EP1044161A1 - Fabrication de particules solides - Google Patents

Fabrication de particules solides

Info

Publication number
EP1044161A1
EP1044161A1 EP98948071A EP98948071A EP1044161A1 EP 1044161 A1 EP1044161 A1 EP 1044161A1 EP 98948071 A EP98948071 A EP 98948071A EP 98948071 A EP98948071 A EP 98948071A EP 1044161 A1 EP1044161 A1 EP 1044161A1
Authority
EP
European Patent Office
Prior art keywords
solids
dry
blend
microns
aqueous slurry
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.)
Withdrawn
Application number
EP98948071A
Other languages
German (de)
English (en)
Other versions
EP1044161A4 (fr
Inventor
Edwin W. Albers
Harry W. Burkhead, Jr.
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Contract Materials Processing Inc
Original Assignee
Contract Materials Processing Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Contract Materials Processing Inc filed Critical Contract Materials Processing Inc
Publication of EP1044161A1 publication Critical patent/EP1044161A1/fr
Publication of EP1044161A4 publication Critical patent/EP1044161A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0072—Preparation of particles, e.g. dispersion of droplets in an oil bath
    • 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
    • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing

Definitions

  • This invention relates to methods for making mixed crystalline solid particles by dry-milling a mixture of coarse particulate metal oxide and/or metal salt raw materials, forming a slurry of the finely-divided, co- milled particles and drying the slurried materials to form agglomerated larger particles.
  • US 4,755,499 (Neal et al) relates the importance of attrition resistance in fluid bed solids.
  • US 5,559,067 (Lerner et al) describes in situ processes for making improved zeolitic fluid cracking catalyst by spray drying a mixture of hydrous kaolin, gibbsite and spinel, essentially free from metakaolin, calcining the resulting microspheres to convert the hydrous kaolin to metakaolin.
  • the gibbsite crystals are ground to less than 5 microns prior to slurrying.
  • Trosta et al oxide catalyst is prepared by: reacting a pentavalent vanadium compound and a pentavalent phosphorus compound in an organic solvent in the presence of a reducing agent capable of reducing the pentavalent vanadium to the tetravalent state to produce the crystalline composite oxide particles containing tetravalent vanadium and pentavalent phosphorus; dry-pulverizing the obtained crystalline composite oxide particles in a high-speed gas flow; mixing the pulverized particles with an aqueous solution containing tetravalent vanadium and pentavalent phosphorus to form a slurry, spray-drying the slurry and then calcining.
  • an intimate mixture of metal oxides and/or metal salts is formed by dry milling an admixture of coarse solid components to form a finely divided blend of comminuted particles having an average size less than 5 microns ( ⁇ ) , typically less than about 2 ⁇ .
  • An aqueous slurry of the admixed solids blend can be spray dried to form larger aggregates having an average size of at least 20 ⁇ having superior attrition resistance and uniform particle distribution.
  • the products are useful as contact solids, such as sorbents or catalysts.
  • metal oxides and salts have been found to be useful for co-milling according to the present invention.
  • zinc oxide calcium sulfate (gypsum) , silica, basic magnesium silicate (talc) , titanium dioxide, USY synthetic faujasite and ZSM-5 zeolites, hydrotalcite, bentonite and various other clays.
  • gypsum calcium sulfate
  • talc basic magnesium silicate
  • titanium dioxide titanium dioxide
  • USY synthetic faujasite and ZSM-5 zeolites titanium dioxide
  • hydrotalcite hydrotalcite
  • bentonite various other clays.
  • US 4,640,825 (Rosenberg) describes ZnO particles in a spray dryer and employed for SOx abatement .
  • the contact solids compositions made by this invention may include a combination of inorganic oxides or salts with an inorganic binder.
  • Desirable inorganic oxides include a member selected from the group consisting of oxides or hydroxides of aluminum, calcium, cobalt, copper, iron, magnesium, molybdenum, silicon, titanium, vanadium, zinc, tungsten, strontium, nickel, manganese, zirconium, barium, members of the lanthanide series and mixtures thereof.
  • the contact solid compositions may be self-bound or may include a binder component to "glue" the inorganic oxides together into the desired shape, such as spheroidal particles. Depending on the application, different binding systems are used, and binders may be added to co-milled metal oxides/salts prior to forming the aquous slurry.
  • a hydrothermally stable inorganic binder such as aluminum chlorohydrol or peptized alumina is used.
  • Effective inorganic binders include sols of aluminum such as aluminum chlorohydrol, peptized aluminas, sols of silica, colloidal silicas, sols of titanium, sols of zirconium clays such as bentonite, calcined kaolinite, kaolinite, metakaolin, montmorillonite, chlorite, talc, and mixtures of these.
  • Desirable inorganic binders include a sol of aluminum, peptized alumina, a sol of silica, colloidal silica, a sol of titanium, a sol of zirconium, a clay, and mixtures thereof.
  • the method for making solid particles provides the intimate mixture of solid crystalline metal compounds by the steps of: a) admixing particulate metal compounds to form a dry solids blend of at least two different crystalline solids; b) dry milling the blended solids to produce finely-divided crystalline solids; c) recovering from the dry milling step a comminuted solids blend having an average particle size of about 1-5 microns; d) storing the recovered comminuted solids blend in a dry storage container for subsequent completion of manufacture; e) transporting a measured portion of the comminuted solids blend from the storage container to a manufacturing facility; f) forming an aqueous slurry of the transported, comminuted solids blend; g) drying the aqueous slurry to form agglomerated particles having an average size range greater than about 20 microns; and h) recovering dry agglomerated particles having enhanced attrition resistance
  • a mixture of zinc oxide and titanium dioxide in a fixed weight ratio of 1.5:1 ZnO:Ti0 2 can be pre-blended and stored for later incorporation into a variety of differenct contact solids formulations.
  • the comminuting step is conducted at ambient temperature or less than 25°C, depending upon the frangibility of the coarse particulates in the feed.
