CN1060098C - Hydrothermal treatment process of zeolite - Google Patents
Hydrothermal treatment process of zeolite Download PDFInfo
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- CN1060098C CN1060098C CN97103967A CN97103967A CN1060098C CN 1060098 C CN1060098 C CN 1060098C CN 97103967 A CN97103967 A CN 97103967A CN 97103967 A CN97103967 A CN 97103967A CN 1060098 C CN1060098 C CN 1060098C
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Abstract
The present invention relates to a hydrothermal treatment method for zeolite, which comprises the following steps: mixing zeolite whose sodium oxide content is smaller than 1 wt% with one or more forming assistants selected from organic carbon-contained compounds having the functions of adhesion and lubrication and water in a weight ratio of 100: (1 to 15): (50 to 140); extruding the mixture into strips; contacting the shaped products with a steam-containing atmosphere for 0.5 to 8 hours at 500 to 870 DEG C and steam weight space velocity of 0.05 to 3.5 per hour. The method is suitable for industrial production.
Description
The invention relates to the method for modifying of molecular sieve, more specifically say so about the hydro-thermal treatment method of Si-Al zeolite.
The catalyst that with the zeolite is active component has been widely used in the various hydrocarbon conversion reactions, the kind difference of reaction, the kind of used zeolite and character also have a great difference in the catalyst, for improving or reduce activity of such catalysts or improving to the differential responses product selectivity, need zeolite is carried out various modifications, and since US3,293,192, US3,402,996 disclose with high-temperature water vapor handle y-type zeolite with the method for preparing super steady Y since, become one of the most frequently used method of modifying of zeolite with the steam treatment zeolite, in this way or contain the zeolite of other method modification of this method, as faujasite, the ZSM-5 zeolite, modenite, Beta zeolite etc. can be used as the active component of various hydrocarbon conversion catalysts, particularly catalytic cracking and hydrocracking catalyst.
EP0,667,185A1 discloses a kind of method for preparing modified Y zeolite, and this method comprises that (a) with a kind of ammonium salt solution exchange NaY zeolite, makes Na in the zeolite
2O content is reduced to below the 7 heavy %; (b) product that (a) obtained contains aluminum water solution with the acidity of a kind of PH2～4 and contacts, and makes in the zeolite and contains, with Al
2O
3Meter, the aluminium in 0.5～6 heavy % exchange; (c), the product that obtains of separating, washing (b), and in 450～800 ℃ of roastings 15 minutes～4 hours under water vapour atmosphere; (d) handle the zeolite that (c) obtains with a kind of phosphorus-containing compound, weigh the phosphorus of % (with P to introduce 0.1～4
2O
5Meter), the modified zeolite for preparing with this method has the selectivity of higher gasoline and light cycle oil, and has reduced coke yield.
Yet, as US 5,288,396 is pointed, if molecular sieve mix with heat-resistant inorganic oxide and moulding before carry out hydrothermal treatment consists, because of molecular sieve is Powdered, particle very little (diameter is generally 0.1～10 micron), when in inclination kiln rotary furnace, carrying out hydrothermal treatment consists, a large amount of particles along the furnace wall or the stove heart flow, and water vapour cross direction profiles in flowing is also inhomogeneous, cause sieve particle in flowing, to be difficult to carry out even contact with water vapour, some sieve particles have contacted too much water vapour and have removed too much framework aluminum, and other sieve particle contact water vapours seldom, and framework aluminum is not removed basically, this has just caused sieve particle is carried out the stable bad of product after the hydrothermal treatment consists, catalytic activity and/or selectivity as the resulting zeolite product of experiment of twice similarity condition have very big difference, with the catalytic activity and/or the selectivity of once testing each sieve particle a great difference are arranged also, are difficult to well in industrial application.Moreover, as molecular sieve powder is carried out hydrothermal treatment consists in fixed bed,, can not use industrial because the too little meeting of sieve particle causes too high pressure drop.
