2S/lb sorbent from a production fluid stream.
- the regenerable sorbent of the present invention may be inexpensively made from materials found within national markets, such as Venezuela.
- the combination of iron mineral, expansive clay and starch may be employed in a variety of sweetening plants to remove acid gases from numerous production fluid streams.
- the acid gas may be any gas in which it is desirable to remove acids, such as hydrogen sulfide, sulphide carbonyl, mercaptans and mixtures thereof.
- regenerable sorbent of the present invention may be implemented in other possible applications.
- the final characteristics of the regenerable sorbent of the present invention may be applied to conventional well technology, and any application that may benefit from the extraction of acid gases from fluid streams.
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Nanotechnology (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
A regenerable sorbent for the removal of acid gas from a fluid stream. The regenerable sorbent is made from raw materials such as iron mineral, expansive clay and starch. Acid gas is removed from the fluid stream by a process where the raw materials are obtained, crushed, sifted, possibly pelletized, calcined and contacted with the fluid stream containing the acid gas.
Description
- This invention relates to a composition for fluid treatment and processes for making and using the composition. In particular, the invention relates to a regenerable sorbent for the removal of hydrogen sulfide from production fluid streams and processes for making and using the sorbent.
- Hydrogen sulfide can be present in various fluid streams and is often found in fluid streams associated with petroleum and gas production. The removal of the hydrogen sulfide from these fluid streams is desirable because of its toxicity, corrosive properties, and unpleasant odor.
- Due to the increased need for greater natural gas production, the removal of hydrogen sulfide from production fluid streams has become essential. Prior art processes can be based upon physical absorption, solid absorption or chemical reaction.
- These prior art processes are associated with numerous problems. Some require sorbents that when exposed to air are self igniting and thus non-renewable. The weak sulfur retention of these non-renewable sorbents leads to an adverse environmental impact and requires that after their use they be treated as hazardous waste. The prior art processes employing non-renewable sorbents that produce hazardous waste have proven to be costly.
- There continues to be a need within the petroleum and gas production industry for a cost effective process for the removal of hydrogen sulfide from production fluid streams. The sorbent for the removal of hydrogen sulfide employed in the current application is not only cost effective through its ability to be easily renewed, the process also exhibits high single pass performance in its ability to remove hydrogen sulfide from a production fluid stream.
- The primary object of the present invention is to provide a renewable sorbent for the removal of acid gas from a fluid stream.
- It is a further object of the present invention to employ the renewable sorbent in a process for the removal of hydrogen sulfide gas from a production fluid stream.
- In accordance with the present invention a composition is provided for the removal of acid gas from a fluid stream comprising iron mineral, vermiculite and starch.
- In further accord with the present invention a process for the removal of acid gas from a fluid stream is provided comprising the steps of: crushing a composition comprising vermiculite and an iron mineral; sifting the crushed vermiculite and iron mineral composition; calcinating the vermiculite and iron mineral composition; and contacting the calcinated vermiculite and iron mineral composition with the fluid stream.
- A detailed description of preferred embodiments of the present invention follows, with reference to the attached drawings, wherein:
-
FIG. 1 illustratively depicts a non limiting process for the manufacture of the renewable sorbent. -
FIG. 2 graphically depicts the H2S adsorption of differing concentrations and compositions of the renewable sorbent. -
FIG. 3 graphically depicts the drop in H2S pressure in the system after regenerization. -
FIG. 4 graphically depicts the trend for the H2S absorption values and regeneration stages. -
FIG. 5 graphically depicts the percentage of sulfur accumulated on the pellets according to the reutilization/regeneration cycle. -
FIG. 6 graphically depicts the H2S adsorption of the renewable sorbent at differing calcinating temperatures. -
FIG. 7 graphically depicts the H2S adsorption of the renewable sorbent at differing experimental conditions. - The invention relates to a cost effective system and process for the removal of acid gas from fluid streams.
- Hereinafter the term “fluid” includes but is not limited to matter in gaseous and/or liquid state. The term “fluid” may refer to any one or all of the following terms: oil, gas, water, liquids in an oil well, gases in an oil well, air and the like.
