DE1545356A1 - Process for the conversion of hydrocarbons - Google Patents

Description

Process for the conversion, of hydrocarbons.

(Addition to patent ...... (patent application S 77 500 IVd / 23b)) The invention is directed to a process for the expansion of hydrocarbons by bringing them into contact of the hydrocarbons under conversion conditions with a catalyst that thereby is characterized in that the catalyst used is an at least partially crystalline one Used aluminosilicate that has 0.4 to 1.0 equivalents of positive ions per gram atom Contains aluminum, the positive ions consisting of a mixture of metal cations of metals from groups IB to VIII of the period census -teins and hydrogen ions or ions capable of being converted into hydrogen ions and the metal cations include rare earth metal cations.

There are already numerous equipment as ca-balysatoren for the Conversion of hydrocarbons into one or more desired products has been proposed been.

For example, in the catalytic cracking of hydrocarbon oils, in the case of hydrocarbon oils with a higher boiling range in hydrocarbons with lower boiling points Boiling range are converted, especially into hydrocarbons, which are in the motor fuel range boiling, the most widely used catalysts are solids that are acidic behave so that hydrocarbons are cracked. Albeit acidic catalysts of this kind possess one or more desirable properties, have a large number these catalysts have undesirable properties, e.g. insufficient thermal resistance, Accessibility or mechanical strength, etc., so a broader range of favorable properties not -: '' obtained can be. Synthetic Siliciundioxy @ alumina compositions, i.e. the Previously used eatalysstors give limited yields of gasoline in combination with a given yield of coke and continue to have the @ disadvantage @@@@ rapid quality deterioration and deactivate @@@@ Geg @@@@@@ vo @ water vapor, especially at Temperatures c: '; .-' C (100F) .Otherwise not, 30 widely used j-. ' !: -... '"gates encompassing!' - ns such materials fromontonartier -..- c-nhe ', see B. 3entonite and montmorillonite, the. @@ @@ andelt @@ rd @ n are, u @ yours laventen soh-ftchervorzubringen.KatalysatorsendieEc "" inenT ,, jsi; -veraältniHsaibillig, ciesare @@ inen T @@ e si @ relatively cheap, they are va'a'c over periods "ielerUmanlans" and reenertioE circuitsSome synthetic materials, e.g., silicon circuits, Some s @ nthetic materials, e.g. silicon dioxide-magnesium oxide @@ omplexe, sin @ more active than conventional silica catalysts and failed to show normal aging ; however, because of their product disclosure, they have, for example, through an i-three Octansh ? d? nsisaneseitwwill, 'ren "-'- uchbar'. ' "; 'cnj': ach" ---? .- de: "-... isnereingeschappenen bilitä @ and product @@ rteilung when attaining erw @@ real sbeutenanbrauch-renProduc.

The invention is based on the @ e @ t- @ ll @, @@ Alu @@@@ cilicate, the s @ w @ hl hydrogen @@@@ en @@ @ @ S @@@ - @@@@@ t @ ll @@ tion @ @@@@ alten, @@@ a @ tive @@ @@ @@ @@@ @@ @@ @@@@@@ @@@@schen @@@@@@ ren are, in particular for those chemical processes that involve hydrocarbon conversion. The catalysts used in the process according to the invention have a wide range in terms of the magnitude of the catalytic activity they can in relatively low concentrations are used and they allow the Performing certain hydrocarbon conversion processes under practical and adjustable speeds at lower temperatures than previously used became. In the catalytic cracking of hydrocarbons into hydrocarbon products Lower .. molecular weight range, for example, the reaction rates per unit volume of catalyst that can be achieved with the catalysts according to the invention are up to thousands of times-the speeds with the best previously proposed silicon-containing catalysts have been achieved.

The catalysts used in the present invention are high activity Aluminosilicate compositions which, as a result of treatment with a gaseous or liquid medium; the at least one rare earth metal cation and one hydrogen ion or contains an ion capable of converting into a hydrogen ion, have a strongly acidic character.Generally inorganic and organic acids are the source of hydrogen ions, Rare earth metal salt the source of rare earth metal cations and ammonium compounds or salts of organic nitrogen bases are the source of cations that can be converted into hydrogen ions The product that results from the treatment with the medium is an activated, at least partially crystalline aluminosilicate, the core structure of which is primarily has been modified so that the protons and rare earth metal cations are chemisorbed or ionically bound to it.

