CA1043539A - Low surface area alumina - Google Patents

Low surface area alumina

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Publication number
CA1043539A
CA1043539A CA190,989A CA190989A CA1043539A CA 1043539 A CA1043539 A CA 1043539A CA 190989 A CA190989 A CA 190989A CA 1043539 A CA1043539 A CA 1043539A
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CA
Canada
Prior art keywords
alumina
per gram
surface area
boehmite
mix
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.)
Expired
Application number
CA190,989A
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French (fr)
Other versions
CA190989S (en
Inventor
Jeffrey W. Meacham
Joseph R. Kiovsky
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Saint Gobain Abrasives Inc
Original Assignee
Norton Co
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Filing date
Publication date
Application filed by Norton Co filed Critical Norton Co
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Expired legal-status Critical Current

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    • 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
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/021—After-treatment of oxides or hydroxides
    • C01F7/025—Granulation or agglomeration
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/612—Surface area less than 10 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/651—50-500 nm
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/653—500-1000 nm
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/11—Powder tap density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/21—Attrition-index or crushing strength of granulates

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

ABSTRACT OF THE DISCLOSURE
High purity, low surface area strong alumina bodies are formed from finely particulate alumina by a self-bonding technique in which acid activated microcrystalline boehmite is employed to bond a finely divided alumina selected from the group consisting of predominately gibbsite, bayerite, alpha alumina and crystalline boehmite. A mix of the bond and the alumina is molded by extrusion or other similar forming technique, and fired to produce a body of alpha, kappa, delta or theta alumina, or a mixture thereof, having desireable porosity characteristics, for use as catalysts and catalyst carriers.

Description

~0~;1539 a fl C~GROUND OF THE INV~NTION
The invention relates to a method for producing shaped bodies of alumina for u8e in catalytic applicationsJ
and to the alumina bodies 80 produced.
It has been proposed in our prior ~rench application Serial No. 72/16,828 filed May 10, 1972 which has been laid open to public inspection, to form alumina bodies of microcrystalline boehmite (as hereinafter defined) by treatment of the microcrystalline boehmite with formic acid or its equivalent, followed by a limited mixing which i5 then followed by extrusion and firing. Such a method produces high purity, strong, high surface area bodies of alumina.
It is an object of the present invention to provide high purity, low surface area, shaped monolithic, strong bodies of alumina, having a total pore volume of at least 0.25 cc/gm and a surface area of from 0.1 to 60 m /gm, preferably from 0.1 to 10 m /gm and a method for this production.

Thus, in accordance with the present teachings, a method is provided for making high purity alumina catalyst bodies which comprises mixing microcrystalline boehmite with from 0 - 90~ by weight, basedon alumina content, of a material selected from the group consisting of gibbsite, bayerite, boehmite, alpha alumina and mixtures thereof, at least one acid selected from the group consisting of formic, acetic, hydrochloric, propionic and nitric, the acid being present in an amount of from 0.128 to 1.28 moles per mole of A1203 in the microcrystalline boehmite and water in the amount of from 15 to 100 part~ per 100 parts of dry mix.
The mix is shaped, dried and fired at a temperature between 950 and 1425C to produce bodies having a surface area of from 0.1 to 60 square meters per gram and composed of alumin~ selected from th~ group consisting of alpha, delta
- 2 ~J~
L~ ~

, 1Q43539 - and kappa aluminas and mixtures thereof.
In accordance with a further teaching there i8 provided a high purity, shaped monolithic, strong body of alumina which has a surface area of from 0.1 to 60 square meters per gram, a pore volume of at least 0.25 cubic centimeters per gram, exclusive of any pores produced by burnout material, a pore volume in pores larger than 1000 angstroms of greater than 0.1 cubic centimeters per gram, exclusive of pores produced by burnout materials, and a total impurity content of less than 1~.