- Referring now to
FIG. 1 there is shown the general steps for manufacturing the renewable sorbent of the present invention. Raw materials are obtained instep 1, for example from a national market such as Venezuela, where raw material, such as iron mineral and an expansive clay, may be easily obtained. - After the raw materials are obtained 1 they are then dried at 100° C. for about 24 hours. After drying the raw materials are then mixed together into a composition before they are crushed and sifted in a
milling process 2. The milling may be carried out under any procedure that is well known within the art. For example, the dried raw material may be milled by a planetary ball mill. The raw material is milled to obtain a desired particle size of between about 50 microns to about 200 microns. The milled material may then be sifted through a 100mesh sieve 3. In order to facilitate pelletization of the iron ore, the milled material is sifted to remove particles or materials that are above about 150 microns. - After the
milling process 2, the raw material composition may be pelletized 4. The pelletization of the composition may be carried out under any procedure that is well known within the art, such as a tilted rotary disk, the pelletizing drum, the pelletizing disk and/or the pelletizing cone. During the pelletization process organic or inorganic binders, such as clays, cassava starch, potato starch and/or corn starch; admixtures, such as organic or inorganic binders in altering proportions; and water may be added to the ground raw material in order to control the binding strength of the pellets, to improve the mechanical properties of the pellets, to diminish thermal shock cracking of the pellets and to increase the strength of the pellets once they are burned. For optimum pelletization the particle size of the raw material may be less than 75 microns (200 mesh). - Two types of factors govern the pelletization process: Mechanical and Process factors. Table 1 details the mechanical factors that govern the pelletization process.
-
TABLE 1 FACTOR EFFECT MECHANICAL Disk Pellets grow less with increasing incli- FACTORS inclination nation because there is less retention time. Slew rate The higher speed, the more retention time. Edge The higher the height, the more retention height time, resulting in bigger pellets. Input area Input is made in the area where the pellet core is formed. Addition Excessive addition of water would result of water in a pellet with too much plasticity and humidity. - Pelletization process factors include the fineness of the ground raw material, input flow of the ground raw material, the humidity content of the ground raw material and the mineralogy of the ground raw material. Process formation of the pellets by pelletizing disk is characterized by the formation of a flow pattern that ranks particles among three classes: Input fineness, the ground raw material entering the disk; Primary agglomerates, the initial pellet core; and Final pellets. Pellets are formed inside the disk due to the disks rotation, inclination and the homogenization of the mixture.
- The pelletizing disk is continuously and steadily fed with the ground raw material as a liquid, such as water, is sprayed over the ground raw material inside the rotating pelletizing disk. The liquid drops collect rotating particles forming a primary agglomerate seed with increased density. The seed becomes denser as the liquid disturbed on its surface continues to collect ground raw material. The newly formed fresh or green pellet is extracted from the pelletizing disk once the desired pellet size is reached. The pelletization process preferably results in iron ore agglomerate pellets of approximately 1 centimeter in size.
- After the
pelletization process 4, the composition is calcined 5. The calcination process may be carried out by any procedure that is well known within the art. In order to prevent evaporation of the liquid and a violent breakage of the green iron ore agglomerate pellets, the temperature of the green pellets is gradually increased at a rate of 10° C. per minute until they are calcined at a temperature of about 500° C. to about 600° C. - The raw material used in this regenerable sorbent may include iron mineral, expansive clays and starch. The iron mineral may be an iron oxide obtained from Planta de Pellas Ferrominera del Orinoco (FMO) in Bolivar State. Other iron minerals that may be employed in the present invention include and are not limited to hematite, magnetite, maghemite and mixtures thereof. The expansive clay may be any expansive clay, such as vermiculite, bentonite, montmorillonite, blends of chlorite, kaolinite and mixtures thereof. The starch may be potato starch, corn starch, cassava, waxy corn and mixtures thereof.
