JP3499678B2 - Method for producing granular composition for sulfur sorption - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to the field of particulate compositions, particularly useful as sorbents for treating sulfur-containing fluid streams.

[0002]

BACKGROUND OF THE INVENTION Removing sulfur from fluid streams has been a long felt desire, as well as being necessary for a variety of reasons. If a sulfur-containing fluid stream is discharged as a waste fluid, removal of such sulfur from the fluid stream is often necessary to meet certain environmental regulations. If a sulfur-containing fluid stream is used in the catalytic process, such removal of sulfur is often necessary because it poisons the catalyst. Sulfur-containing fluid streams are sometimes used in fluidized bed reactors. Fluidized bed reactors have advantages over fixed bed reactors in terms of better heat transfer and better pressure drop. Fluidized bed reactor
Reactants that are generally granular are used. The size of these granules generally ranges from about 1 to about 1000 microns. However, for all applications, the reactants used generally do not have sufficient thermal stability and sufficient abrasion resistance.

[0003]

The present invention provides a method of making a particulate composition.

The present invention provides a method of making a particulate composition having improved thermal stability and improved abrasion resistance, which is also widely used in a variety of applications.

[0005]

In accordance with the present invention, there is provided a method of making a particulate composition containing zinc aluminate. The method comprises: (a) contacting a zinc component, an alumina component, a dispersant component to form a mixture; and (b) then spray drying the mixture to form the particulate composition. . The present invention also comprises an optional step (c) of contacting the particulate composition thus obtained with a zinc compound, which zinc compound may be converted to zinc oxide or zinc oxide. It is a compound.

Generally, the zinc component used in step (a) is zinc oxide. However, it can be any zinc compound that will combine with alumina to form zinc aluminate under the manufacturing conditions described herein. Examples of such compounds include zinc sulfide, zinc sulfate, zinc hydroxide, zinc carbonate, zinc acetate, zinc nitrate, zinc chloride,
Examples include, but are not limited to, zinc bromide, zinc iodide, zinc oxychloride, and zinc stearate. Mixtures of such compounds can also be used. The amount of zinc component used is in the range of about 5 to about 75 weight percent based on the total weight of the component. However, amounts in the range of about 15 to about 60 weight percent are preferred, and amounts in the range of about 25 to about 45 weight percent are most preferred.

The alumina component can be any suitable alumina or aluminosilicate. The alumina component should combine with the zinc component under these production conditions to form zinc aluminate. Suitable alumina components include, but are not limited to, hydrated alumina and flame-hydrolyzed alumina. The amount of alumina component used ranges from about 5 to about 90 weight percent based on the total weight of the component. However, about 25 to about 75
Amounts in the range of weight percent are preferred, and about 40 to
Most preferred is an amount in the range of about 65 weight percent.

The dispersant component can be any suitable compound, which helps to enhance the spray drying ability of the mixture. In particular, these ingredients are useful in preventing the precipitation, precipitation, sedimentation, agglomeration, adhesion and solidification of solid particles in a fluid medium. Suitable dispersants include, but are not limited to, condensed phosphates, and sulfonated polymers. The term condensed phosphate refers to any dehydrated phosphate, with H ₂ O: P ₂ O ₅ of about 3: 1 or less. Specific examples of suitable dispersants include, but are not limited to, sodium pyrophosphate, sodium metaphosphate, and sulfonated styrene maleic anhydride polymer. The amount of ingredient used is from about 0.01 to about 10 weight percent based on the total weight of the ingredient. However, an amount in the range of about 0.1 to about 8 weight percent is preferred, and an amount in the range of about 1 to about 3 weight percent is most preferred.