  • Air or inert gas is usually employed as the source of fluid engergy for the micronizer milling. Dry gas having a dew point of less than -50°C can assure that no free water is added to the solids during milling.
  • the finely-divided co-milled solids components are mixed with water, preferably containing about 0.1 to 1 wt% surfactant prior to forming and drying the contact soldis product herein.
  • Surface hydrolysis can be a sigificant detriment to many materials, and it is an advantage of the present invention to provide pre-blended, dry-milled materials for dispersion in water and spray dried or otherwise manufactured as dry particles in a short time period, usually less than 1 hour from initial contact with free water.
  • Hydrolyzable metal oxides and salts are advantageously pre-blended and stored in the substantial absence of added water. It is understood that ostensibly dry components, such as CaS0 4 .H 2 0 (calcium sulfate monohydrate) contain bound water; however, such materials do not interfere with long term storage of pre-blended metal oxide/salt mixtures. Batchwise or continuous inline feeding of slurry components is well known. Thereafter, the slurry is pumped or otherwise transported to the spray dryer feed tank.
  • Prefered acid stable surfactants are fluorohydrocarbons manufactured under the trade name "DuPont Zonyl TBS” or 3M “FC-95", and 0.01-1 wt % is satisfactory. The use of surfactant is believed to contribute to attrition resistance by decreasing the 'blow holes' during spray drying.
  • Spray Drying Conventional spray drying techniques are known to the industry, usually withdrawing a slurry containing sufficient water to form a fluent mixture of solids and liquid phases, advantageously incorporating a surfactant to impart homogeneity and mechanical properties to the resulting dry products.
  • Heat and low pressure permit flashing or rapid evaporation of the liquid phase from a slurry mist, resulting in agglomeration of smaller particles to form larger solid, typically having a spheroidal shape and a particles size distribution in the 20-250 micron ( ⁇ ) range or larger.
  • the particles typically have an average size of 20-100 ⁇ .
  • sorbent particles for fluid bed processes a larger particle having an average size of about 150-200 ⁇ may be desired.
  • the following examples are given.
  • contact solids consisting essentially of zinc oxide and calcium sulfate, along with a minor amount of bentonite clay are compounded, dry milled and spray dried to obtain SOx-absorbent particles.
  • the blended metal oxides contain about 15-65 wt% ZnO, 10-35 wt% Ti0 2 and 0-10 wt% bentonite clay or similar binder.
  • the blended metal compounds contain about 15- 65 wt% ZnO, 10-35 wt% CaS0 4 and 0-10 wt% bentonite clay.
  • the comminuting step is usually conducted under ambient conditions at a temperature of about -25 to 25°C.
  • the aqueous slurry containing about 35 wt% solids is spray dried to form agglomerated particles having an average size of about 120-200 microns.
  • the comminuted solids blend is in contact with free water less than 1 hour before the drying step, thereby minimizing hydration reactions.
  • EXAMPLE A An attrition-resistant contact solids sulfur oxide sorbent material useful as FCC additive was prepared according to the present invention.
  • the blend of mixed metal oxide powders were fed, using a vibratory tray feeder, to a Sturdevant micronizer jet mill operated under ambient conditons, at air and feed rates to achieve a ground powder average particle size of less than 3 microns, as measured by laser light scattering, ASTM method D4464.
  • the ground blend of mixed metal oxides was slurried under high shear to achieve 25-30 percent solids dispersin in a solution containing vanadyl sulfate and cerium oxide to equal 2% vanadium and 12% cerium oxide on the finished catalyst.
  • DuPont 'Zonyl TBS' acid-stable fluorohydrocarbon surfactant is added to the spray drier feed at a rate of about 0.1 part per 100 parts of spray dried powder product.
  • the slurry is then spray dried to yield a 70-80 micron ( ⁇ ) particle product, having an Attrition Index (Al) of 6.
  • EXAMPLE Bl A blend of mixed metal oxides, consisting of 55 wt% zinc oxide, 9% bentonite, 28% gypsum (CaS0) , and 8% Drierite were dry blended and dry milled in a micronizer to achieve a ground powder average particle size of less than 3 microns.
  • the ground blend of mixed metal oxides was slurried in water to achieve 25-35% solids. Acid-stable surfactant is added, and the slurry is spray dried using a pressure nozzle system to achieve an average spray dried particle of 130 ⁇ .
  • EXAMPLE B3 - Drierite and calcium sulfate were individually ground to an average particle size of less than 3 microns using the procedure of Example Bl .
  • a blend of mixed metal oxides, consisting of 56% unground ZnO, 9% unground Bentonite, 28% ground gypsum, and 7% ground Drierite were dry blended.
  • the blend of powders was slurried in water to 25-35% solids.
  • Acid-stable surfactant is added to the slurry.
  • the slurry is spray dried using a pressure nozzle system to achieve an average spray dried particle of 130 ⁇ .
  • EXAMPLE B4 - Example B3 is repeated, except the preparation is made without the surfactant addition.
  • EXAMPLE C A zinc oxide/titanium dioxide mixture having a 1.5:1 ZnO:Ti0 2 wt. ratio (95 wt%) is blended with 5wt% bentonite and co-milled. The dry milled mixture is slurried with a minor amount of organic binder and surfactant prior to spray drying.
  • EXAMPLE D A zinc oxide/titanium dioxide mixture having a 1.5:1 ZnO:Ti0 2 wt. ratio (35 wt%) is blended with 10% hydrotalcite powder component (LaRoche HTC) having a particle size range of about 4 to 90 microns (predominantly 15-40 microns) , produced by the method of US Patent 5,399,329, with 15% talc and 40% fine kaolin clay.
  • 10% hydrotalcite powder component LaRoche HTC
  • EXAMPLE E A dry mixture of 40 wt% ultrastable Y zeolite, 20% silica, 10% Grace CA alumina, and 30 wt% kaolin clay is co-milled and slurried with binder in water. Surfactant is added to feed slurry during spray drying.
  • EXAMPLE F A dry mixture of 20 wt% ultrastable Y zeolite, 10% clinotilite clay, 20% silica, 10% Grace WCA alumina, and 40 wt% kaolin clay is co-milled and slurried with binder in water. Surfactant is added to feed slurry during spray drying.
  • EXAMPLE G A dry mixture of 10 wt% ZSM-5 zeolite (Alsi-Penta 55) , 20% silica, 9% monoammoniuim phosphate, and 61% kaolin clay is co-milled and slurried with Ludox in water. Surfactant is added to feed slurry during spray drying.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

L'invention porte sur un procédé de fabrication de particules solides consistant en un mélange d'oxyde métallique cristallin et/ou de composés de sels, comportant les étapes suivantes: malaxage de composés métalliques pour former un mélange d'au moins deux solides cristallins; pulvérisation du mélange précédent de préférence à l'aide d'un microniseur dans lequel les particules sont projetées par un gaz inerte sec contre une surface dure de manière à produire des solides cristallins ultrafins; récupération du mélange des susdits solides cristallins ultrafins dont la taille moyenne est comprise entre 1 et 5ν; formation d'une pâte aqueuse dont le rapport eau/solides est inférieur à 2:1; séchage de la pâte aqueuse pour former des particules agglomérées d'une gamme de tailles moyennes supérieures à environ 20ν; et récupération des particules agglomérées séchées qui présentent une résistance à l'usure améliorée et une taille uniforme. Ledit procédé est particulièrement utile pour la fabrication de solides de contact à plusieurs composants.
EP98948071A 1997-10-10 1998-09-14 Fabrication de particules solides Withdrawn EP1044161A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US948358 1992-09-21
US94835897A 1997-10-10 1997-10-10
PCT/US1998/018169 WO1999019251A1 (fr) 1997-10-10 1998-09-14 Fabrication de particules solides

Publications (2)

Publication Number Publication Date
EP1044161A1 true EP1044161A1 (fr) 2000-10-18
EP1044161A4 EP1044161A4 (fr) 2002-07-10

Family

ID=25487710

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98948071A Withdrawn EP1044161A4 (fr) 1997-10-10 1998-09-14 Fabrication de particules solides

Country Status (3)

Country Link
EP (1) EP1044161A4 (fr)
AU (1) AU9472098A (fr)
WO (1) WO1999019251A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0127517D0 (en) * 2001-11-16 2002-01-09 Statoil Asa Catalysts
US6998100B2 (en) * 2003-11-19 2006-02-14 Toll Processing And Consulting, Llc Sulfur oxide sorption with layered chlorite-type contact solids

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4640825A (en) * 1985-03-26 1987-02-03 Battelle Memorial Institute Process for simultaneous removal of SO2 and NOx from gas streams
US4931264A (en) * 1986-11-07 1990-06-05 Board Of Regents, The University Of Texas System Process for removing sulfur from sulfur-containing gases
US5330943A (en) * 1989-03-10 1994-07-19 Thiele Kaolin Company Process for improving the physical and catalytic properties of a fluid cracking catalyst
US5498731A (en) * 1993-06-29 1996-03-12 Mitsubishi Chemical Corporation Oxide catalyst and process for producing maleic anhydride by using oxide catalyst
US5512097A (en) * 1994-04-08 1996-04-30 Emmer; Wayne W. Removal of sulfur oxides from waste gases by scrubbing with an aqueous slurry of finely comminuted limestone
US5559067A (en) * 1995-03-31 1996-09-24 Engelhard Corporation Modified microsphere FCC catalysts and manufacture thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
No further relevant documents disclosed *
See also references of WO9919251A1 *

Also Published As

Publication number Publication date
WO1999019251A1 (fr) 1999-04-22
AU9472098A (en) 1999-05-03
EP1044161A4 (fr) 2002-07-10

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