- After the ground raw material composition is pelletized and calcined, the resultant sorbent may then be exposed to a fluid stream containing acid gases. Due to a chemical reaction between the molecules of the acid gases in the fluid stream and the sorbent, gaseous particles are attracted to the sorbent. The acid gas particles in the fluid stream react with the molecules of the sorbent and are thus removed from the fluid stream. Some reactions which illustrate this process as applied to the acid gas hydrogen sulfide (H2S) are as follows:
-
4H2S(g)+Fe3O4(s)→4H2O(l)+S(s)+3FeS(s) -
6H2S(g)+Fe3O4(s)→4H2O(l)+2H2(g)+3FeS2(s) -
3H2S(g)+Fe2O3(s)→3H2O(l)+FeS3(s) - The
pelletization step 4 ofFIG. 1 may be skipped or altered. The pelletization step is employed as a preferred shape for the inventive sorbent; however, the resultant shape of the sorbent may be any shape or design that is suitable for use in the removal of acid gas from a fluid stream. These shapes and designs include pellets, fine particles, shavings, calcined chips and muds. - Referring now to
FIG. 2 , samples were prepared and tested against commercial sorbents. A sorbent made from material taken from Planta de Pellas containing an agglomerate of dolomite, bentonite and iron ore calinated at about 500° C. to about 600° C. (CVG) 12, Sulfatreat XLP distributed by MI L.L.C. 11, and Sulfatreat STD distributed by MI L.L.C. 10 exhibit an H2S absorption of 0.28 lb H2S/lb sorbent 12, 0.24 lb H2S/lb sorbent 11, and 0.21 lb H2S/lb sorbent 10 respectively. - In
FIG. 2 , the absorption of the commercial sorbents is compared to a pelletized sorbent containing raw material comprising iron oxide and 2.5% w/w (by weight) vermiculite VPE 2.5, a sorbent containing raw material comprising iron oxide and 5% w/w vermiculite VPE 5, a sorbent containing raw material comprising iron oxide, 2.5% w/w vermiculite, 2.5% w/w starch MPE 2.5, a sorbent containing raw material comprising iron oxide, 5% w/w vermiculite and 5% w/w starch MPE 5 and a sorbent containing raw material comprising iron oxide and 2.5% w/w starch APE 2.5. -
FIG. 2 shows the H2S adsorption capacity of pellets with 5% vermiculite to be 0.21 lb H2S/lb sorbent VPE 5 and pellets prepared with 5% vermiculite and 5% starch have an increased adsorption capacity of 0.23 lb H2S/lb sorbent MPE 5. These adsorption capacities place the raw material composition of iron mineral, vermiculite and starch within the efficiency range of the adsorption capacities of commercial sorbents. - After the sorbent has been exposed to the fluid stream, the sorbent may be removed and regenerated. The sorbent is regenerated by treating the reacted sorbent with hydrogen peroxide. Hydrogen peroxide in the presence of an iron catalyst results in an oxidation known as Fenton's reaction. The procedure involves the oxidation of Fe2+ to Fe3+ by hydrogen peroxide, yielding hydroxyl radicals:
-
Fe2++H2O2→Fe3++−OH+.OH - After the pellets are exposed to the acid gas stream and/or oil stream they are composed of iron sulfurs. The pellets are regenerated by exposing them to H2O2:
-
FeS+H2O2→S(0)+Fe(OH)3 - The black exposed pellets are embedded in hydrogen peroxide (3% m/v) for 24 hours. The pellets recover their initial red color as a result of the oxidation of iron to maghemite and hematite, respectively. Traces of sulfur were found in the oxygenated water after washing out the pellets.
- After testing the H2S adsorption capacity of the first-time use of a group of 5% VPE pellets, the pellets were subjected to a basic analysis of sulfur. Next, the pellets were washed with H2O2 to reassess their adsorption capacity. This process was repeated three times in order to get a trend of values with regard to the H2S removal capacity and the sulfur profile of the pellets.