In a preferred embodiment of the invention a binder is used. The binder component has a cement-like property,
Alternatively, it can be any suitable compound having clay-like properties, and this serves to bind the particulate compositions together. Suitable examples of such binder components include cements such as gypsum, regular lime, hydraulic lime, natural cement, Portland cement, and high-alumina cement, and, for example, attapulgite, bentonite, halloysite, hectorite. Clays such as, but not limited to, kaolinite, montmorillonite, pyrophyllite, sepiolite, talc, and vermiculite. A particularly preferred binder component is calcium aluminate cement. The amount of binder component used ranges from about 0.1 to about 30 weight percent based on the total weight of the component. However, an amount in the range of about 1 to about 20 weight percent is preferred, and an amount in the range of about 5 to about 15 weight percent is most preferred.

In another preferred embodiment of the invention an acid component is used. The acid component can be any suitable acid that aids in the formation of zinc aluminate from the zinc and alumina components. Generally, the acid component is an organic or mineral acid. If the acid component is an organic acid, it is preferably a carboxylic acid. If the acid component is a mineral acid, it is preferred if it is nitric acid, phosphoric acid or sulfuric acid. Mixtures of these acids can likewise be used.
Generally, acid is used with water to make a dilute aqueous acid solution.
The amount of acid in the acid component is about 0. 0 based on the total volume of the acid component.
It ranges from 01 to about 20 volume percent. However, an amount in the range of about 0.1 to 10 volume percent is preferred, and most preferred if the amount is in the range of about 1 to about 5 volume percent. Generally, the amount of acid component used is based on the amount of dry component. That is, the ratio of the total dry component (gram) to the acid component (milliliter) is about 1.
It should be 75: 1 or less. However, it is preferred if this ratio is less than or equal to about 1.25: 1, and more preferably less than or equal to about 0.75: 1. These ratios help form a pasty mixture that can be dispersed in a liquid solution, slurry, or free-flowing spray.

The zinc component, the alumina component, and the dispersant component are contacted together by any method known in the art to make a pasty mixture that can be dispersed in a liquid solution, slurry, or flowable spray. Can be made. When the zinc component, the alumina component, and the dispersant component are solids, they should then be contacted in a liquid medium to form a paste-like mixture that can be dispersed in a liquid solution, slurry, or fluid spray. is there. In another embodiment of the present invention, the zinc component and the alumina component can be contacted together to form a composition of zinc aluminate, which is then contacted with the dispersant. Suitable means for contacting these components are, for example, tumblers, stationary shells, troughs,
It is already known in the art, such as muller mixers, impact mixers, etc. If desired, the binder can be contacted with other ingredients to create, among other things, compositions with improved abrasion resistance. Generally, these ingredients are
After contacting to form a mixture, it is contacted with an acid component. However, the dry and acid components can be contacted together either simultaneously or separately. The ratio of total dry ingredients (grams) to liquid ingredients (ml) is about 1.7.
It should be 5: 1 or less. However, this ratio is preferably about 1.25: 1, and more preferably about 0.75: 1. These ratios help make a mixture of pastes that can be dispersed in a liquid solution, slurry, or fluid spray.

After contacting the components together to form a mixture, they are spray dried to form particles having a size of from about 1 to about 1000 microns. Spray drying is well known in the art and can be found in Perry's Chemical Engineers Handbook 6th edition, published by MacGlow-Hill, (PERRY'S CHEMICAL ENGINEER'S HANDBOOK, 6th e
dition, McGraw-Hill, Inc.) pages 20-54 to 20-
Discussed on page 58. The above information, especially the Handbook of Industrial Drying, published by Marcel Decker (HANDBOOK OF INDUST
RIAL DRYING, by Marcel Dekker. Inc.) pp.243-29
Obtained from page 3. The particulate composition formed is about 10
Has a size of about 1000 microns. However, it is preferred that the particle size be from about 30 to about 300 microns, and most preferred if the size is from about 50 to about 100 microns.