At US 5,288, disclosed a kind of hydrothermal modification method of zeolite in 396 in the disclosed method for hydrogen cracking.This method for hydrogen cracking is included under the condition that hydrocracking and outer hydrogenation exist hydrocarbon raw material is contacted with a kind of catalyst, described catalyst contains the zeolite that unit cell dimension is 24.20～24.40A, this prepare zeolite method comprises: (a) with at least a heat-resistant inorganic oxide and a kind of crystal silicon-aluminate zeolite component extrusion molding with cracking activity, the unit cell dimension of described crystal silicon-aluminate zeolite is 24.40～24.95 dusts, and it is selected from one group that is made up of Y zeolite, modified Y zeolite, X zeolite and modification X zeolite; And (b) be higher than roasting article shaped under the 5.0Psia at steam partial pressure, roasting condition should make the unit cell dimension of crystal silicon-aluminate zeolite be contracted to 24.20～24.40 dusts.For example, at least 500 ℃ of sintering temperatures, common 600～870 ℃, best 700～850 ℃, gross pressure 7.5～3000Psia, best 15～1500Psia, the steam partial pressure usual range is 200～150Psia, best 5.0～35Psia.Adopt at least 1/32 inch of the diameter of the catalyst granules of this method preparation, more much bigger than sieve particle, thereby, when being carried out hydrothermal treatment consists in rotary furnace, this catalyst granules can evenly pass through body of heater, each catalyst granules can touch approximately equalised quantity of steam, thereby the character of the catalyst after steam treatment is even and good reproducibility, and this processing method also can be carried out in fixed bed.Yet what obtain in this way is a kind of hydrocracking catalyst composition, rather than pure zeolite, in addition, adopts the non-molecular sieve component of this mode carrier (being heat-resistant inorganic oxide) to be handled by high-temperature water vapor simultaneously and its character is changed.The normal employing is broken into particle again with the zeolite compression molding earlier in the laboratory, sieve is got the zeolite of suitable granularity, is carried out the method for steam treatment at last then, this method can obtain pure molecular sieve, but complicated operation, yield rate was very low when the broken again sieve of the zeolite after the moulding was got suitable granularity, and this method obviously can't be in industrial large-scale application.
The zeolite that the objective of the invention is after a kind of the processing is provided on the prior art basis has uniform nature, good reproducibility, and is more suitable for the hydro-thermal treatment method of the zeolite of commercial Application.
Method provided by the invention comprises that sodium oxide content is selected from organic help forming agent and the water that contains the charing compound with bonding, lubrication less than the zeolite of 1 heavy % with one or more to be mixed by 100: 1～15: 50～140 weight ratio, extruded moulding, is 0.05～3.5 hour at 500～870 ℃ with article shaped and water vapour weight space velocity then
-1The atmosphere contact 0.5～8 hour of moisture vapor.
According to method provided by the invention, described zeolite can be any existing zeolite, as faujasite natural or that manual method is synthetic, the ZSM series zeolite, modenite, the Beta zeolite, omega zeolite etc., preferred X type zeolite, y-type zeolite, modenite or ZSM-5 zeolite, more preferred y-type zeolite, modenite or ZSM-5 zeolite, y-type zeolite preferably, described zeolite can be the zeolite that contains the component of other needs, as contain the rare-earth type zeolite of rare earth, the zeolite of alkaline including earth metal, nickeliferous, cobalt, iron, the zeolite of elements such as zinc and contain aluminium type zeolite that adds aluminium etc., method provided by the invention is specially adapted to contain the AlY zeolite that adds aluminium, other component in the described zeolite that contains other component (as aluminium) can adopt conventional ion-exchange, infusion process is introduced, but also can be with the salt of this ion of high-temperature roasting acid group burn off or the method introducing of its aqueous solution and zeolite mechanical mixture, when this ion is aluminium ion, aluminum ions introducing amount (in aluminium oxide) is not more than 20 heavy %, best 0.05～10 heavy %; Describedly contain zeolite that sodium oxide molybdena is lower than 1 heavy % and na-pretreated zeolite can be carried out ion-exchange (as ammonium ion exchange) and obtain.
It is described that to be selected from organic forming agent that helps that contains the charing compound can be that any one has bonding, lubrication, but organic charing compound that contains of high temperature burn off, in preferable methyl cellulose, polyvinyl alcohol, the plant amylum one or more, zeolite and the weight ratio preferred 100: 2～10: 60～120 that helps forming agent and water.
Preferred 550～700 ℃ of the temperature of described hydrothermal treatment consists; The atmosphere of moisture vapor can be water vapour and Air mixing gas, the gaseous mixture of water vapour and oxygen, the gaseous mixture of water vapour and other inert gas such as nitrogen, it also can be 100% water vapour, preferably water vapour and Air mixing gas, this can guarantee that the overwhelming majority helps forming agent by burn off after steam treatment, when the atmosphere of moisture vapor is water vapour and Air mixing gas, and preferred 0.1～2.45 hour of the weight space velocity of water vapour
-1, the volume space velocity of air can be 0.1～1500 hour
-1, preferably 1～1200 hour
-1Preferably 2～6 hours time that described zeolite granular contacts with moisture vapor atmosphere.When moisture vapor atmosphere did not contain air or oxygen, part helped in the article shaped after forming agent is still stayed processing, but roasting removes and helps forming agent under this moment nationality air atmosphere.
According to method provided by the invention, earlier with zeolite, help forming agent and water to mix, extruded moulding, again article shaped is carried out hydrothermal treatment consists, the mechanical radial strength of article shaped before hydrothermal treatment consists is not less than 6.0 kilograms per centimeter, radial strength is not more than 10 kilograms per centimeter after the hydrothermal treatment consists, the article shaped of intensity guarantees that on the one hand article shaped is difficult for crushed or breaks up in the hydrothermal treatment consists process like this, zeolite is easy to grind after having guaranteed hydrothermal treatment consists on the other hand again, be convenient to the preparation of zeolite containing catalyst, thereby be more suitable for industrial needs.
Analyze theoretically, in the method provided by the invention, can regulate the granularity of zeolite article shaped according to used activation furnace and concrete experiment condition, bigger as the granularity that when being used for fixing a bed activation furnace, then need regulate zeolite, phenomenons such as channel can not appear again simultaneously to reduce bed pressure drop, when being used for rotary furnace, can determine the granular size of article shaped according to air velocity or other reaction condition, and press US 5,288,396 method want to take into account catalyst in reaction granularity and the granularity during hydrothermal treatment consists consistent be difficult.Moreover with US 5,288,396 described reasons are identical, the zeolite that obtains by method provided by the invention has uniform nature and good reproducibility.
Can be widely used as various hydrocarbon conversion catalysts such as catalytic cracking catalyst with the zeolite after the method processing provided by the invention, hydrotreating catalyst, hydrocracking catalyst, alkylation catalyst, the active component of isomerization catalyst, be specially adapted to active component as hydrotreatment and hydrocracking catalyst, for example, the y-type zeolite after handling according to method provided by the invention or the lattice constant of AlY zeolite can be retracted to from 24.56A and be lower than 24.43A, the secondary porosity is more than or equal to 24.5%, the hydrocracking catalyst that contains this zeolite is compared with the prior art industrial catalyst in the close isomerization of maintenance optionally simultaneously, has higher lytic activity, as being reaction raw materials with the normal heptane, 350 ℃ of reaction humidities, hydrogen pressure 2.5MPa, volume space velocity 1 hour
-1Reaction condition under, when containing the zeolite hydrotreating catalyst of 5 heavy % the inventive method preparations, keeping the isomery close while optionally with the prior art catalyst, the conversion ratio of normal heptane is brought up to 35.06～45.18 heavy %, and the normal heptane conversion ratio has only 20.49 weight % during with the prior art catalyst.
The following examples will the present invention will be further described.
Example 1
By method provided by the invention y-type zeolite is carried out hydrothermal treatment consists.
With 800 gram NaY zeolite (SiO
2/ Al
2O
3=3.5, Chang Ling oil plant catalyst plant product) placing 4000 ml concns is that the ammonium chloride of 1.0M (is analyzed pure, Beijing Chemical Plant's product) in the aqueous solution, exchange 1 hour down at 90 ℃, filter, spending deionised water is not detected to there being chlorion, 120 ℃ of oven dry, 550 ℃ of roastings 4 hours, repeat twice of said process, get the y-type zeolite A ' of sodium oxide content 0.35 heavy % (flame atomic absorption spectrometry mensuration), the lattice constant of measuring this zeolite with x-ray diffraction method is 24.56A, and relative crystallinity is decided to be 100%.
With y-type zeolite A ' 100 grams after the above-mentioned ammonium exchange; 70 milliliters of deionized waters and methylcellulose (trade mark M20; Shanghai chemical reagent factory produces;) mix; on banded extruder, be extruded into the bar shaped of 3 millimeters of diameters; it is 10.0 kilograms per centimeter that its radial strength is surveyed in dry back; dried article shaped is placed vertical activation furnace; speed with 250 Grams Per Hours and 1 liter/hour feeds water and air respectively; be warming up to 650 ℃ and constant temperature 2 hours; y-type zeolite A after must handling after the cooling, its physico-chemical property is listed in the table 1.Wherein the radial strength assay method is referring to " petrochemical industry analytical method " (RIPP test method) P66～67, Science Press, 1990, lattice constant, relative crystallinity, framework si-al ratio adopt x-ray diffraction method to measure, micro pore volume, pore volume adopt cryogenic nitrogen absorption BET method to measure secondary porosity=(pore volume-micro pore volume)/pore volume * 100%.
Example 2
According to method provided by the invention AlY type zeolite is carried out hydrothermal treatment consists.
Take by weighing aluminum nitrate (chemical pure, Beijing Chemical Plant's product) 11 grams are dissolved in 65 ml deionized water and are made into aluminum nitrate solution, zeolite A ' 100 grams and methylcellulose 3.0 grams of this solution and example 1 preparation are mixed, on banded extruder, be extruded into the bar shaped of 3 millimeters of diameters, it is 12.0 kilograms per centimeter that its radial strength is surveyed in dry back, dried article shaped is placed vertical activation furnace, speed with 200 Grams Per Hours and 0.5 liter/hour feeds the deionization water and air respectively, be warming up to 600 ℃ and constant temperature 4 hours, AlY zeolite B after must handling after the cooling, its physico-chemical property is listed in the table 1.
Example 3
According to method provided by the invention AlY type zeolite is carried out hydrothermal treatment consists.
Taking by weighing aluminum nitrate (with example 2) 31 gram is dissolved in 70 ml deionized water and is made into aluminum nitrate solution, zeolite A ' 100 grams and sesbania powder (Shanghai local products company product) 3 grams of this solution and example 1 preparation are mixed, on banded extruder, be extruded into the bar shaped of 3 millimeters of diameters, it is 10 kilograms per centimeter that its radial strength is surveyed in dry back, dried article shaped is placed vertical activation furnace, speed with 150 Grams Per Hours and 5 liters/hour feeds the deionization water and air respectively, be warming up to 550 ℃ and constant temperature 6 hours, AlY zeolite C after must handling after the cooling, its physico-chemical property is listed in the table 1.
Example 4 carries out hydrothermal treatment consists according to method provided by the invention to AlY type zeolite.
Taking by weighing aluminum nitrate (with example 2) 77 gram is dissolved in 100 ml deionized water and is made into aluminum nitrate solution, zeolite A ' 100 grams and sesbania powder 3 grams with this solution and example 1 preparation, polyhexene alcohol (chemical pure, Shanghai Petrochem. General Plant's product) 5 grams mix, on banded extruder, be extruded into the bar shaped of 3 millimeters of diameters, it is 15 kilograms per centimeter that its radial strength is surveyed in dry back, dried article shaped is placed vertical activation furnace, speed with 10 Grams Per Hours and 110 liters/hour feeds the deionization water and air respectively, be warming up to 650 ℃ and constant temperature 4 hours, AlY zeolite D after must handling after the cooling, its physico-chemical property is listed in the table 1.
Example 5
Carry out hydrothermal treatment consists according to method provided by the invention to containing the modenite that adds aluminium.
Take by weighing aluminum nitrate 11 gram and be dissolved in 112 ml deionized water and be made into aluminum nitrate solution, with this solution and modenite (SiO
2/ Al
2O
3=20, sodium oxide content: 0.01 heavy %, Fushun oil-refining chemical three factories product) 150 grams, sesbania powder 3 grams and methylcellulose 3 grams mix, be extruded into the bar shaped of 3 millimeters of diameters on banded extruder, it is 17 kilograms per centimeter that its radial strength is surveyed in dry back, and dried article shaped is placed vertical activation furnace, speed with 70 Grams Per Hours and 10 liters/hour feeds water and air respectively, be warming up to 550 ℃ and constant temperature 4 hours, the modenite E after must handling after the cooling, its physico-chemical property is listed in the table 1.
Example 6
According to method provided by the invention ZSM-5 is carried out hydrothermal treatment consists.
With 150 gram ZSM-5 zeolite (SiO
2/ Al
2O
3=40, sodium oxide content: 0.1 heavy %, dying of Shanghai seven factories produce) 120 ml deionized water, 3 restrain the sesbania powder and 3 gram methylcellulose mix, on banded extruder, be extruded into the bar shaped of 3 millimeters of diameters, it is 13 kilograms per centimeter that its radial strength is surveyed in dry back, dried article shaped is placed vertical activation furnace, speed with 100 Grams Per Hours and 7.5 liters/hour feeds the deionization water and air respectively, be warming up to 550 ℃ and constant temperature 4 hours, ZSM-5 zeolite F after must handling after the cooling, its physico-chemical property is listed in the table 1.
Table 1
| Example number | 1 | 2 | 3 | 4 | 5 | 6 |
| The zeolite product numbering | A | B | C | D | E | F |
| Mechanical radial strength, kilograms per centimeter | 2．0 | 3．0 | 5．0 | 6．0 | 2．5 | 4．0 |
| Lattice constant, dust | 24．43 | 24．39 | 24．36 | 24．32 | - | - |
| Relative crystallinity, % | 95 | 78 | 64 | 54 | 93 | 96 |
| Framework si-al ratio, moles/mole | 7．4 | 8．9 | 9．5 | 11．8 | - | - |
| Micro pore volume, milliliter/gram | 0．2345 | 0．2450 | 0．2080 | 0．2220 | - | - |
| Pore volume, milliliter/gram | 0．3120 | 0．3500 | 0．2870 | 0．3300 | - | - |
| The secondary porosity, % | 24．8 | 30．0 | 27．5 | 32．7 | - | - |
Example 7～8
The following examples explanations contains the catalytic performance of hydrotreating catalyst of the zeolite of the inventive method preparation.
The AlY zeolite of example 2 and example 5 preparations and modenite (are contained boehmite 85 weight % with the SB powder respectively by the weight ratio of 5: 95 (butt), Germany Condea company produces) mix, add an amount of extrusion aid and water, on banded extruder, extrude the bar shaped of 2 millimeters of diameters, 120 ℃ of oven dry, 600 ℃ of roastings 4 hours must contain the catalyst carrier of AlY and modenite, taking by weighing each 100 gram of carrier that contains the AlY zeolite and the carrier that contains modenite, is the NH of 23.1 heavy % with 65 gram concentration respectively
4F (chemical pure, the Beijing Chemical Plant produces) solution impregnation is after 120 ℃ of oven dry, again with containing WO
3638.5 the ammonium metatungstate (NH of grams per liter and NiO 63.85 grams per liters
4W
4O
318H
2O, chemical pure, the Sichuan Zigong Hard Alloy Foundry is produced) and nickel nitrate (Ni (NO
3)
26H
2O, chemical pure, Beijing Chemical Plant's product) 65 milliliters of dippings of solution, 120 ℃ of oven dry, 500 ℃ of roastings 4 hours must contain the catalyst I of AlY zeolite and contain the catalyst II of modenite, heavy %, WO of fluorine-containing 5 heavy %, NiO2.7 in the catalyst
327.0 heavy % (calculated value).
Catalyst II and II are broken into 40～60 purpose particles respectively, and mix with equigranular quartz sand by 1: 1 volume ratio respectively, the 2 milliliters of reactors of packing into, with the normal heptane is that model compound is estimated respectively the catalytic performance of catalyst I and II, under 300 ℃ of nitrogen atmosphere, catalyst is given sulfuration 2 hours earlier before estimating with the normal heptane that contains 3 heavy % carbon disulfide, appreciation condition is 350 ℃ of reaction temperatures, hydrogen pressure 2.5MPa, volume space velocity 1 hour
-1, hydrogen flowing quantity 400 ml/min, the product gas chromatographic analysis, normal heptane conversion ratio and isomerization selectivity are listed in the table 2, here, isomery selectivity=isomerized products yield/conversion ratio * 100%.
Comparative Examples 1
This Comparative Examples illustrates that the catalyst of the zeolite of method provided by the invention preparation is compared with existing industrial catalyst and is keeping high isomery optionally to have higher catalytic activity simultaneously.
(RL-1, the Chang Ling oil plant is produced, alumina support, fluorine-containing 4.9 heavy %, NiO 2.9 heavy %, WO to the industrial catalyst III under the condition identical with example 7～8
328.3 heavy %) estimate, the conversion ratio of normal heptane and isomerization selectivity are listed in the table 2.Table 2
| Example number | 7 | 8 | Comparative Examples 1 |
| The catalyst numbering | Ⅰ | Ⅱ | Ⅲ |
| Conversion ratio, % | 45．18 | 35．06 | 20．49 |
| The isomerization selectivity, % | 92．0 | 91．0 | 92．0 |
Claims (9)
1. the hydro-thermal treatment method of a zeolite, it is characterized in that this method comprises mixes with help forming agent and the water that one or more are selected from the organic carbonaceous compound with bonding, lubrication the zeolite of sodium oxide content less than 1 heavy % by 100: 1～15: 50～140 weight ratio, extruded moulding, be 0.05～3.5 hour at 500～870 ℃ with article shaped and water vapour weight space velocity then
-1The atmosphere contact 0.5～8 hour of moisture vapor.
2. according to the described method of claim 1, it is characterized in that described zeolite refers to y-type zeolite, modenite or ZSM-5 zeolite.
3. according to the described method of claim 2, it is characterized in that described zeolite refers to y-type zeolite.
4. according to the described method of claim 3, it is characterized in that described zeolite refers to contain the AlY zeolite that adds aluminium.
5. according to the described method of claim 4, it is characterized in that, with Al
2O
3Meter, the introducing amount of aluminium is not more than 20 heavy % in the described AlY zeolite.
6. according to the described method of claim 5, it is characterized in that introducing amount 0.05～10 heavy % of aluminium in the described AlY zeolite.
7. according to the described method of claim 1, it is characterized in that the described forming agent that helps is selected from methylcellulose, polyvinyl alcohol and the plant amylum one or more, zeolite is 100: 2～10: 60～120 with helping the weight ratio of forming agent and water.
8. according to each described method in the claim 1～7, it is characterized in that the atmosphere of described moisture vapor refers to water vapour and Air mixing gas, the volume space velocity of air is 0.1～1500 hour
-1
9. described according to Claim 8 method is characterized in that described water vapour weight space velocity is 0.1～2.45 hour
-1, volume of air air speed 1～1200 hour
-1, be 2～6 hours the time of contact of moisture vapor and Air mixing gas and zeolite article shaped.
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|---|---|---|---|
| CN97103967A CN1060098C (en) | 1997-04-09 | 1997-04-09 | Hydrothermal treatment process of zeolite |
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|---|---|---|---|
| CN97103967A CN1060098C (en) | 1997-04-09 | 1997-04-09 | Hydrothermal treatment process of zeolite |
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| CN1060098C true CN1060098C (en) | 2001-01-03 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3838040A (en) * | 1971-10-20 | 1974-09-24 | J Ward | Hydrocracking with zeolite in a silica-magnesia matrix |
| US3945943A (en) * | 1971-10-20 | 1976-03-23 | Union Oil Company Of California | Zeolite containing compositions, catalysts and methods of making |
| WO1982003571A1 (en) * | 1981-04-10 | 1982-10-28 | Hettinger William P Jr | Large pore catalysts for heavy hydrocarbon conversion |
| US5288396A (en) * | 1979-10-15 | 1994-02-22 | Union Oil Company Of California | Hydrocracking process using a catalyst selective for making middle distillates |
-
1997
- 1997-04-09 CN CN97103967A patent/CN1060098C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3838040A (en) * | 1971-10-20 | 1974-09-24 | J Ward | Hydrocracking with zeolite in a silica-magnesia matrix |
| US3945943A (en) * | 1971-10-20 | 1976-03-23 | Union Oil Company Of California | Zeolite containing compositions, catalysts and methods of making |
| US5288396A (en) * | 1979-10-15 | 1994-02-22 | Union Oil Company Of California | Hydrocracking process using a catalyst selective for making middle distillates |
| WO1982003571A1 (en) * | 1981-04-10 | 1982-10-28 | Hettinger William P Jr | Large pore catalysts for heavy hydrocarbon conversion |
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| CN1197691A (en) | 1998-11-04 |
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