FIG. 3 graphically depicts the pressure drop values for three subsequent uses of the pellets. -
FIG. 3 shows a H2S pressure drop for each stage of reutilization/regeneration of pellets containing 5% of vermiculite. The pressure drop is an indicator of the H2O2 regenerative capacity of the 5% VPE pellets.FIG. 4 displays the experimental trend for the H2S adsorption capacity values estimated from the H2S pressure drop. -
FIG. 4 shows that while the number of regenerations of the pellets increases, the mass of H2S that can be removed from the system decreases; however, after three regenerations the same pellet is still able to remove acid gas. - As depicted in
FIG. 5 , the percentage of sulfur accumulated on the pellets grows according to the reutilization/regeneration cycles. It can be inferred fromFIG. 5 that following three cycles of regeneration, the pellets adsorption capacity is affected, diminished or depleted, possibly due to Fenton's reaction, i.e. sulfur obstructs the pellets active collection centers. However, upon further testing, after reacting to H2S and being subject to a bath with hydrogen peroxide for approximately 24 hours, the pellets mechanical strength was higher than the initial mechanical strength. - Table 2 lists some physical and chemical characteristics of the 5% MPE sample (5MPE) and the 5% VPE sample (5VPE).
-
TABLE 2 ANALYSIS 5MPE 5VPE X RAY Aluminium Hematite (Fe2O3), DIFRACTION Magnesumferrite Silica (SiO2) (XRD) (MgAl0.74 Fe1.26)O4, Hematite (Fe2O3), Silica (SiO2) MACROPOROSITY Average Diameter Average Diameter Pore = 0.39 μm Pore = 2.67 μm BED RESISTANCE Has Not 1.90 Kg/f REAL DENSITY 4.7 gr/mL 4.6 g/mL (HELIUM PICNOMETRY) APPARENT DENSITY 4.5 gr/mL 4.0 gr/mL SUPERFICIAL AREA Determined by Determined by BET = 8.56 m2/gr BET = 12.76 m2/gr METAL ANALYSIS Ca = 2877, K = 393, No realized IN PPM BY ATOMIC Na = <350, Mn = 2085, SPECTROSCOPY P = 661 (ICP-OES) IRON % ANALYSIS 44% 46% BY ATOMIC SPECTROSCOPY ICP-OES) CUALITATIVE *Fe, Mn, Ti, *Fe, Zr, Mn, Ti, ANALYSIS OF Ca, K, P, Si Ca, K, S, P, Si ELEMENT BY X RAY FLUORESCENCE -
FIG. 6 depicts the adsorption capacity of pellets calcined at about 500° C. to about 600° C. The absorption ofCVG 12 and the commercial sorbents,Sulfatreat XLP 11, andSulfatreat STD 10, is compared to a pelletized sorbent containing raw material comprising iron oxide and 5% w/w (by weight) vermiculite calcined at 500° C. VPE 5-500 and 600° C. VPE 5-600, along with a sorbent containing raw material comprising iron oxide, 5% w/w vermiculite and 5% w/w starch calcined at 500° C. MPE 5-500 and 600° C. MPE 5-600. -
FIG. 6 confirms that raw material compositions VPE 5-500, VPE 5-600, MPE 5-500 and MPE 5-600 exhibit an efficiency that is either within the range of the commercial sorbents or comparable to the commercial sorbents. The raw material composition comprising iron oxide, 5% w/w vermiculite and 5% w/w starch calcined at 500° C. MPE 5-500 exhibits the most efficient adsorption capacity of approximately 0.23 lb H2S/lb sorbent. -
FIG. 7 evaluates the raw material composition comprising iron oxide, 5% w/w vermiculite and 5% w/w starch calcined at 500° C. MPE 5-500 at differing experimental conditions. The MPE 5-500 composition was evaluated againstCVG 12 and the commercial sorbents,Sulfatreat XLP 11, andSulfatreat STD 10, for the absorption capacity of pellets with a diameter of 0.5cm 20, for the effect of 0.6 ml of water on thepellets 21, and for the effect of regeneration after treatment with hydrogen peroxide. - As shown in
FIG. 7 , the MPE 5-500 composition remains effective at a pellet diameter of 0.5 cm. Additional tests have shown that as the diameter of the pellet diminishes in the fluid stream the adsorption capacity can increase.FIG. 7 also shows that after the MPE 5-500 composition has been exposed to the fluid stream, the composition may be reacted with hydrogen peroxide to again obtain a H2S removal efficiency of 0.20 lb H2S/lb sorbent. - The regenerable sorbent of the present invention is used within a cost effective process for the removal of hydrogen sulfide from production fluid streams. The regenerable sorbent for the removal of acid gas employed in the current application is not only cost effective through its ability to be easily renewed through a reaction with hydrogen peroxide, the process also exhibits high single pass performance in its ability to remove up to 0.23 lb H2S/lb sorbent from a production fluid stream.