The dried, particulate composition is then calcined to form a calcined particulate composition. Calcination is carried out under any suitable conditions, which removes residual water, oxidizes any combustibles and results in the binding of zinc and alumina components to form zinc aluminate. Usually, the dry composition is then calcined under an atmosphere containing oxygen. Generally, the temperature at which calcination is performed is about 300-
It is in the range of 1200 ° C. However, the temperature is about 45
More preferably, it is in the range of 0 to about 1000 ° C. Calcination should occur for a range of about 0.5 to about 12 hours.

The zinc compound can be contacted after the dry particulate composition is formed or after calcination. Generally, the zinc compound is zinc oxide. However, any zinc compound can be used as long as it can be converted into zinc oxide under the production conditions of the step (a). Examples of such compounds include zinc sulfide, zinc sulfate, zinc hydroxide, zinc carbonate, zinc acetate, zinc nitrate, zinc chloride, zinc bromide, zinc iodide, zinc oxychloride, and zinc stearate. , But is not limited to this. Mixtures of such compounds can likewise be used. The amount of zinc compound used ranges from about 5 to about 75 weight percent based on the total weight of the components. However, amounts in the range of about 15 to about 60 weight percent are preferred, and about 25 to about 4
Most preferred is an amount in the range of 5 weight percent. In a preferred embodiment, the dry particulate composition, or the calcined and dried particulate composition, can be contacted with a liquid medium consisting of a soluble zinc compound. Generally, a soluble zinc compound is a compound that can be converted to zinc oxide during the manufacture of the sorbent composition. As the liquid medium, any medium such as water and an organic solvent can be used. Examples of soluble zinc compounds include, but are not limited to, zinc sulfide, zinc sulfate, zinc carbonate, zinc acetate, zinc nitrate, zinc chloride, zinc bromide, and zinc iodide. Mixtures of these soluble zinc compounds can also be used.

The liquid medium containing the soluble zinc compound is
Contacting with the particulate composition can be by any means known in the art. One such method is to saturate the particulate composition with a liquid medium. After mixing the particulate composition with the liquid medium containing the soluble zinc compound, the composition is dried and calcined. The composition preferably has a temperature in the range of about 50 ° C to about 300 ° C, more preferably a drying temperature of about 100 ° C to about 250 ° C.
In the range of about 0.5 hours to about 8 hours, more preferably about 1 hour to about 5 hours. Thereafter, the dry composition is about 30% in the presence of oxygen or in an oxygen-containing gas.
0 ° C to about 800 ° C, more preferably about 450 ° C
Calcinated at a temperature of about 750 ° C to remove residual water,
Any combustible material oxidizes and converts at least a portion of the zinc compound to zinc oxide. The time required for this calcination step ranges from about 0.5 hours to about 4 hours, and preferably ranges from about 1 hour to about 3 hours.

If desired, a metal oxide component can be added to the composition. These metal oxide components can improve the physical and chemical properties of the particulate composition. For example, these metal oxide components can increase the ability to hydrogenate various compounds of the particulate composition. Examples of suitable metal oxide components include iron oxide, cobalt oxide, nickel oxide, ruthenium oxide, rhodium oxide, palladium oxide, osmium oxide, iridium oxide, platinum oxide, copper oxide, chromium oxide, titanium oxide,
Included, but not limited to, zirconium oxide, tin oxide, and manganese oxide. The amount of metal oxide component in the particulate composition is about 0.0 based on the weight of the particulate composition.
It ranges from 1 to about 20 weight percent. However, it is more preferred if the amount is in the range of from about 0.1 to about 15 weight percent, and most preferably the amount is from about 1 to about 1.
It is in the range of about 10 weight percent.

The metal oxide component is a particulate component, an element metal,
It can be added in the form of a metal oxide and / or a metal-containing compound that can be converted to a metal oxide under the calcination conditions described herein. Some examples of such metal-containing compounds include metal acetates, metal carbonates, metal nitrates, metal sulfates, metal thiocyanates, and mixtures of any two or more thereof.