Details of the manufacture of the catalyst are in the patent ......... (Patent application S 86 608 IVd / 23b) indicated that the catalyst itself and the Process for its creation concerns. Such details are not given here listed againa The catalysts used according to the invention are at least partially crystalline aluminosilicates that are either hydrogen or conversion contain ions capable of hydrogen ions as well as rare earth metal cations, the only limitation being that in no case should it exceed 0.25 Equivalents of alkali metal per gram atom of aluminum are combined with the aluminosilicate should be.

Within the limits given above, it is preferred that only a minimal amount of alkali metal cations associated with the aluminosilicates is there. the.

Presence of these metals to depress or limit catalytic properties tends, with the activity usually increasing with increasing Alkali metal cation content decreases. Furthermore: it. preferred that the novel aluminosilicates at least 0.4 and better 0fi6 to 1.0 equivalents each Gram atom of aluminum have positive ions, at least a portion of which Rare earth metal cations and hydrogen ions or convertible to hydrogen ions Ions are. In those cases where the catalyst composition of rare earth metal cations Contains different metal cations, it is further preferred that these at least are divalent, where the cations of divalent metal-s, such as calcium, magnesium and manganese, are particularly advantageous. Polyvalent metal ions leading to deeper Valence levels can be reduced, are also for catalysts with double Function (dual function catalysts) particularly advantageous.

The rare earth metals are characterized by cerium, lanthanum, praseodymium, Neodymium, Illinois, Samarium, Europium, Gadolinium, Terbium, Dysprosium, Holmium, Erbium, Thulium, Scandium, Yttrium and Lutecium.

A particularly preferred embodiment of the invention is in the use of such catalyst compositions, the 0.5 to -1, 0 equivalents åe gram atom of aluminum have positive ions, which are made up of hydrogen ions or ions capable of converting to hydrogen ions and rare earth metal cations exist.

In the most preferred embodiment of the invention, Rare earth metal cations are essentially the only metallic cations associated with the aluminosilicate.

The relative amount of hydrogen ions or for conversion to water capable ions in the ratio su rare earth ions, which in accordance with the in the process The aluminosilicates used in the invention are not closely related critical and over a fairly broad range v?.: 'icBut particularly effective Catalysts when the rare earth content is in the range of 10 - 95% of the total equivalents of positive ions, with 25-95% preferred and -35% particularly preferred The most preferred embodiment of the invention therefore lies in the use of such aluminosilicates as catalysts which 0.8 to 1.0 equivalent a-: ions "-Iti-verSalons contain; which SOZIO = .. c ..: 2, ^ r ic. a. sf:: =. j'i'r 'Cii. li sCit .. '' 1 ~ 'e ~?. q; "WG '' 'ii: z..!' = ~ changeable Ions and rare earth metal cations exist, with 40-85% of the total equivalent e of rare earth metal cations and particularly useful of lanthanum ions, Praseodymes, Samariums, Gadoliniums, Neodymes or mixtures in which one or several of the above-mentioned cations predominate.

Although the invention is not bound to any theory, It seems that the rare earth metal cations tend to cause the To give aluminosilicate compositions resistance and thereby. O far more useful for catalytic purposes, especially catalytic Conversion processes such as Kraokung. Not entirely known until now Rare earth cations are all other metallic cations in this regard to a great extent superior, especially when using hydrogen ions or hydrogen ion precursors are united. It can be seen that the degree of stability imparted varies in the general can change with the particular catalyzed reaction.

The catalysts according to the invention can be powdered, granulated or formed state, e.g. in the form of beads or pellets from fine particles @ with a particle @@@@@ from 2 - 500 Meshes (mesh). When the catalyst is molded, e.g. B. by extrusion, the aluminosilicate be extruded before drying, or it can be dried or partially dried and then extruded merdent The catalyst product is then preferably in a inert atmosphere close to the temperature in question for the conversion precalcined, but it can also be used initially in the conversion process calcined vierden. In general, the aluminosilicate is grown at one temperature between about 65 ° and 3'16 ° C (150-600 ° F) and then dried in air or a inert atmosphere of nitrogen, hydrogen, helium, abas or another inert gas at temperatures ranging from about 260-315 ° C (500-1500 ° F) for periods in the Calcined for 1-43 hours or more.