- The regenerable sorbent of the present invention may be inexpensively made from materials found within national markets, such as Venezuela. The combination of iron mineral, expansive clay and starch may be employed in a variety of sweetening plants to remove acid gases from numerous production fluid streams. The acid gas may be any gas in which it is desirable to remove acids, such as hydrogen sulfide, sulphide carbonyl, mercaptans and mixtures thereof.
- The regenerable sorbent of the present invention may be implemented in other possible applications. The final characteristics of the regenerable sorbent of the present invention may be applied to conventional well technology, and any application that may benefit from the extraction of acid gases from fluid streams.
- It is to be understood that the invention is not limited to the illustrations described and shown herein, which are deemed to be merely illustrative of the best modes of carrying out the invention, and which are susceptible of modification of form, size, arrangement of parts and details of operation. The invention rather is intended to encompass all such modifications which are within its spirit and scope as defined by the claims.
Claims (10)
1-13. (canceled)
14. A process for removing acid gas from a fluid stream, comprising the steps of:
contacting the fluid stream with pellets comprising iron mineral, vermiculite and a starch, wherein the iron mineral comprises an iron oxide selected from the group consisting of Fe2O3, Fe3O4 and combinations thereof, and wherein the iron oxide is present in particle sizes less than 75 microns so as to remove acid gas from the fluid stream and produce deactivated pellets;
regenerating the pellets; and
repeating said contacting step with regenerated pellets.
15. The process of claim 14 , wherein the regenerating step comprises treating the deactivated pellets with hydrogen peroxide.
16. The process of claim 14 , further comprising carrying out the contacting and regenerating steps at least three times with the same pellets.
17. The process of claim 14 , wherein the composition further comprising starch.
18. The process of claim 14 , wherein the acid gas is selected from the group consisting of a gas stream, oil stream and mixtures thereof.
19. The process of claim 14 , wherein the fluid stream is selected from the group consisting of a gas stream, oil stream and mixtures thereof.
20. The process of claim 14 , wherein the iron oxide is non-hydrated iron oxide.
21. The process of claim 19 , wherein the non-hydrated iron oxide is selected from the group consisting of hematite, magnetite, maghemite and mixtures thereof.
22. The process of claim 14 , wherein the vermiculite is present in an amount of 5% w/w and the starch is present in an amount of 5% w/w.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/614,487 US20150151237A1 (en) | 2009-03-31 | 2015-02-05 | Use of iron ore agglomerates for acid gas removal |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/415,389 US20100248941A1 (en) | 2009-03-31 | 2009-03-31 | Use of iron ore agglomerates for acid gas removal |
US12/779,808 US8246722B2 (en) | 2009-03-31 | 2010-05-13 | Use of iron ore agglomerates for acid gas removal |
US14/614,487 US20150151237A1 (en) | 2009-03-31 | 2015-02-05 | Use of iron ore agglomerates for acid gas removal |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/779,808 Continuation US8246722B2 (en) | 2009-03-31 | 2010-05-13 | Use of iron ore agglomerates for acid gas removal |
Publications (1)
Publication Number | Publication Date |
---|---|
US20150151237A1 true US20150151237A1 (en) | 2015-06-04 |
Family
ID=42785002
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/415,389 Abandoned US20100248941A1 (en) | 2009-03-31 | 2009-03-31 | Use of iron ore agglomerates for acid gas removal |
US12/779,808 Expired - Fee Related US8246722B2 (en) | 2009-03-31 | 2010-05-13 | Use of iron ore agglomerates for acid gas removal |