The elemental metal, metal oxide, and / or metal-containing compound can be added to the particulate composition by any method known in the art. One such method is to saturate the particulate composition with a liquid medium, either water or organic, containing elemental metals, metal oxides, and / or metal-containing compounds. After the elemental metal, metal oxide, and / or metal-containing compound is added to the particulate composition, the composition is dried and calcined.

The elemental metal, metal oxide, and / or metal-containing compound can be added to the particulate composition as a component of the initial mixture, or after the particulate composition has been spray dried and calcined. It can also be added. If the metal oxide is added to the particulate composition after it has been spray dried and calcined, the composition is dried and calcined twice. The composition is generally dried at a temperature in the range of about 0.5 to about 8 hours, more preferably about 1 hour to about 5 hours, preferably about 50 ° C to about 300 ° C. More preferably, it is in the range of about 100 ° C to 250 ° C. The dry composition is then calcined in the presence of oxygen or an oxygen-containing gas at a temperature in the range of about 300 ° C to about 800 ° C, more preferably about 450 ° C to about 750 ° C to remove volatiles. And continues until at least a portion of the elemental metal and / or metal-containing compound is converted to a metal oxide. The time required for this calcination step generally ranges from about 0.5 to about 4 hours, and preferably ranges from about 1 hour to about 3 hours.

The particulate composition of the present invention can be widely used in various applications. For example, they can be used as a component of the zinc oxide sorbent used in the sulfur removal step, where the zinc oxide particulate composition is contacted with a sulfur-containing gas feed fluid, and then the zinc oxide particulate composition. The article is contacted with oxygen or an oxygen-containing gas used to regenerate the zinc oxide particulate composition. An example of such a sulfur removal process is U.S. Pat. No. 4,990,318.
No. 5,0777,261; No. 5,102,8.
No. 54; No. 5,108,975; No. 5,130,
No. 288; No. 5,174,919; No. 5,17.
No. 7,050; No. 5,219,542; No. 5,2.
44,641; 5,248,481; and 5,281,445.

On top of that, the particulate composition formed without the additional step (c) of contacting the composition with a zinc compound is (1) an alkane dehydrogenation reaction; (2) an olefin and a diamine. It can be used as a catalyst component used in the production of olefins; (3) hydrogenation reaction of alkenes and alkynes in a hydrocarbon stream; (4) dehydrocyclization reaction of paraffins to aromatics. These, it can be used as components of compounds used for waste water treatment, and these are, for example NO _X from refining and chemical processes, H ₂ S, and compounds used in the purification of exhaust gases, such as the removal of hydrides Can be used as a component.

[0022]

DETAILED DESCRIPTION OF THE INVENTION These examples are provided by way of explanation of the invention and are not meant to be construed as limiting the invention.

Example 1 This example describes the preparation of zinc aluminate particles of the present invention. This example also describes the preparation of the mixture which can be spray dried and makes these zinc aluminate particles.

Part A; 120 grams of zinc oxide, 18
8 grams of Vista Dispal alu
mina), 30 grams of Secar 71 calcium aluminate cement, 3.42 grams of sodium pyrophosphate, and 4.0 grams of tin oxide are dry mixed. This dry mixture is slowly added to 500 ml of 2.0 volume percent aqueous acetic acid with stirring. 20 more of the resulting slurry mixture
Stir for 1 minute and then filter through a 60 mesh screen. The filtered slurry mixture was spray dried using a Yamato DL-41 type spray dryer, adjusted as follows. Inlet temperature 220 ℃ Outlet temperature 120 ℃ Temperature set point 300 ℃ Supply pump 2.5 Atomized air 0.6 Aspirator air 0.8 (Rotamer) Needle knocker 1.0 Nozzle SU-2A

The temperature of the spray-dried microspheres thus obtained was raised from the surrounding environment at a gradient of about 3 ° C. per minute to obtain 843.
It was calcined at 0 ° C for 5 hours. The calcined material exhibited the following properties. Particle size distribution mesh weight% +120 0.1 +270 53.2 +325 13.1 +400 18.6 -400 15.1

Bulk density (filled) is 1.0 grams /
cc (several experiments identical to the method described were combined and the +270 and +325 mesh portions of the re-sieved product were measured).