According to the invention it has further been found that partial flow Catalysts with improved selectivity and other favorable properties used in the conversion of hydrocarbons, these catalysts can be obtained by subjecting the treated aluminosilicate to a mild steam treatment subject to that at elevated temperatures of 427-81500 (800-1500 °) and preferably is performed at temperatures of about 5v8-704 ° C (1000-1500 ° F). The treatment can in an atmosphere made up of 100% water vapor or in an atmosphere made up of water vapor and a gas substantially inert to the aluminosilicate. The steam treatment apparently creates beneficial properties in the aluminosilicate. Similar treatment can be used for deeper ones. Temperatures and elevated pressures, e.g. B. about 177-371 ° C (350-700 ° F) and 10 to about 200 atmospheres will.

The high catalytic activities in the invention aluminosilicate compositions used are described below in Associated with cracking of a representative hydrocarbon feed. In the examples given below, the reference catalyst used was the one used from a conventional "pearl" type silica-alumina cracking catalyst. The silica-alumina catalyst e @ contained about 10% Al2O3 and the rest SiO2. In some cases it also contained a trace amount of Cr2O3, i.e. about 0.15 Wt%.

The cracking activity of the catalyst is further enhanced by its ability illustrates the conversion of a mid-continent gas oil with a boiling range Catalyze from 232-51Ö ° C (450-950 ° F) in gasoline with an end point of 210 ° C (41qu) zi. Vapors of the gas oil at temperatures of 468 ° or 432 ° C (875 or 900 ° F) and substantially atmospheric pressure at a feed rate from 1.5 - 16.0 volumes of liquid oil per volume of catalyst and hour 10 minutes long passed through the catalyst. The method of studying the invention The catalyst used was the different product yields that obtained with such a catalyst, with the yields of the same Products made with the conventional silica-alumina catalyst the same conversion level can be obtained, to compare. The following angle, Differences (# values) mean those of the catalyst used according to the invention given yields minus the yields given by the conventional catalyst. The catalyst composition used according to the invention was used for these tects pre-caicinated at about 530 ° C (1000 ° F) before testing as a cracking catalyst.

(1000 ° F) precalcined. a variety of carbon dioxide conversion processes, including Iso @ erisierung, Doal @@ lierung, Alkyli @@@@, Disproortio: '!. ic:.' u'.T.j, Eydratisic: .. u: \ vo: iOlefincn, A: 'niiiJ-erun vonCicfic:; I'.lc: .t. \ 7af3CGrGtoffo: .. io.i, Dchdrierunj, Dehydratati @ @n alcohols, Entusch @@@ clung, H @ dri @@@@@, Hydroforming, reforming, hydrocracking, Oxidation, polymerization and adsorption, absorption and the like The catalysts used in the invention are exceptionally stable and they are particularly useful with those of the aforesaid and related ones. procedure those at temperatures in the range of ambient temperatures in the region of 21 ° X (70 ° F? Up to 760 ° C (1400 ° F), including those Processes in which the catalyst periodically regenerates by burning off combustible deposits will. The catalysts are suitable because of their high catalytic activities especially for carrying out various hydrocarbon conversion processes, z. B. the alkylation, at relatively low temperatures with small amounts of catalyst and in this way result in the lowest possible level of undesired side reactions and operating costs.

For example, the dehydrogenation of hydrocarbons, such as Propane, butylene, butane, pentane, cyclopentane, cyclohexane, methylcyclohexane and the like. eq., at temperatures ranging from about 149-552 ° C (v00-1025 ° F) below atmospheric or superatmospheric pressures with a space velocity (L @ SV) from 0.2 to 5000 to be carried out. Metals can be used for dehydration and Oxides and sulphides of metals, e.g. B. platinum, palladium, rhodium, tungsten, iron, Copper or nickel, as promoters in conjunction with the active aluminosilicate to be used.

For the desulfurization of hydrocarbons, which is largely a Hydrogenation, the oxides and sulfides of such metals as cobalt, Molybdenum, chromium, iron, manganese, vanadium, copper and their mixtures, in connection find application with the aluminosilicate.

The desulfurization of slate distillates and the like can at temperatures between about 316 ° and 538 ° C (600-1000 F) below atmospheric or superatmospheric pressures with a space velocity (LESV) between 0, 2 and 50 are carried out. The special conditions within these areas depend on the feed material to be desulphurized and the desired one Product.

The method according to the invention can be used for the @@ dration of unsaturated aliphatic hydrocarbons, e.g. monolefins, diolefins, etc. applied are to form the corresponding saturated hydrocarbons su; the same applies to the hydrogenation of unsaturated cyclic hydrocarbons and the Hydrogenation of unsaturated alcohols, ketones, acids, etc. For hydrogenation reactions the temperature can range up to 538 ° C (1000 ° F) at a pressure of about 0.7 to 210 kg / cm2 (10 to 3000 pounds per square inc) or more and a space velocity (LHSV) of about 0.5 to 5.0.

The promoters normally used with the aluminosilicate will close. the oxides and sulfides of nickel, swabs and iron, and platinum group metals a, Hydrocracking of heavy petroleum residue materials, recycle materials, etc. can be done with active aluminosilicates that are about 0.05 to 10 % By weight of a platinum metal such as platinum, palladium, rhodium, osmium, iridium and Contain ruthenium as a promoter. The petroleum feed is in the presence of the Catalyst cracked at temperatures between 204 and 440 C (': 00-825 ° F), wherein molar ratios of hydrogen to hydrocarbon feed in a range between 2 and 80 can be applied. The pressure applied is between 0.7 and 176atü (10-2500psig) and the space velocity is between 0.1 and 10.

The process according to the invention can also be used for alkylation of aromatic hydrocarbons or phenols and the conversion of olefinic, acetylenic and naphthenic hydrocarbons can be used. The alkylation of aromatics and phenols can be used at temperatures between about -10 ° and 454 ° C ('15 under pressures of about 0-70 atmospheres (0-10GO psig) be performed. The aromatization reaction took place at temperatures between about 177 ° and 593 ° C (350-1100 ° B) be effected under atmospheric or elevated pressures.

To other b. Reactions for which the catalysts are suitable include the isomerization, polymerization, hydrogen transfer, oxidation of olefins to form the corresponding oxide, e.g. B. from xethylene to ethylene oxide, from propylene to propylene oxide, etc., as well as the oxidation of alcohols and ketones, etc. The invention also found in processes for the oxidation of cyclohexane to adipic acid via the precursors Cyclohexanone and cyclohexanol, as well as in the production of caprolactam from caprolactone and ammonia application. The invention also relates to methods of manufacture of vinyl chloride by oxidative dehydrogenation reactions including lithane and hydrogen chloride useful.

The implementation of the invention is illustrated by the following examples further explained: Example 1 A synthetic, identified as Zeolitli 13-X crystalline. Aluminosilicate underwent 12 two hour treatments at 82 ° 0 (180 ° F) with an aqueous solution subjected the 5 wt .-% to a mixture of Seltellen earth chlorides and 2% by weight ammonium chloride. That Was aluminosilicate then washed with water until the draining liquid ran out of chloride ions , dried, and then at 662 ° C (1225 ° F) for 20 hours with 100% atmospheric Steam treated; it resulted in a catalyst with a water content of 0.31% by weight and a rare earth content of 23.5% by weight, determined as rare earth oxides.

The table below shows the cracking values obtained when the Catalyst for cracking gasol at 482 ° C (900 ° F).

.. '. ".

Table Cracking Values Conversion,% by volume 60.9 flow rate, LHSV 16 petrol, 10RVP, vol .-% 54.6 excess C4, vol .-% 9.5 C5 + petrol, vol .-% 51, 7 Total C4,% by volume 12.5 Dry gas,% by weight 5, 6 Coke,% by weight S 2, 3 lI2,% by weight 0.02 A-advantage gasoline, 10 RVP, vol .-% + 9.3 excess C4, vol .-% - 4.5 05 + gasoline,% by volume + 7, 4 total C4,% by volume, 7 dry gas,% by weight - 2.2 coke, Weight-, -2, 4 Example 2 1 A synthetic, identified as zeolite 13X crystalline aluminosilicate was treated with an aqueous solution for 72 hours in a row treated, the 10 wt .-% ammonium chloride, 1, 0 wt .-% ammonium acetate and 1 wt .-% Contained rare-earth chloricle. The aluminosilicate was then washed with water, until the effluent contained no chloride or acetate ions, dried and then 24 Hours at 648 ° C (1200 ° F) with water vapor at a pressure of 1.05 atm (15 psi @) treated, it resulted in a composition with an ancient earth content, determined as rare earth oxides, of 22.0% by weight.

The table below shows the cracking values obtained during the investigation of the gas oil cracking catalyst at 482 ° C (900 ° F).

Table Kraok conversion values, vol .-% 56, 6 flow rate, LHSV 16.0 petrol, 10 RVP, vol .-% 5Q, 9 t surplus C4 vol .-% 9.2 C5 + 'petrol, Yol .-% 48.3 total C4,% by volume 11.8 dry gas,% by weight 5, 4 coke,% by weight 1.4 rI2,% by weight 0.01 advantage petrol, 10 RVP, vol .-% + 7, 9 excess C4, vol .-% -3.4 C5 + petrol, % By volume + 7.4 total C,% by volume - 3.0 dry gas,% by weight 6 coke,% by weight -2.5 Example 3 A synthetic crystalline aluminosilicate identified as Zeolite 13X was 24 two-hour treatments with an aqueous solution consisting of 5 wt .- ° ó Lanthanum chloride and 2% by weight ammonium chloride at 82 ° C (180 ° F). The aluminosilicate was then washed with water until the effluent was free of chloride ions , dried, and then at 662 ° 0 (1225 ° F) for 20 hours at 100% atmospheric Steam treated; it resulted in a catalyst with a Sodium content of 0.36% by weight and a rare earth content of 26.2% by weight, determined as rare earth oxides, The table below shows the cracking values obtained when the catalyst was tested for cracking gas oil at 482 ° G (900 ° Fj.

Table Cracking Values Conversion, Vol .-% 63.1 Flow Rate, VISU 16 petrol, 10RVP, vol .-% 52.6 aberschufl C4, vol .-% 12.3 Ce + petrol, vol .-% 50, 4 total C +,% by volume 14.5 dry gas,% by weight 6.8 coke,% by weight 3.6 H2,% by weight 0.04 # -Vorieil gasoline, 10 RYP, vol .-% + 6.2 excess C4, vol .-% -2.7 C5 + gasoline, vol .-% + 6, 2 total 0.,% by volume - 2.5 dry gas,% by weight -1.4 coke,% by weight -1.5 Example 4 A technical synthetic aluminosilioate identified as liatrium mordite had been, was with a combined aqueous solution of 5 percent by weight of a Mixture of rare earth chlorides and 2 weight percent ammonium chloride at 82 ° C- (180 ° F) treated. The composition was then washed free of chloride ions at 110 ° C Dried (230 ° F) in air and then caicinated for 10 hours at 556 ° 0 (1000 ° F); it resulted in e. in catalyst with a sodium content of 0.19% by weight and a rare earth oxide content of 3.0% by weight.