US14/614,487 Abandoned US20150151237A1 (en) | 2009-03-31 | 2015-02-05 | Use of iron ore agglomerates for acid gas removal |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/415,389 Abandoned US20100248941A1 (en) | 2009-03-31 | 2009-03-31 | Use of iron ore agglomerates for acid gas removal |
US12/779,808 Expired - Fee Related US8246722B2 (en) | 2009-03-31 | 2010-05-13 | Use of iron ore agglomerates for acid gas removal |
Country Status (1)
Country | Link |
---|---|
US (3) | US20100248941A1 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BR112012011771B1 (en) * | 2009-11-17 | 2019-10-08 | Vale S.A. | ORE FINISH AGGLOMERATED TO BE USED IN A SYNTERIZATION PROCESS, AND METHOD FOR PRODUCTION OF ORE FINISH AGGLOMERATED |
EP2664376A1 (en) * | 2012-05-14 | 2013-11-20 | Universität Bayreuth | An adsorbent comprising schwertmannite, a method of preparing the adsorbent and the use of the adsorbent for purifying water or gas |
CN102992442A (en) * | 2012-12-12 | 2013-03-27 | 常州大学 | Organic wastewater treatment method by cooperation of bentonite and Fenton reaction |
CN103055834B (en) * | 2013-01-28 | 2014-10-29 | 长沙理工大学 | Regeneration method for spent ferric oxide desulfurizer |
CN112439389B (en) * | 2020-10-30 | 2022-07-05 | 广西大学 | Magnetic starch bentonite wastewater treatment agent and preparation method thereof |
CN112316894B (en) * | 2020-11-02 | 2023-02-03 | 内蒙古大学 | Method for preparing magnetic mesoporous composite adsorbent by using natural mixed clay |
CN113789320A (en) * | 2021-09-29 | 2021-12-14 | 淮阴工学院 | Preparation method of immobilized enzyme with magnetic starch as carrier |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4311680A (en) * | 1980-11-20 | 1982-01-19 | The Goodyear Tire & Rubber Company | Method for removal of sulfur compounds from a gas stream |
US4774213A (en) * | 1985-12-16 | 1988-09-27 | Sud-Chemie Aktiengesellschaft | Ferruginous catalyst for decreasing the content of nitrogen oxides in flue gases |
US4977123A (en) * | 1988-06-17 | 1990-12-11 | Massachusetts Institute Of Technology | Preparation of extrusions of bulk mixed oxide compounds with high macroporosity and mechanical strength |
US6743405B1 (en) * | 1999-09-30 | 2004-06-01 | The United States Of America As Represented By The United States Department Of Energy | Low temperature sorbents for removal of sulfur compounds from fluid feed streams |
US20040149634A1 (en) * | 2003-02-05 | 2004-08-05 | Hughes Kenneth D. | Composite materials for fluid treatment |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4201751A (en) * | 1975-05-06 | 1980-05-06 | Heinz Gresch | Gas purification |
US4283373A (en) * | 1980-03-17 | 1981-08-11 | The Goodyear Tire & Rubber Company | Method for removal of sulfur compounds from a gas |
US4721582A (en) * | 1986-03-11 | 1988-01-26 | Sanitech, Inc. | Toxic gas absorbent and processes for making same |
US4786484A (en) * | 1987-02-03 | 1988-11-22 | Sanitech, Inc. | Process for absorbing toxic gas |
US6500237B2 (en) * | 1997-08-12 | 2002-12-31 | Adi International Inc. | Removing hydrogen sulfide from a gaseous mixture using ferric ions bonded to calcined diatomite |
US6719828B1 (en) * | 2001-04-30 | 2004-04-13 | John S. Lovell | High capacity regenerable sorbent for removal of mercury from flue gas |
US7081434B2 (en) * | 2001-11-27 | 2006-07-25 | Sinha Rabindra K | Chemical formulations for the removal of mercury and other pollutants present in fluid streams |
US20070129240A1 (en) * | 2003-12-05 | 2007-06-07 | Jayalekshmy Ayyer | Novel catalyst useful for removal of hydrogen suiplhide from gas and its conversion to sulphur. A process for preparing such catalyst and a method for removing of hydrogen sulphide using said catalyst |
-
2009
- 2009-03-31 US US12/415,389 patent/US20100248941A1/en not_active Abandoned
-
2010
- 2010-05-13 US US12/779,808 patent/US8246722B2/en not_active Expired - Fee Related
-
2015