Both the above calcined material and the control material (Davison GXP-5, a commercially available fluid cracking catalyst used for petroleum cracking) are described in US Pat. No. 4,010,116 ( Abrasion resistance (percentage abrasion) was tested by the same procedure as the method described in this disclosure, which is incorporated herein by reference. A sample of the material of the invention used was a combination of several of the same experiments described here and re-sieved product +270.
Obtained from the mesh. This +270 mesh part again-
Sifted through 80 and +230 mesh and 50 grams of the resulting material was used in the abrasion test. The abrasion test was 5 hours long. Percent attrition represents the amount of material lost to fines due to attrition as a result of the 5 hour test. Attrition Percentage Inventive Substance 7.66 Control Catalyst 4.59

Part B: Another method of the present invention comprising:
120 grams of zinc oxide, 188 grams of Vista Dispar Alumina, 30 grams of Secal 71 calcium aluminate cement, 3.42 grams of sodium metaphosphate, and 4.0 grams of tin oxide were dry mixed. The dry mixture was added slowly with stirring to 500 ml of a 2.0 volume percent aqueous acetic acid solution. The resulting slurry mixture was mixed for an additional 30 minutes and then filtered through a 60 mesh screen. The filtered slurry mixture gelled slightly but was easy to pour and pump. The filtered slurry was spray dried using the same equipment and conditions set forth above, except that the nozzle was SU-2 instead of SU-2A. Spray-dried material is approximately 3 ° C from the surrounding environment
The temperature was increased at a gradient of 1 / min and calcined at 835 ° C. for 5 hours. Sieve analysis of the calcined material gave the following particle size distribution. Particle size distribution mesh weight% +120 2.1 +270 33.2 +325 24.1 +400 18.0 -400 22.7

Part C: 120 grams of zinc oxide, 18
8 grams of Vista Dispar Alumina, 30 grams of Sekar 71 calcium aluminate cement, 3.42 grams of sulfonated styrene maleic anhydride polymer, and 4.0 grams of tin oxide were dry mixed. The dry mixture was slowly added to 500 ml of 2.0 volume percent aqueous acetic acid with stirring. The resulting slurry mixture was mixed for an additional 30 minutes. At this point, the slurry had no visible gelation and still had a very low viscosity. The slurry was filtered through a 60 mesh screen and spray dried using the same equipment and conditions described above. The spray dried material was calcined at 835 ° C. for 5 hours at a ramp of about 3 ° C. per minute from ambient temperature. Sieve analysis of the calcined material showed the following results in particle size distribution. Mesh weight% +120 16.2 +270 27.4 +325 8.8 +400 13.7 -400 33.9

Comparative Example 1 This example demonstrates the important properties of the dispersant component of the present invention. 5 describes five unsuccessful attempts at making a mixture suitable for spray drying, in which the sodium pyrophosphate of Example 1, Part A was replaced by another substance. is there.

Part A: 120 grams of zinc oxide, 18
3. 8 grams of Vista Dispal Alumina, 30 grams of Secal 71 calcium aluminate cement, and 4.
0 grams of tin oxide was dry mixed. The dry mixture was added to 2.
To 500 ml of 0 volume percent aqueous acetic acid was added slowly with stirring. To this was added 3.42 grams of sodium silicate. Stirring was continued for 5 minutes, at which point the mixture gelled to a point of very high viscosity to be pumped for spray drying.

Part B: 120 grams of zinc oxide, 18
8 grams of Vista Dispar Alumina, 30 grams of Secal 71 calcium aluminate cement, 3.42
Gram of poly (acrylic acid) (molecular weight 200,000 ~
450,000), and 4.0 grams of tin oxide were dry mixed. The dry mixture was slowly added with stirring to 500 ml of a 2.0 volume percent aqueous acetic acid solution. During the addition, the mixture started to gel and when all of the powder mixture was added to acetic acid (about 5 minutes), the mixture was very thick to pump due to spray drying.