By employing formic acid (or equivalent acid) treated microcrystalline boehmite as a bond for gibbsite (alpha alumina trihydrate3, bayerite (beta alumina trihydrate), boehmite (alpha alumina monohydrate), or alpha alumina we have found that forming, drying and firing at a temperature of from 950C to 1425C novel products of kappa, delta, theta and alpha alumina can be formed.
As used in the present application the term micro-crystalline boehmite refers to what is sometimes called pseudo-boehmite. The material is made up of aggregates of platy crystallites such aggregates typically ranging from 1 to 40 microns in diameter, and in all cases averaging under 30 microns in diameter. The crystals in the aggregates are platy in habit -2a-~ 0~3539 and smaller than 750 angstroms in diameter, preferably less than 100 angstroms in diameter. Furthermore microcrystalline boehmite is distinguished by having a molar ratio of chemically combined water to Al2O9 of between 1.16 and 2, preferably between 1.2 and 1.6. This product is distinguishable from boehmite produced by controlled calcination of gibbsite, which is more well crystallized and has a typical average crystal size of over 1000 angstroms.
One commercially available microcrystalline boehmite is sold under the trademark Catapal S or Catapal SB, by Continental Oil Company, and is produced by the hydrolysis of aluminum alcoholates. Another microcrystalline boehmite is sold by Kaiser Chemical Company under the designation XCSA-M alumina.
Suitable boehmites (i.e. microcrystalline boehmites) are further characterized by their ability to be dispersed by certain monobasic acids~ The dispersability of any given sample of boehmite, and thus its active microcrystallinity, can be determined by treating the sample with dilute nitric acid, centrifuging the sample to separate the coarser crystals and agglomerates from the liquid, and measuring ~he light transmittance of the liquid. By the specific test described below the transmittance for active microcrystalline boehmite i9 le~s than 50% and preferably less than 20~.
The method for determining the transmittance is a~
follows:
1. Weigh a 3.0 gram sample into a 150 ml. beaker, add 25 ml.-of 0.5 normal HN03, add a stirring bar and cover with a watch glas~.
2. Place the beaker on a magnetic stirrer and stir for 10 mimutes at a speed of 900 to 1100 rpm.

~.04353~ .
3. Transfer the contents of the beaker to a centrifuge bottle and dilute with distilled water to bring the volume to 90 ml.
4. Centrifuge the sample in a 9-7/8 inch radius centrifuge at 1000 rpm for 20 minutes.
5. Measure the transmittance of the supernatent liquid in a 10 mm. test cell at a wave length of 450 millimicrons, as a percent of the transmittance of distilled water.
Pore volume and pore size measurements as used h~reiE are made by the mercury porosimetry method,~and take no account of pores smaller than 44 angstroms in diameter. The median pore diameter is defined as the pore diameter at which 50% of the total accessible (that is: open pore volume) pore volume is accounted for by larger p;o~-~, and 50% of the total pore volume is represented by smaller pores (exclusive of the pore volume represented by pores smaller than 44 angstroms in diameter).
Instead of formic acid, other monobasic acids may be used such as acetic, hydrochloric, nitric, and propionia.
Acids with anions larger than the anion of propionic acid are not suitable, however, The acid is used in dilute form 2 parts of 90~ formic acid being typically added to 30 parts of water, for example. The dry microcrystalline boehmite can be mixed with the alumina to he bonded, (hereinafter referred to as grain) and the dilute acid added to the dry mix. Mixing is continued until a granular, free flowing mix is obtained.
Continuation of mixing eventually can result in a Pasty, doughy mix, unsuitable for certain types of extrusion. After extrusion the pellets or other shapes are dried and fired to ~e~ratures ranging from 950C to 1425C, depending upon the desired pore structure and alumina phases.
The mole ratio of acid to alumina as A1203 in the bonding material can vary from 0.128 to 1.28. The bond may constitute from 10 to 100~ of the mix, based on alumina content, and the water content can vary from 15 to 30 parts by weight for bonding gibbsite and bayersite to from 35 to 100 parts per hundred parts for bonding monohydrated or anhydrous aluminas, Where the bodies are all microcrystalline boehmite (no added grain) the water content would be as for bonding boehmi~e.
Although the aluminas of this invention are them-selves catalysts for many reactions, the bodies may be impreg-nated~with additional catalytically active materials. Alternatively the catalyst material may be added to the mix of bond and grain prior to forming.
For some applications it is desirable to incr~ase the large pore porosity of the bodies by including an organic burnout material in the mix. This adds porosity to the bodies without affecting the pore size distribution of the inherent pores in the bond-grain matrix. The "burnout" material need not necessarily be one which actually burns, for example a volatile material such as paradichlorabenzene could be used in some cases.
Whether including a burnout material or not, the surface area of the produc~s produced by this invention have a surface area, as measured by the B.E.T. nitrogen adsorption method, of at least 0.1 square meters per gram.
The preferred novel products of this invention have a surface area of from 0~1 to 60 square meters per gram, a pore volume, exclusive of any pores produced by burnout material 10~3539 of greater than 0.25 cubic centime~ers per gram, a pore volume in pores larger than 1000 angstroms of greater than 0.1 cubic centimeters per gram, exclusive of burnout material, and a total impurity content of less than from 0.2 to 1%. Although such porosity properties have been achieved in the past by the use of clay type bonds for alumina, we are aware of no such prior art productæ having an impurity level as lows as 1h.
m e flat plate crushing strength referred to herein was measured on a standard commercially available apparatus, Research Products Crush Tester. The pellets tested were 1/8 inch diameter 1/4 inches long, with the force being applied perpendicular to the axis of the pellets.
ILLUSTRATIONS OF TH~ INVENTION
ExamPle I
80 parts Alcoa C-331 Aluminum trihydrate (gibbsite) and 20 parts Catapal sa microcrystalline boehmite alumina were added to a conical liquid solids blender (Abbe) and mixed.
In a separate vessel, 3 parts 90% formic acid and 24 parts water were mixed. The dilute acid solution was then added to the dry ingredients in the mixer. Mixing continued for several minutes subsequent to liquid addition to en~ure uniform mixing. This mix was then extruded and formed into 1 mm diameter spaghetti, dried to the pxoper moisture ~level and spheridized into 1/32" diameter spheres. The spheres were dried in air and fired to 1390C. These dried 1/32" diameter spheres had the following properties:
Surface Area, M~/gm ~ 2.09 VT~ cc/gm - 0.297 Median Dp, microns - 0.35 Tapped Bulk Density, gm/cc -1.256 ``` ~04~S3g ExamPle II
80 parts Alcoa C-331 aluminum trihydrate (gibbsite~
and 20 parts Catapal SB microcrystalline boehmite alumina were added to a high intensity mixer (Hobart) and mixed. In a separate ve~sel, 3 parts 90% formic acid and 26.7 parts water were mixed. The dilute acid solution was then added to the dry ingredients in the mixer. Mixing was continued for about 30 seconds. This mixture was then extruded and formed into 1/8" diameter pellets. These pellets were then air dried and fired to 537C. They next were refired to a final temperature of 950C and had the following properties:
Surface Area, M2/gm - 56.8 Crush Strength, lbs. - 10.4 XRD - Kappa and Delta Aluminas VT, cc/gm - 0.481 Median Dp, microns - 0.029 xamPle III

.

80 parts Alcoa C-331 aluminum trihydrate (gibbsite) and 20 parts Catapal SB microcrystalline boehmite alumina were added to a high intensity mixer (Ho~art) and mixed. In a separate vessel, 3 parts 90h formic acid and 29 parts water were mixed. The dilute acid solution was then added to the dry ingredients in the mixar. Mixing continued for 30 seconds subsequent to liquid addition. The mix was then extruded and formed into 1/8" diameter pellets. The pellets were air dried and fired to 500C. They next were refired to a final temperature of 1250C. Their fired properties were as follows:
Surface Area, ~/gm - 5.56 Crush Strength, lbs. - 21.5 VT, cc/gm - 0.410 Median ~, microns - 0.204 Example IV
80 parts Alcoa C-331 aluminum trihydrate (gibbsite), 20 parts Catapal S microcrystalline boehmite alumina and 1 part cellulose binder were added to a conical liquid ~olids blender (Abbe) and mixed. In a separate vessel, 2.73 parts 90/O formic acid and 25.4 parts water were mixed. ~he dilute acid solution was then added to the dry ingredients in the mixer. Mixing continued for several minute~ subsèguent to liquid addition,to ensure uniform mixing. Thi8 mix was then extruded and formed into 1/8" diameter pellets. The pellets were air dried, then placed in a furnace and calcined at 1427C. These fired pellets had the ollowing properties:
Surface Area, M2/gm - 0.28 c VT, cc/gm - 0.304 Median Dp, microns - 0.82 Crush Strength, lbs. - 35.6 Data from the four examples can be better represented in the following table.

~ Final -I 20 Firing Surface ¦ Temp. Area Crush YT Med. Dh ', C M2/am Lbs. cc/am Microns XRD
950 56.80 10.4 0.481 0.029 kappa, delta 1250 5.56 21.5 0.410 0.204 alpha , 1390 2.09 - 0.297 0.35 alpha ' 1427 0.28 35.6 0.304 0.82 alpha These carriers have a typical chemlcal analysls of:
Al2Os - 99-79%
SiO2 ~ 0.02%
Fe203 = 0.01%
Na20 = 0.~8%

The carriers described in our ~x~mple~ 1 through 4 are unique in purity, pore volume and pore distribution. The method we use to make these carriers is a novel way or producing high purity low surface area alumina carriers.
By raising the calcination temperature, we can lower the pore volume, increase the median pore diameter and increase the bodies~ crush strength. ~hi~ i9 due to the increased sintering and densification of alpha alumina which takes place at elevated temperatures.
With our novel method, we are capable of producing carriers with identical properties in a wide variety of shapes, such as saddles, rings and pellets. So far, we have alæo pr~duced ~uite a range of diameters. We have extruded pellets as small as 1/32" in diameter and rings as large as 5/8" in diameter.

_ 9 _ ~:,

Claims (5)

  1. The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
    l. A method of making high purity alpha alumina catalyst bodies comprising mixing microcrystalline boehmite with from 0 - 90% by weight, based on alumina content, of a material selected from the group consisting of gibbsite, bayerite, boehmite, and alpha alumina and mixtures thereof at least one acid selected from the group consisting of formic acetic, hydrochloric, propionic and nitric, said acid being present in an amount of from 0.128 to 1.28 moles per mole of Al2O3 in the microcrystalline boehmite, and water in the amount of from 15 to 100 parts per hundred parts of dry mix, shaping said mix, drying the shaped mix, and firing at a temperature between 950 and 1425°C to produce alpha alumina bodies having a surface area of from 0.1 to 60 square meters per gram.
  2. 2. The method of claim 1 wherein the alpha alumina bodies have a surface area of from 0.1 to 10 square meters per gram.
  3. 3. A method of making high purity alumina catalyst bodies comprising mixing microcrystalline boehmite with from 0 - 90% by weight, based on alumina content, of a material selected from the group consisting of gibbsite, bayerite, boehmite, alpha alumina and mixtures thereof, at least one acid selected from the group consisting of formic, acetic, hydrochloric, propionic and nitric, said acid being present in an amount of from 0.128 to 1.28 moles per mole of Al2O3 in the microcrystalline boehmite, and water in the amount of from 15 to 100 parts per hundred parts of dry mix, shaping said mix, drying the shaped mix, and firing at a temperature between 950 and 1425°C to produce bodies having a surface area of from 0.1 to 60 square meters per gram and composed of alumina selected from the group consisting of alpha, delta and kappa aluminas and mixtures thereof.
  4. 4. A high purity, shaped monolithic, strong body of alumina having a surface area of from 0.1 to 60 square meters per gram, a pore volume of at least 0.25 cubic centimeters per gram, exclusive of any pores produced by burnout material, a pore volume in pores larger than 1000 angstroms of greater than 0.1 cubic centimeters per gram, exclusive of pores produced by burnout material, and a total impurity content of less than 1%.
  5. 5. A high purity, shaped monolithic, strong body of alumina having a surface area of from 0.1 to 60 square meters per gram, a pore volume of at least 0.25 cubic centimeters per gram, exclusive of any pores produced by burnout material, a pore volume in pores larger than 1000 angstroms of greater than 0.1 cubic centimeters per gram, exclusive of pores produced by burnout material, and a total impurity content of less than 0.2%.
CA190,989A 1973-01-26 1974-01-25 Low surface area alumina Expired CA1043539A (en)

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JP (1) JPS507797A (en)
BE (1) BE810103A (en)
CA (1) CA1043539A (en)
DE (1) DE2403638A1 (en)
FR (1) FR2215389B1 (en)
GB (1) GB1465523A (en)
IT (1) IT1009123B (en)
NL (1) NL7400966A (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2449474A1 (en) * 1979-02-26 1980-09-19 Rhone Poulenc Ind DOUBLE POROSITY ALUMINA BEADS, THEIR PREPARATION PROCESS AND THEIR APPLICATIONS AS CATALYST SUPPORTS
DE3374666D1 (en) * 1983-03-08 1988-01-07 Dow Chemical Co Catalyst for selective hydrogenation of alkynes in the presence of dienes
NL8600959A (en) * 1986-04-16 1987-11-16 Veg Gasinstituut Nv CATALYST FOR THE SELECTIVE OXYDATION OF SULFUR-CONTAINING COMPOUNDS, IN PARTICULAR SULFUR HYDROGENIC TO ELEMENTAL SULFUR; METHOD FOR PREPARING THE CATALYST AND METHOD FOR SELECTIVE OXIDIZATION OF SULFUR CONTAINERS, IN THE PARTICULAR SULFUR HYDROGENIC SODIUM SULFUR.
CN1009437B (en) * 1988-02-03 1990-09-05 中国石油化工总公司 High-efficiency silver catalyst for oxidizing ethylene into epoxy ethane
DE4311650C2 (en) * 1993-04-08 1996-06-05 Sued Chemie Ag Highly porous moldings based on aluminum oxide and their use
JP7259846B2 (en) * 2018-04-06 2023-04-18 Dic株式会社 alumina particles
CN111019605A (en) * 2019-12-05 2020-04-17 青岛瑞克尔新材料科技有限公司 Ceramic microcrystalline abrasive material with low bulk density and preparation method of abrasive tool product thereof

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* Cited by examiner, † Cited by third party
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US3669904A (en) * 1970-05-28 1972-06-13 Air Prod & Chem Particles featuring gamma alumina
US3652449A (en) * 1970-06-24 1972-03-28 Union Oil Co Hydrocarbon conversion processes using alumina-bonded catalysts

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JPS507797A (en) 1975-01-27
BE810103A (en) 1974-07-24
FR2215389A1 (en) 1974-08-23
GB1465523A (en) 1977-02-23
DE2403638A1 (en) 1974-08-15
NL7400966A (en) 1974-07-30
IT1009123B (en) 1976-12-10

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