- 2015-02-05 US US14/614,487 patent/US20150151237A1/en not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4311680A (en) * | 1980-11-20 | 1982-01-19 | The Goodyear Tire & Rubber Company | Method for removal of sulfur compounds from a gas stream |
US4774213A (en) * | 1985-12-16 | 1988-09-27 | Sud-Chemie Aktiengesellschaft | Ferruginous catalyst for decreasing the content of nitrogen oxides in flue gases |
US4977123A (en) * | 1988-06-17 | 1990-12-11 | Massachusetts Institute Of Technology | Preparation of extrusions of bulk mixed oxide compounds with high macroporosity and mechanical strength |
US6743405B1 (en) * | 1999-09-30 | 2004-06-01 | The United States Of America As Represented By The United States Department Of Energy | Low temperature sorbents for removal of sulfur compounds from fluid feed streams |
US20040149634A1 (en) * | 2003-02-05 | 2004-08-05 | Hughes Kenneth D. | Composite materials for fluid treatment |
Also Published As
Publication number | Publication date |
---|---|
US8246722B2 (en) | 2012-08-21 |
US20100313756A1 (en) | 2010-12-16 |
US20100248941A1 (en) | 2010-09-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20150151237A1 (en) | Use of iron ore agglomerates for acid gas removal | |
AU2018203359B2 (en) | Magnetic adsorbents, methods for manufacturing a magnetic adsorbent, and methods of removal of contaminants from fluid streams | |
Pinto et al. | Biochar from carrot residues chemically modified with magnesium for removing phosphorus from aqueous solution | |
Khraisheh et al. | Remediation of wastewater containing heavy metals using raw and modified diatomite | |
US5914292A (en) | Transport desulfurization process utilizing a sulfur sorbent that is both fluidizable and circulatable and a method of making such sulfur sorbent | |
CA2141491C (en) | Fluidizable sulfur sorbent and fluidized sorption | |
JP5844784B2 (en) | Sulfur removal using iron carbonate absorbent | |
CA2675323C (en) | Thermally treated expanded perlite | |
Sadegh et al. | Low-cost materials with adsorption performance | |
US6500237B2 (en) | Removing hydrogen sulfide from a gaseous mixture using ferric ions bonded to calcined diatomite | |
Pandey et al. | Pb (II) removal from aqueous solution by Cucumis sativus (Cucumber) peel: kinetic, equilibrium & thermodynamic study | |
AU2014369487B2 (en) | Method for preparing a sorbent | |
CN107666956B (en) | Method for preparing sorbent | |
Theydan | Effect of process variables, adsorption kinetics and equilibrium studies of hexavalent chromium removal from aqueous solution by date seeds and its activated carbon by ZnCl2 | |
US8603215B2 (en) | Composition of amorphous iron oxide hydroxide, desulfurizer comprising the same, and methods for preparing and regenerating the desulfurizer | |
CN107810052B (en) | Method for preparing sorbent | |
Mazurek et al. | Application of sulphate and magnesium enriched waste rapeseed cake biochar for recovery of Cu (II) and Zn (II) from industrial wastewater generated in sulphuric acid plants | |
AU2001291103B2 (en) | Compressed metal oxide composition | |
Sethupathi et al. | Preliminary study of sulfur dioxide removal using calcined egg shell | |
AU2001291103A1 (en) | Compressed metal oxide composition | |
Abdullah et al. | Rhodamine 6G removal from aqueous solution with coconut shell-derived nanomagnetic adsorbent composite (Cs-nmac): Isotherm and kinetic studies | |
JP7299844B2 (en) | Zinc oxide-based adsorbent using alkali metal hydroxide, and its preparation and use process | |
CA2334505C (en) | Removing hydrogen sulfide from a gaseous mixture using iron hydroxide bonded to calcined diatomite | |
Mehrvar et al. | Magnetically modified activated carbon prepared from pine cones for treatment of wastewater containing heavy metals | |
Van Thuan Le et al. | Removal of nickel and methylene blue from aqueous solutions by steel slag as a low cost adsorbent |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |