DK160134B

DK160134B - Method for improving the activity of an inorganic oxide material and use thereof as a catalyst

Info

Publication number: DK160134B
Application number: DK370883A
Authority: DK
Inventors: Joseph Nicolas Miale; Clarence Dayton Chang
Original assignee: Mobil Oil Corp
Priority date: 1983-08-15
Filing date: 1983-08-15
Publication date: 1991-02-04
Also published as: DK370883A; DK160134C; DK370883D0

Description

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Den foreliggende opfindelse angår en fremgangsmåde til forbedring af aktiviteten af et uorganisk oxid-materiale, såsom aluminiumoxid eller galliumoxid, for at forbedre dets katalytiske aktivitet samt anvendelse af dette 5 som katalysator.The present invention relates to a process for improving the activity of an inorganic oxide material, such as alumina or gallium oxide, to improve its catalytic activity and its use as a catalyst.

Det uorganiske oxid aluminiumoxid har tidligere været forsynet med katalytisk aktivitet ved behandling med borfluorid (BF^). Behandlingen har været efterfulgt af hydrolyse og kalcinering. Krystallinske aluminiumsili-10 cater, såsom zeolitterne X og Y, er blevet aktiveret katalytisk ved behandling med flygtige metalhalogenider, såsom angivet i USA patentskrifterne nr. 3 354 078 og 3 644 220.The inorganic oxide alumina has previously been provided with catalytic activity in the treatment with boron fluoride (BF 2). The treatment has been followed by hydrolysis and calcination. Crystalline aluminum silicates, such as the zeolites X and Y, have been catalytically activated by treatment with volatile metal halides, such as disclosed in U.S. Patent Nos. 3,354,078 and 3,644,220.

Ifølge den foreliggende opfindelse tilvejebringes for-15 skellige uorganiske oxider, såsom aluminiumoxid og gal liumoxid, med væsentligt højere syre-katalytisk aktivitet, end det er muligt ved hidtil kendte metoder. Dette gør det muligt at tilvejebringe matricer med langt større områder for syre-aktivitet for kommercielle zeolit-kata-20 lysatorer til anvendelse ved krakning, alkylering og isomerisering.According to the present invention, various inorganic oxides, such as alumina and gallium oxide, are provided with substantially higher acid catalytic activity than is possible by methods known in the art. This allows matrices with far greater ranges of acid activity to be provided for commercial zeolite catalysts for use in cracking, alkylation and isomerization.

Ved fremgangsmåden ifølge opfindelsen, der er ejendommelig ved det i den kendetegnende del af krav 1 anførte, behandles det oxidholdige materiale med ammoniumfluorid 25 eller flygtig borfluorid, hvorefter det fluorid-behandlede materiale bringes i berøring med en vandig ammoniumbytter-opløsning, såsom hydroxid eller et salt, f. eks. nitrat, hvorpå materialet kalcineres. Det dannede produkt udviser en forøget Brønsted-syrestyrke og derfor en forbedret 30 syreaktivitet ved katalyse af talrige kemiske reaktioner, f. eks. alkylering, transalkylering, krakning eller isomerisering af organiske forbindelser, såsom carbon-hydrider. Materialet med forbedret syreaktivitet erIn the process according to the invention, characterized in that in the characterizing part of claim 1, the oxide-containing material is treated with ammonium fluoride 25 or volatile boron fluoride, after which the fluoride-treated material is contacted with an aqueous ammonium exchange solution such as hydroxide or an aqueous solution. salt, e.g., nitrate, on which the material is calcined. The resulting product exhibits an increased Brønsted acid strength and therefore an improved acid activity by catalysing numerous chemical reactions, e.g., alkylation, transalkylation, cracking or isomerization of organic compounds such as hydrocarbons. The material with improved acid activity is

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2 velegnet som matrix eller bærer for forskellige zeolit-materialer til fremstilling af katalysatorer for syrekatalyserede omdannelsesprocesser for organiske forbindelser .2 suitable as matrix or carrier for various zeolite materials for preparing catalysts for acid catalyzed conversion processes for organic compounds.

5 Behandlingen med ammoniumfluorid eller flygtigt borfluo rid udføres ved en temperatur fra 0 - 100 °C, fortrinsvis mellem stuetemperatur og 50 °C. Det med bor- eller ammoniumfluorid behandlede materiale behandles derefter med en vandig ammoniumhydroxidopløsning eller saltopløs- 10 ning, f. eks. 1 N NH^NO^ eller 1 N NH^OH, hvorpå der kalcineres ved en temperatur mellem 200 °C og 600 °C i en inert atmosfære af luft eller nitrogen ved et tryk over, ved eller under atmosfærens tryk i et tidsrum fra 1 minut til 48 timer.The treatment with ammonium fluoride or volatile boron fluoride is carried out at a temperature of from 0 to 100 ° C, preferably between room temperature and 50 ° C. The boron or ammonium fluoride treated material is then treated with an aqueous ammonium hydroxide solution or brine, e.g., 1 N NH 2 NO 2 or 1 N NH 2 OH, then calcined at a temperature between 200 ° C and 600 ° C. C in an inert atmosphere of air or nitrogen at a pressure above, at or below atmospheric pressure for a period of from 1 minute to 48 hours.

15 Fluoridbehandlingen kan udføres ved blanding af flygtigt borfluorid eller borfluoridetherat med en inert gas, såsom nitrogen eller helium, ved temperaturer mellem 0 °C og 100 °C. Det kan ske ved vakuumimprægnering af det uorganiske oxidmateriale med ammoniumfluorid i vand.The fluoride treatment can be carried out by mixing volatile boron fluoride or boron fluoride etherate with an inert gas such as nitrogen or helium at temperatures between 0 ° C and 100 ° C. This can be done by vacuum impregnating the inorganic oxide material with ammonium fluoride in water.

20 Mængden af fluoridreagens, der anvendes, er ikke særligt kritisk, men sædvanligvis benyttes fra 0,2 til 2 g borfluorid eller ammoniumfluorid pr. g uorganisk oxid-materiale .The amount of fluoride reagent used is not very critical, but is usually used from 0.2 to 2 g of boron fluoride or ammonium fluoride per liter. g of inorganic oxide material.

Behandlingen med vandig ammoniumbytter-opløsning kan 25 udføres i et tidsrum fra en time til 20 timer ved en temperatur fra stuetemperatur til 100 °C. Arten af ammo-niumbytter-materiale er ikke særligt kritisk, og normalt benyttes et uorganisk salt, såsom ammoniumnitrat, ammoniumsulfat, ammoniumchlorid, eller ammoniumhydroxid. 1The treatment with aqueous ammonium exchange solution can be carried out for a period of one hour to 20 hours at a temperature from room temperature to 100 ° C. The nature of ammonium exchange material is not very critical and usually an inorganic salt such as ammonium nitrate, ammonium sulfate, ammonium chloride, or ammonium hydroxide is used. 1

Anvendelsen af borfluorid i nærværelse af siliciumhol- dige materialer er et problem, fordi borfluorid let hydrolyserer, og det derved frigjorte HF angriber si-The use of boron fluoride in the presence of silicon-containing materials is a problem because boron fluoride readily hydrolyzes and the thus released HF attacks the

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3 liciumoxid. Det uorganiske oxid, der skal behandles med borfluorid, bør derfor ikke indeholde siliciumoxid eller blandinger af dette oxid. Hvis det uorganiske oxid-materiale indeholder siliciumoxid, foretrækkes 5 det ved fremgangsmåden ifølge opfindelsen at anvende et reagens af ammoniumfluorid.3 cesium oxide. Therefore, the inorganic oxide to be treated with boron fluoride should not contain silica or mixtures of this oxide. If the inorganic oxide material contains silica, it is preferable to use an ammonium fluoride reagent in the process of the invention.

Det uorganiske oxid-materiale, der skal behandles ved fremgangsmåden ifølge opfindelsen, kan om ønsket kalci-neres forud for behandlingen med fluorid-reagenset ved 10 en temperatur fra 200 °C til 600 °C i en atmosfære af luft eller nitrogen i et tidsrum mellem 1 minut og 48 timer.The inorganic oxide material to be treated by the process of the invention may, if desired, be calcined prior to treatment with the fluoride reagent at a temperature of 200 ° C to 600 ° C in an atmosphere of air or nitrogen for a period of time between 1 minute and 48 hours.

Det ved fremgangsmåden ifølge opfindelsen aktiverede uorganiske oxid-materiale er velegnet som katalysatorkom-15 ponent for syrekatalyserede omdannelsesreaktioner af organiske forbindelser. Eksempler på sådanne reaktioner er krakninger af carbonhydrider, hvor reaktionsbetingelserne omfatter en temperatur fra 300 °C til 800 °C et tryk fra 15 psia til 500 psia og en rumfangshastig-20 hed efter vægt pr. time fra 0,1 - 20. Et andet eksempel er omdannelsen af methanol til carbonhydrider, hvor reaktionsbetingelserne omfatter en temperatur på 300 -550 °C, et tryk fra 5 psia - 500 psia og en rumfangshastighed udtrykt i vægt pr. time på 0,1 - 100.The inorganic oxide material activated by the process of the invention is well suited as a catalyst component for acid-catalyzed conversion reactions of organic compounds. Examples of such reactions are hydrocarbon crackings, the reaction conditions comprising a temperature of 300 ° C to 800 ° C, a pressure of 15 psia to 500 psia and a volume rate by weight per unit weight. Another example is the conversion of methanol to hydrocarbons where the reaction conditions comprise a temperature of 300-550 ° C, a pressure of 5 psia - 500 psia and a volume rate expressed in weight per minute. hourly 0.1 - 100.

Ved gennemførelse af den ønskede kemiske omdannelses-25 proces er det hensigtsmæssigt at benytte det som ovenfor beskrevet aktiverede uorganiske oxid-materiale, især når det anvendes som matrix i en zeolit-holdig katalysator-komposition, sammen med en yderligere matrix, bestående af endnu et materiale, der er bestandigt ved 30 den ved processen anvendte temperatur og øvrige betingel ser. Sådanne yderligere matrix-materialer er velegnedeIn carrying out the desired chemical conversion process, it is convenient to utilize the activated inorganic oxide material as described above, especially when used as a matrix in a zeolite-containing catalyst composition, together with a further matrix consisting of yet another material that is resistant to the temperature and other conditions used in the process. Such additional matrix materials are suitable

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4 som bindemiddel og tildeler katalysatoren yderligere bestanddighed ved de skrappe betingelser i henseende til temperatur, tryk og hastighedsbetingelser for gennemstrømning af reaktanter, som benyttes ved mange krak-5 ningsprocesser. Sådanne egnede matricer er beskrevet i EP-A-16 95.4 as a binder and imparts additional resistance to the catalyst under the harsh conditions of temperature, pressure and velocity conditions for the flow of reactants used in many cracking processes. Such suitable matrices are described in EP-A-16 95.

Fremgangsmåden ifølge opfindelsen skal i det efterfølgende illustreres nærmere ved hjælp af nogle udførelseseksempler .The process according to the invention will be illustrated in the following with the aid of some exemplary embodiments.