Part C: 120 grams of zinc oxide, 18
8 grams of Vista Dispar Alumina, 30 grams of Secal 71 calcium aluminate cement, 3.42
Gram of poly (acrylic acid) (molecular weight 200,000 ~
450,000), and 4.0 grams of tin oxide were dry mixed. The dry mixture was slowly added to 500 grams of distilled water with stirring. The mixture gelled to a very dark spot for pumping due to spray drying.

Part D: 120 grams of zinc oxide, 18
3. 8 grams of Vista Dispal Alumina, 30 grams of Secal 71 calcium aluminate cement, and 4.
0 grams of tin oxide was dry mixed. Separately, 3.42 grams of 65 weight percent aqueous poly (acrylic acid) (molecular weight 2000) was mixed with 500 grams of distilled water. The solution was tested on pH paper to be weakly acidic. The dry mixture was gradually added to the weakly acidic solution with stirring. Before the addition of the dry mixture was complete, the liquid became a gel and was very thick to pump for spray drying.

Part E: 120 grams of zinc oxide, 18
3. 8 grams of Vista Dispal Alumina, 30 grams of Secal 71 calcium aluminate cement, and 4.
0 grams of tin oxide was dry mixed. Separately, 3.42 grams of 65 weight percent poly (acrylic acid) (molecular weight 2000) was mixed with 500 grams of distilled water and 0.50 grams of caustic soda. The solution was tested to be weakly basic with pH paper. The dry mixture was gradually added to the weakly basic solution with stirring. Before the addition of the dry mixture was complete, the liquid became a gel and was very thick to pump for spray drying.

Comparative Example 2 This example illustrates the important properties of the dispersant component in the present invention. This experiment shows that without a dispersant component, no mixture is formed that can be dispersed in a fluid such as a spray.

60 grams of zinc oxide, 94 grams of Vista Dispar Alumina, 15 grams of Secal 71 calcium aluminate cement, and 2.0 grams of tin oxide were dry mixed. The dry mixture was slowly added with stirring to 500 ml of 1.0 volume percent aqueous acetic acid. During stirring, the mixture gelled to a point where it was thick enough to be spooned. I tried spray drying but the nozzle clogged almost immediately.

Example 2 This example demonstrates the use of zinc aluminate particles in forming a zinc oxide sorbent. Fifty grams of zinc aluminate particles made according to Example 1, Part A were spray saturated with a solution of 46 grams of zinc nitrate hexahydrate in 7 grams of warm deionized water. The surface of the saturated fine particles was first dried using a heat gun, and then calcined at 450 ° C. for 1 hour. The sorbent of this example was made by performing the above saturation / drying / calcination step once more.

Next, 37 grams of the above saturated material was added to 10.69 grams of nickel nitrate hexahydrate.
A solution dissolved in 86 grams of deionized water was used to spray and saturate. The material was then dried and allowed to rise from ambient temperature by 5 ° C / min and calcined at 635 ° C for 1 hour.

The nickel-saturated material from above was tested for sulfur loading. The test is 20 mm O. D. It was carried out in an apparatus consisting of a quartz reactor and a 2 mm thermocouple well. The reactor was operated in fixed bed upflow mode with 10 grams of test sorbent. Sorbent is 53 in nitrogen flow
Heated to 8 ° C. Nitrogen gas was converted to a simulated sulfur plant feed gas fluid containing 4.2 volume percent hydrogen sulfide, 40.0 volume percent carbon dioxide, and 55.8 volume percent nitrogen when the desired temperature was obtained. Replaced. The hourly space velocity of gas is 1450c
c / cc sorbent / hour. Sulfur loading was monitored by measuring the concentration of hydrogen sulfide in the reactor effluent using a conventional monitoring device that monitors hydrogen fluid suitable for the concentration range encountered. Once the sorbent was completely saturated, hydrogen sulfide had passed through as evidence of this, so the flow of simulated sulfur plant gas into the reactor was stopped and the reactor was purged with nitrogen for 45 minutes, during which Regeneration temperature 593
Heated to ° C. The loaded sorbent was regenerated in a flow of 200 cc / min in about 5 hours. After that, 538 ℃
The reactor was then purged with nitrogen for about 40 minutes. Thereafter, the nitrogen fluid was stopped and the simulated sulfur plant gas fluid supply was resumed to initiate another absorption cycle. This method was repeated for as many cycles as desired.
The test results are shown in Table 1 below.

Table 1 Sulfur absorption test results Temperature ℃ Cycle Sulfur load% ^* 538 1 3.9 538 2 6.9 538 3 8.0 538 4 8.4 ^* : Sulfur in the absorbent when hydrogen sulfide passed through Weight percent of

The results shown in Table 1 show that the sorbents made with the zinc aluminate particles of the present invention have a very high effect on the removal of sulfur from the gas.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI B01J 2/28 B01J 2/28 (56) References JP-A-56-111044 (JP, A) JP-A-6-144918 (JP , A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) B01J 20/00-20/34

Claims (15)

(57) [Claims] 1. A method for producing a granular composition, comprising the steps of : (a) contacting (1) a zinc component, (2) an alumina component, and (3) a dispersant component to form a mixture;
Then (b) the mixture is spray dried to form particles.
The above method comprising the steps of : 2. The zinc component is zinc sulfide, zinc sulfate, zinc hydroxide, zinc carbonate, zinc acetate, zinc nitrate, zinc chloride, zinc bromide, zinc iodide,
The method according to claim 1, which is zinc oxychloride, zinc stearate, or a mixture of any two or more of the zinc components. 3. The method of claim 1 or 2, wherein the amount of zinc component used ranges from about 15 to about 60 weight percent, based on the total weight of the component. Wherein said alumina component comprises alumina, the method according to any one of claims 1 to 3. 5. The method of any one of claims 1 to 4, wherein the amount of alumina component used ranges from about 30 to about 75 weight percent based on the total weight of the component. Wherein said dispersant component, condensed phosphates, sulfonated polymers, or a mixture of any two or more of these dispersants components, according to any one of claims 1 to 5 Method. 7. The method of any one of claims 1-6, wherein the amount of dispersant component used ranges from about 0.1 to about 8 weight percent based on the total weight of the component. Method. 8. In step (a), a binder component is added .
8. Any of claims 1-7, also contacting to form a mixture.
The method according to any one of claims. 9. Before fang Indah component, gypsum, usually lime, hydraulic lime, natural cement, Portland cement,
The method according to claim 8, which is a high-alumina cement, attapulgite, bentonite, halloysite, hectorite, kaolinite, montmorillonite, pyrophyllite, sepiolite, talc, vermiculite, or a mixture of any two or more of these binder components. . 10. The method of claim 8 or 9 wherein the amount of binder component used ranges from about 1 to about 20 weight percent based on the total weight of the component. 11. The method according to any one of claims 1 to 10, wherein in step (a) the acid component is also contacted to form a mixture. 12. Before hexane component, a carboxylic acid, nitric acid, phosphoric acid, sulfuric acid, or a mixture of any two or more of these acids, The method of claim 11. 13. The method of claim 12, wherein the amount of acid in the acid component ranges from about 0.1 to about 10 volume percent based on the total volume of the acid component. 14. The (c) said particles are zinc oxide
Or any of claims 1 to 14 , further comprising the step of contacting with a zinc compound which is a compound that can be converted into zinc oxide.
The method according to any one of claims. 15. The method of claim 14, wherein the zinc compound is as defined in claim 2.