Example 5 A synthetic identified as XY aluminosilicate crystalline aluminosilicate made by converting a pearl hydrogel into a caustic solution was prepared, was treated with an aqueous solution, that of 5% by weight of a mixture of rare earth chlorides and 2% by weight ammonium chloride duration ;. it was then washed with water until the effluent did not contain chloride ions , dried, and then at 648 ° C (1200 ° F) for 24 hours with 1.05 steam atü (15 psig) treated. The resulting aluminosilicate contained 0.52% by weight Sodium and gave in the test for the KracLuuj of gas oil at 482 ° C (° 00 ° B) the following results: Table Cracking Values Conversion,% by volume 61.6 Flow velocity, LHSV 16 gasoline, 10 RVP, vol .-% 54, 9 excess C4, vol .-% 9.8 C5 + gasoline, vol .-% 52, 1 'total 04, vol .-% 12, 5 dry gas, wt Coke, wt .-% 1.9 H2 wt .-% 0.02 - advantage gasoline, 10 RVP, vol .-% + 9.0 excess C4, vol .-% -4.6 C5 + gasoline, vol .-% +8.6 total C, vol .-% - 4.1 dry gas, wt .-% -1.8 Coke, wt% - 2.9 Example 6 A natural crystalline aluminosilicate available as Gmelinit 'was identified to have an ex particle size of less than Crushed 32 meshes and calcined in air at 544 ° C (650 ° F) for 2 hours. 5 g of the caicinated crushed gmelinite was treated ten times with 70 cm "of a solution containing 4% by weight of a mixture of rare earth chlorides and 1% by weight of ammonium chloride contained. Each of the treatments lasted 1 hour at a temperature of about 78-86 ° C (173-186 ° F). The alumino. The silicate was then washed with water until the discharge no chloride ions contained, dried over at 88 ° C (190 ° y), pelletized, again to particle size of less than 12 mesh and crushed for 3 hours in air at 482 ° C (900 ° F) calcined. The resulting proclul. Lt. was used as a catalyst for cracking of decane at a catalyst concentration of 3) 3 cm, a feed rate of 3.0 LHSV unfine temperature of 482 ° C (900 ° F) used. It became a transformation of 91.6% by weight achieved.

Example 7 A synthetic identified as Y-aluminosilicate crystalline aluminosilicate was continuously using for 96 hours at 82 ° C (180 ° F) treated with an aqueous solution consisting of 5% by weight of a mixture of rare earth chlorides and 2% by weight of ammonium chloride. It was then washed with water until the The effluent was free of chloride ions, dried and then in air at 538 ° C for 10 hours (1000 ° F) followed by steaming at 648 ° C for 24 hours (1200 ° F) with 1.05 atm (15 psig) steam. The resulting catalyst contained 1.4% by weight sodium and 16.1% by weight Beltene earth oxides.

When tested for cracking gasoil at 482 ° C (900 ° F) and a liquid hourly space velocity of 4 became the obtained the following results: Catalytic investigation conversion, vol .-% 62, 4 gasoline, 10RVP, vol .-% 57.0 excess C4, vol .-% 8.7 C5 + gasoline, vol .-% 53.7 7 total C4,% by volume 11.9 dry gas,% by weight 5.5 coke,% by weight 2.0 H2,% by weight 0.03 # advantage over Si / Al gasoline, 10 RVP, vol .-% + 11, 0 excess C4, vol .-% -6.0 Cc + gasoline, vol .-% + 9, 8 Total C4,% by volume 419 Dry gas,% by weight - 3.0 Coke,% by volume - 2, 6

Claims (5)

Patent claims @@ @er @ to @ @@@@@@@@ @rstoffen .lri "i'J:" r dur @ @@@@@@@@ @@ el @ @@@@@ @@ .. rojf-e? .11-at'loH SdteD, -l -. '' j.iet & l .-: -'- r- iou.i '-. "- r-.". .Vr. ' :. 'a-: rcnnacArc, aduc' denotes thatnaneiner, talyatorYernendetine..iepositive . ~~ .. ~ t ... ~., J ~ @ to @ @@@@ @@ n ~~, ~~ a '.. ~ "' Ions in a @ an @ e from 0.6 to 1 , 0 Equivalents per gram atom of aluminum are present. 3. The method according to claim 1 or 2, characterized @ e-J kennseichnet that a catalyst is used in which up to rare earth metal cations 10 to 95 % and preferably 25 to @ 5 of the total equivalents of position ions in the catalyst turn off. 4. The method according to any one of claims 1 - 3, characterized in, that a catalyst is used in which the rare earth metal cations are essentially the only metal cabions in the catalyst. 5. The method according to any one of claims 1-4, characterized in that that the hydrocarbon conversion is a cracking of hydrocarbons performs under cracking conditions,