10 EKSEMPEL 1EXAMPLE 1

Et g gamma-aluminiumoxid af typen Kaiser blev vakuumimprægneret med 0,9 g ammoniumfluorid (NH^F) i vand ved en temperatur på 25 °C. Der udvikledes betydelige mængder ammoniak. Efter behandling i 30 minutter blev det 15 med ammoniumfluorid behandlede materiale tørret ved 130 °C og derefter behandlet tre gange med 1 N vandig ammo-niumnitratopløsning (NH^NO^). Hver ammoniumnitrat-behand-ling blev efterfulgt vask med vand. Det færdige vaskede produkt blev derpå tørret ved 130 °C og kalcineret i 20 30 minutter ved 538 °C i luft.One gram of Kaiser gamma alumina was vacuum impregnated with 0.9 g of ammonium fluoride (NH4 F) in water at a temperature of 25 ° C. Significant amounts of ammonia developed. After treatment for 30 minutes, the material treated with ammonium fluoride was dried at 130 ° C and then treated three times with 1 N aqueous ammonium nitrate solution (NH 2 NO 2). Each ammonium nitrate treatment was followed by washing with water. The finished washed product was then dried at 130 ° C and calcined for 20 30 minutes at 538 ° C in air.

EKSEMPEL 2EXAMPLE 2

Et g af det i eksempel 1 benyttede aluminiumoxid blev mættet med borfluorid (BF^). Denne behandling blev udført ved 25 - 95 °C. Mætningspunktet blev bestemt som det 25 punkt, hvor der ikke længere udvikledes adsorptionsvarme.One gram of the alumina used in Example 1 was saturated with boron fluoride (BF 3). This treatment was carried out at 25 - 95 ° C. The saturation point was determined as the 25 point at which no adsorption heat was developed.

Enhver yderligere tilsætning af BF^ udover dette punkt ville have afkølet aluminiumoxidet. Ved mætningspunktet blev strømmen af borfluorid afbrudt og luft ved 25 °C (stuetemperatur) blev ført gennem aluminiumoxidet i 30 30 minutter. Det med borfluorid behandlede materialeAny further addition of BF ^ beyond this point would have cooled the alumina. At the saturation point, the flow of boron fluoride was interrupted and air at 25 ° C (room temperature) was passed through the alumina for 30 minutes. Boron fluoride treated material

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5 blev derefter tørret ved 130 °C i 30 minutter til fjernelse af sidste spor af ikke-omsat eller løst tilbageholdt borfluorid. Det tørrede produkt blev derpå behandlet med 1 N vandig opløsning af NH^NO-j og kalcineret som 5 angivet i eksempel 1.5 was then dried at 130 ° C for 30 minutes to remove last traces of unreacted or loosely retained boron fluoride. The dried product was then treated with 1 N aqueous solution of NH 2 NO-j and calcined as indicated in Example 1.

EKSEMPEL 3EXAMPLE 3

En prøve af UOP bimodal gamma-aluminiumoxid i form af perler blev behandlet med BF^ som angivet i eksempel 2, men uden NH^NO^-behandling. Det med borfluorid behand-10 lede aluminiumoxid blev kalcineret som ovenfor angivet.A sample of UOP bimodal gamma alumina in the form of beads was treated with BF ^ as set forth in Example 2 but without NH ^ NO ^ treatment. The boron fluoride treated alumina was calcined as indicated above.

Dette var en hidtil kendt proces for aktivering af aluminiumoxid, udført for sammenligning.This was a hitherto known process for activating alumina, performed for comparison.

EKSEMPEL 4EXAMPLE 4

Endnu en prøve af de bimodale aluminiumoxid-perler blev 15 behandlet med BF-j som angivet i eksempel 3, hydrolyseret med demineraliseret vand og kalcineret som ovenfor angivet. Der var ingen behandling med vandig ammoniumhydroxid eller salt. Også dette var en hidtil kendt fremgangsmåde til aktivering af aluminiumoxid, udført for sammenligning.Another sample of the bimodal alumina beads was treated with BF-j as indicated in Example 3, hydrolyzed with demineralized water and calcined as indicated above. There was no treatment with aqueous ammonium hydroxide or salt. This too was a known method of activating alumina, performed for comparison.

20 EKSEMPEL 5EXAMPLE 5

Endnu en prøve af de bimodale aluminiumoxid-perler blev behandlet som angivet i eksempel 2.Yet another sample of the bimodal alumina beads was treated as given in Example 2.

EKSEMPEL 6EXAMPLE 6

Slutprodukterne af uorganisk oxid-materialer, behandlet 25 som angivet i eksemplerne 1-5, sammen med prøver af de to ubehandlede aluminiumoxidmaterialer blev underkastet α-prøve med følgende resultat:The final products of inorganic oxide materials, treated as given in Examples 1-5, together with samples of the two untreated alumina materials were subjected to α test with the following result:

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66

Produkter fra eksempler a-værdi gamma-aluminiumoxid (base) 0,2 bimodal aluminiumoxid-perler (base) 0,2 5 1 (NH^F/NH^NOj/kalcinering) 4,5 2 BF^/NH^NO^/kalcinering 15 3 (BF^/kalcinering ) 2,8 4 (BF^/H^O/kalcinering) 8,7 5 (BF-j/NH^NO^/kalcinering) 23 10 Af de ovennævnte resultater fremgår det, at fremgangs måden ifølge opfindelsen er velegnet til at forøge den syre-katalytiske aktivitet af visse uorganiske oxid-materialer. Sammenligning af α-værdierne for produkterne fra eksemplerne 1 og 2 med de tilsvarende værdier for 15 ikke-behandlet gamma-aluminiumoxid udviser en forøgelse af aktiviteten på 2150 - 7400¾. Sammenligning af a-vær-dien for produktet fra eksempel 5 med den tilsvarende værdi for ikke-behandlet bimodal aluminiumoxid-perler viser en forøgelse af aktiviteten på 11400¾. Sammenlig-20 ning af resultaterne for det i eksempel 5 angivne ma teriale med de tilsvarende værdier for materialerne ifølge eksempel 3 og 4 viser det ved fremgangsmåden ifølge opfindelsen opnåede fremskridt i forhold til kendt teknik, a- prøven er beskrevet i USA patentskrift 25 nr. 3 354 078 og tidsskriftet The Journal of Catalysis,Products from Examples a-value gamma alumina (base) 0.2 bimodal alumina beads (base) 0.2 5 1 (NH 2 F / NH 2 NO 2 / calcination) 4.5 2 BF 2 / NH 2 NO 2 calcination 15 3 (BF ^ / calcination) 2.8 4 (BF ^ / H ^ O / calcination) 8.7 5 (BF-j / NH ^ NO ^ / calcination) 23 10 From the above results it appears that progress the method of the invention is well suited to increase the acid catalytic activity of certain inorganic oxide materials. Comparison of the α values of the products of Examples 1 and 2 with the corresponding values of 15 untreated gamma alumina shows an increase in activity of 2150 - 7400¾. Comparison of the α-value of the product of Example 5 with the corresponding value for untreated bimodal alumina beads shows an increase in activity of 11400¾. Comparison of the results of the material of Example 5 with the corresponding values for the materials of Examples 3 and 4 shows the progress achieved in the process of the invention in the prior art compared to the prior art. 3,354,078 and the journal The Journal of Catalysis,

Vol. IV, pp. 522 - 529 (august 1965).Vol. IV, pp. 522 - 529 (August 1965).

Claims

A process for improving the activity of an inorganic oxide material, characterized in that the oxide-containing material is treated with ammonium fluoride or non-fluoride at a temperature of 0-500 ° C, after which the fluoride-treated material is introduced. contact with an aqueous ammonium exchange solution, after which the material is calcined at a temperature of 200-600 ° C.

Process according to claim 1, characterized in that the inorganic oxide material is alumina or gallium oxide.

Process according to claim 1 or 2, characterized in that the aqueous ammonium exchange solution contains ammonium hydroxide or an ammonium salt.

Process according to claim 3, characterized in that the ammonium salt is ammonium nitrate, ammonium sulphate or ammonium chloride.

Process according to claim 1, characterized in that the inorganic oxide material is calcined prior to the treatment with the fluoride at a temperature between 200 ° C and 600 ° C.

Process for the conversion of an organic compound, characterized in that it is treated under conversion conditions with a catalyst comprising an inorganic oxide material whose activity is improved and obtained by the process of claims 1-5.