PL105505B1 - METHOD OF REACTIVATION OF THE HYDROGEN CRACKING CATALYST - Google Patents

Description

The invention relates to the reactivation process catalyst for the hydrocarbon cracking process ditch, reduced as a result of sedimentation time of the cracking process on a metal catalyst, such as nickel, vanadium and iron.

Hydrocarbons with a high molecular weight, is subjected to the cracking process to a greater degree at low temperature and in the presence of a catalyst, with more desirable light distillates.

During the cracking process, the catalytic activity is tora gradually decreases due to deposition on it, coke and metals such as nickel, wa¬ over and iron, which causes the quantity to increase produced hydrogen, dry gas and coke, a at the same time, the amount of carbon produced decreases hydrocarbons with lower molecular weight, such as gasoline.

In known catalyst regeneration processes, involving the treatment of spent catalyst oxygen at elevated temperature, burns and only removes the coke deposited on the catalyst, while the deposited metals are not removed, and this thus does not restore the catalyst to the set point efficiency.

From US patent specification US Am. no.3711422 it is known that the detrimental effect of deposited metals on the catalyst during the can cracking process to some extent be removed by treatment the spent catalyst with some anti- monu, especially triphenylantimony (e.g. clade 3 of the above-mentioned patent).

Surprisingly, it was found to be much better results are obtained if the passivation of metals, such as nickel, vanadium and iron, deposited on the cracking catalyst uses an thymone of the general formula given in the figure, wherein R are the same or different ne and denote hydrocarbon radicals of 1-18 carbon atoms and the total number of carbon atoms in the molecule of this compound it is 6-90.

According to the invention, a cracking catalyst can be treated with an antimony compound rose by any means. One of them is that carrying out the cracking process using known methods, at elevated temperatures, usually at 427 ° -650 ° C and under atmospheric pressure to several hundred atmospheres, the catalyst is separated from the products received and directs it to the regeneration zone in which the regeneration is carried out Nation in a known manner with the aid of oxygen in the higher temperature, and then returns the boiler talcum to the cracking process and contacts it with an antimony compound of the formula given in drawing, or a mixture of such compounds. May also to add an antimony compound already in the zone fie regeneration, as well as you can conduct pro¬ cracking process against the catalyst until the moment, when kataHd / monitor decreases activity and then it is off he is withdrawn from the trial and subjected to a known 105 505 105 505 oxygenation at an elevated temperature nature in the regenerative device is not related directly with the cracker.

The regenerated catalyst is then contacted not with an antimony compound before the introduction to a cracking zone or an anti- monu moves into the cracking area.

The cracking catalyst can be contacted with antimony compound by various known methods to me. One of them is the saturation of the catalyst a solution of an antimony compound in a solvent ku, e.g. in cyclohexane. Another way is subjected to the dosing of the antimony compound into the oil to the cracking process in front of the pump transferring this oil to the cracking zone. In this way by diluting and mixing the compound antimony with oil is avoided to deposit it connection, e.g. on a wall of a heat exchanger. After introducing a sufficient amount of anti-compound mon and put enough of it on the channel the talc the dosing is regulated in order to maintain the mac The desired amount of antimony compound for catalysis track. In this way, the shaft can be held constantly cracking and regeneration processes, increased significantly increasing the efficiency of the cracking process.

The method according to the invention can be used in the cracking of any raw materials, usually cracked, such as naphtha ta, heating oil, gas oil, shale oil or the fractions remaining after removal of the volatile nodes hydrocarbons. This process is carried out in presence known cracking catalysts, preferably from forms of rare earth metals such as cerium and lan- tan, embedded in small amounts to activate my cop.

As mentioned above, in accordance with the invention a hundred can be used for passivation of metals on the catalyst there is not only one of the compounds of the formula po given in the drawing, but also the mixtures some relationships. For this reason the amount of antimoy nu contained in this compound or mixture Compounds are usually defined as percentages by weight It is preferably 6 to 21 percent by weight relative to the total amount of compound or mixed nina.

The amount of antimony compound or compounds to be used according to the invention can be changed to quite wide limits, but usually used less than 1.5% by weight, especially 0.1-1.3% by weight of antimony in relation to the amount of kata lyser. If the antimony compound is added to hydrocarbon being cracked, then this additive is 0.1-15,000 parts by weight antimony to 1 million parts by weight of carbon hydrogen, but larger amounts can also be used antimony compound. Amount of compound added an¬ thymon depends on the ease with which it is deposited compound on the catalyst and on the speed of withdrawal catalyst spent and adding fresh evil.

The antimony compounds used according to the invention bed are known compounds. Especially ko Preferably the antimony compounds above are used given formula, wherein R are Chai alkyl radicals with 2-10 carbon atoms, especially n-propyl or octyl radicals. or optionally substituted cycloalkyl radicals of 5 or 6 carbon atoms, or optionally freely substituted phenyl radicals. Examples of such radicals are the following radicals: ethyl, n-propyl, isopropyl, n-, iso-, II-order. and III- -before butyl, amyl, n-hexyl, isohexy- low, 2-ethylhexyl, n-heptyl, n-octyl, isoctyl, Ill-row. octyl, dodecyl, ok- thydecyl, cyclopentyl, methylcyclopenty- cyclohexyl, methylcyclohexyl, ethyl locyclohexyl, phenyl, tolyl, cresylic, ethylphenyl, butylphenyl, amylphenyl,. octylenyl and vinyl phenyl.

Dithiophosphate compounds used in accordance with the invention can be produced by reacting it alcohol, e.g. phenol, with phosphorus pentasulfide, whereby the dihydrocarbon acid is obtained dithiaphosphoric. In order to get the salt of it 2Q acid with antimony, this acid can be neutralized with antimony trioxide and the mixture obtained from sniff the antimony salt. You can also neutralize the acid with ammonia and the resulting ammonium salt is subjected to 6 reaction with antimony trichloride to give salt antimony that is emerging.

The process of the invention is illustrated in, for example, clades, where shown in example II * the benefits that are obtained using the method of w the debt of the invention compared with the use The 3P of triphenylantimony or tributylphosphine is known mi from the above-cited U.S. Patent Specification

US Am. no.3 711422.

Example I. Sample of spent catalyst on an activated clay carrier containing the deposited contaminating metals were dried in a fluidized bed at a temperature of 482 ° C. Catalysis this path, being a known catalyst, before its start using it in the rock cracking process, technical grade contained about 0.4% by weight of cerium and about 1.4% by weight of lanthanum based on on metals and smaller amounts of other compounds metallic, namely 0.01% nickel, 0.03% vanadium, 0.36% iron, 0.16% calcium, 0.27% sodium, 0.25% potassium and less than 0.01% lithium in ratio 45 by weight, also in terms of metals. IN the same conversion of the consumed catalyst 0.38% nickel, 0.60% vanadium, 0.90% iron, 0.28% calcium, 0.41% sodium, 0.27% potassium and less than 0.01% lithium. The passivating metals were ^ not with the above discussion of nickel, vanadium and iron. Before use, the catalyst was in volume pores about 0.4 ml / g and specific surfaces about 200 m * / h. The spent catalyst was approx same pore volume and surface area 55 proper around 72 m2 / g.

The dried catalyst was divided into 10 portions and 5 of these portions were used in the first series of tests tions. Except for 1 portion used in the sample of the comparator, all the other 4 in saturated at room temperature with solutions of 0.0- - antimony dihydrocarbyl dithiophosphate in anhydrous cyclohexane, using solutions of o different concentrations. Antimony compound was used It was necessary to proceed with the preparation of these solutions gg of solution in neutral hydrocarbon oil, .105 505 6 known as Vanlube 622 preparation. This solution it contained 10.9% by weight of antimony, 9.05% by weight phosphorus, 19.4 wt.% sulfur and less than 100 parts of halogens per million parts by weight out. This corresponds roughly to a relationship antimony of the general formula given above, w and wherein R are propyl radicals in. The saturated catalyst was dried by irradiating n; oving it with a lamp and then warm it was brought to a temperature of 482 ° C in a fluidized bed and nitrogen. Saturated catalyst samples contained raly antimony in the amounts given in Table 1.

Each sample was subjected to stanzemia in such a way that in a laboratory device including a fluidized bed reactor, w "in which the catalyst was fluidized with nitrogen, was carried out cyclical cracking processes were carried out with the catalyst and regeneration, being cracked the raw material used was crude oil without oil fraction from Borger, Texas.

One cycle normally included delivery cracking oil within 30 seconds, then hydrocarbons were removed from the system with azo ^ here in about 3-5 minutes and then take off heated foam bath reactor and chilled to temperature while flushing with nitrogen in about 10 minutes. Next The reactor and its contents were weighed for determination the amount of coke that may have deposited on the catalyst during the cracking and then a new reactor was placed on the sand bath and heated to the temperature used during regeneration while passing through air reactor. Total regeneration time off he wore about 60 minutes. The reactor was then cooled to the temperature used during cracking and purged with nitrogen, then the next one was started cycle of cracking and regeneration.

Each of the samples of the catalyst subjected to pre-aging was then evaluated by reaction fluidized bed track, using as raw material Cracking Oil Borger, Texas, Po¬ saved from lighter factions. This raw material was introduced the reactor was heated within 30 seconds up to 510 ° C. Regene catalyst was heated at 649C ° as described above in relation to aging. Weight owned of the oil fed to the reactor was 0.925 g / ml at 16 ° C, its temperature the liquidity was 17 ° C and the viscosity was 1.8 centi- slopes at 99 ° C.

Catalyst on a clay carrier, saturated with antimony compound, it had a pore volume of 0.29 ml / g and a specific surface area of 74.3 m2 / g. It included he metal oxides in the amount of 0.38% by weight of nickel, 0.90 wt.% Iron and 0.60 wt.% Vanilla per metal. Weight ratio catalyst to the amount of supplied oil in 5 prólbaich were adjusted to obtain a degree transformations amounting to 70% by volume. Result and the cracking process with the use of a catalyst about different levels of antimony compounds are given in Table 1. In this table the amount of added anti- monu is given in weight percent based on to the weight of the cracking catalyst, the amount of coke is given in weight percent based on mass of hydrocarbon oil supplied, and gasoline yield is given in percent by volume in relation to the lead volume oil.

Table 1. 1 Quantity added - ] him antimony J. 0. 0.1 0.25 0.5 1 i, o Catalyst quantity ratio tor the amount of oil , 2 , 7 6.2 6.5 6.7 Performance coke 13.0 12.2 11.6 11.4 , 8 hydrogen volume (liters) processed volume oil 125 85 63 55 53 gasoline 56 <0 56.0 56.7 58.7 60.3 The results given in Table 1 show that as the concentration of the antimony compound increases the amount produced in the processed oil decreased of hydrogen and coke and gasoline efficiency increased ny.

Carry on with the remaining 5 catalyst samples impregnation, pretreatment, aging and the proper process as described above but the ratio the oil catalyst was adjusted to for of all these catalyst samples, the degree of conversion was changes amounted to 75% by volume. The results were given no in table 2, with individual values was established as stated in the discussion of Tab face1. . ¦¦ ' 56 The results given in Table 2 show that as the concentration of the antimony compound increases the amount of hydrogen and coke produced decreases, a the amount of gasoline produced increases. Comparison these results with the results given in Table 1 indicates that with a conversion rate of 75% by volume of the catalyst is atktywinosicc slightly lower than at the conversion of 70% by volume, although the yield is just as beneficial.

Example. ' A. This example shows the effect of the applied according to the invention antimony 0,0-dialkyl diphosphate. 05 compared to known additives. Prepared eo105 505 Table 2.

Quantity added him antimony 0 0.1 0.25 0.5 1.0 Catalyst quantity ratio tor the amount of oil 7.4 7.3 7.2 7.2 7.5 Performance coke 16.4 13.9 13.2 121.7 1H.6 hydrogen volume (liters) processed volume oil 142 89 71 61 56 gasoline 54.8 57.0 59.3 61.6 63.0 18 catalyst samples were collected and processed ce, saturation and pre-aging in a manner described in Example 1, 6 of these samples were saturated with varying amounts of 0,0-dialkyl diphosphate antimony used in Example 1, 6 na saturated with triphenolantimony and the remaining 6 tylophosphine. All these compounds used in solutions in anhydrous cyclohexane. Quantities the compounds used for impregnation are given in Table 3 in percent by weight of antimony or phosphorus, where in this table the symbol A stands for but that 0.0-dialkyl two- Antimony Phosphate containing 10.9% by weight of antimony, B means that to saturate the table triphenylantimony was used and C is used not trybutylphosphine.

The prepared catalyst samples were used for Cracking Kansas City Gaseous Oil proper at a temperature of 16 ° C 0.875 g / ml, a viscosity of 2.9 centimeters and slopes at a temperature of 99 ° C and 38 ° C liquid temperature. Kra¬ The hunting was carried out in a laboratory reactor with a fixed bed at a temperature of 482 ° C.

The ratio of oil to catalyst was adjusted to 36 for the conversion to be 75% by volume out. Quantities were measured; manufactured gasoline, coco su and hydrogen and all results were compared with the results obtained with the use of catalysts ra without additives, agreed by contract not for 1.00. Selectivity of the manufacturing process gasoline was determined by measuring the volume of products by boiling point below 204 ° C and divide it by the volume of oil converted times 100.

The converted oil is the volume processed oil, reduced by the volume of the liquid fractions at boiling point greater than 204 ° C. For example, if; this selectivity in the case of an untreated catalyst was 50% by volume, the selectivity of in the case of a treated catalyst, bearing as shown in Table 1.04, the value of the selection efficiency 52% by volume. The amount of coke was measured do not weigh the dry catalyst after the cracking process and the amount of hydrogen produced was determined as by means of known methods, measuring the Volume of a g tones flowing out of the reactor and denoting v their hydrogen content.

The test results are given in Table 3.

Table 3.

Amount of additive% by weight 0.1 0.2 0.3 0.4 0.5 1.0 Selectivity of the process gasoline production AND 1.04 1.06 1.07 1.08 1.09 1.12 B 1.00 1.00 ls00 1.00 1.00 1.02 C. 1.02 1.04 1.05 1.04 1.04 1.01 Coke quantity in% weight to the load AND 0.95 0.92 0.88 0.87 0.85 0.85 B 0.92 0.87 0.83 0.81 0.80 0.80 c l ', 00 0.98 0.97 0.97 0.96 0.92 Hydrogen volume ratio to volume processed oil AND 0.12 0.11 0.11 0.10 0.10 0.10 B 0.15 0.13 0.12 0.11 0.11 0.10 c | 0.16 0.15 0.15 0.14 0.14 0.13 The results given in Table 3 show that of the tested additives, the best results are given by the additive used in the invention, titer It gives the highest selectivity of the process weakens toerosite and reduces the pity of hydrogen, while the amount of coke produced is of value the intermediate value between the values obtained when using the other 2 additives. 66 B. To determine if a mixture was other regenerating agents give better results than the individual agents used, triphenylane thymone and tributylphosphine were dissolved in an- aqueous cyclohexane and a mixture of these solutions samples of the spent catalyst were saturated, description described in Example 1. Catalyst samples was given a pre-aging as described in 9 105 505 for example I, lead to HO cycles of cracking - regeneration, while cracking Borger, Texas crude oil, drained big frictions. Naisitejpinie each sample of catalyser was used to crack Kansas gas oil Gits at 482 ° C, feeding oil in each cycle for approximately 30 seconds. To the achievements of the various degrees of conversion were varied oil to catalyst ratio. Prepared 3 catalyst samples, the first containing Rala 0.25 wt.% phosphorus and 0.75 wt.% antimony, the other contained 0.5% by weight of phosphorus forium and 0.5% by weight of antimony and the third by weight about 0.75% by weight of phosphorus and 0.25% by weight antimony.

With a conversion of 75% by volume using a catalyst saturated with two compounds, 25-40% less hydrogen was obtained than when using a catalyst, they do not contain of additives, where this amount of hydrogen was substantially equal to the amount obtained in a hundred with the same amount of triphenylane alone thymone, that is, without the addition of tri-n-butylphosphine.

Also the amount of coke and the selectivity of the process In these tests, gasoline production was such alone, regardless of whether or not an additive was used tri-n-butylphosphine or also only triphen- loantimony. This shows that treatment catalyst mixture of antimony compound and The phosphorus compound gives no better results than the use of triphenylantimony alone. WITH on the other hand, examples I and II show that treatment of the catalyst according to the method the invention gives much better results than the use of not in a known manner of triphenylantimony alone.

Example III. For the tests, a known cat a talisman containing a gline as a carrier. Used the catalyst contained about 0.6% by weight of cerium, 0.4% by weight of lanthanum, 0.33% by weight of nickel, 0.56% by weight of vanadium and 0.89% by weight of zinc lasa. This catalyst was used for cracking Kansas City gas oil in the test reactor on a field of technical studies. Add to gas oil the same antimony compound was used as in example clade I at about 10.8% by weight per table relative to the amount of gas oil and at such time, to deposit 0.37% or 0.67% by weight on the catalyst head of antimony. Two catalytic samples were obtained tora - one containing 0.37% by weight of anti- monu and the other containing 0.67% by weight of anti- monu. These samples were removed from the reactor and tested dish in a laboratory stationary reactor my deposit. Cracking Kansas City Gas Oil at 482 ° C for approximately 30 seconds and cracking Borger oil, stripped of lighter fractions in a fluidized bed reactor at a temperature of 510 ° C for about 30 seconds kund. Aging and test cycles in the method described in example I. Area of the untreated catalyst wore 67.4 m2 / g and a pore volume of 0.31 ml / g. Ka¬ talcumbler containing 0.67% by weight of antimony after treatment, it had a specific surface of 57.5 m * / g and a pore volume of 0.26 ml / g. The test results are given in tables 4 and 5 with the antimony content in the catalyst is given in weight percent based on the weight of the catalyst.

Table 4.

The content of anti¬ monu in catal congestion 0 (trial control) 0.37 1 0.67 Quantity ratio catalyst to the oil 6.3 7.5 9.4 Degree of conversion % vol. changes quantitative 73.4 73.4 73.4 Performance of gasoline% vol quantitative 52.4 57.5 51.4 coke % by weight 8.0 6.9 7.3 The volumetric ratio of H2 to convert the oil formed 84.9 47.9 56.7 T a b 1 i c a 5.

| The content of anti¬ monu in catal congestion 0 (trial control) 1 0.67 Quantity ratio catalyst to the oil 8.2 8.2 Degree of conversion % vol. changes quantitative 72.5 69.9 Performance i of gasoline% vol quantitative 68.0 63.3 coke % by weight 13.8 11.0 The volumetric ratio of H2 to convert the oil formed 121.9 96.3 These results prove that by following the method according to invention, with the same degree transformation of the amount of produced coke and hydrogen were smaller than with the catalyst no treated and the gasoline yield was 65 almost the same when using age higher antimony concentration in the catalyst. In case of the case when the ratio of catalyst to oil was kept constant, the compound of antimony was due reduced the amount of coke produced105 505 11 12 and hydrogen. Lower catalyst activity incl containing 0.67% by weight of antimony is law possibly the result of the fact that this catalyst had smaller surface area and less volume The pore size is used compared to the catalyst in the control sample.

Example IV. This example shows a pro the process carried out according to the invention on a rock technical. In the cracker, fail consuming 181 tons of catalyst on activated carbon not as a carrier, cracked oil with a weight of its own 0.929 g / ml at 16 ° C, in quantity 3 863 700 liters / day. In order to introduce to catalyst. 0.5% by weight of antimony (in hundred catalyst weight ratio), antimony compound was added to the oil in an amount of 20 parts by weight antimony on. 1 million parts of oil in 17 days or 30 parts out of 1 million in 10 days. IN to maintain the antimony content of 0.5% by weight you should add 10 parts of anti-fog nu / million, if 7.2 tons are withdrawn from the reactor catalyst for 1 day and is replaced by a catalyst rem untreated. If you leave 5.4 tons of catalyst are withdrawn, then the same has an amount of antimony compound added to make it possible and keep the antimony content in the system of 0.66% by weight. This means that on it is necessary to add 985 kg of catalysis to the oil tora Vanlube 622 within 10 or 17 days, while v to maintain an antimony concentration of 0.5 wt 328 kg of this catalyst must be added during this time congestion during the day.

Claims (12)

Patent claims 1. A method of reactivating the catalyst of the hydrocarbon cracking process, carried out at elevated temperature and under pressure from atmospheric to several hundred atmospheres, consisting in separating the products obtained from the catalyst and directing it to the regeneration zone, where the regeneration is carried out by means of with the aid of oxygen at an elevated temperature, the catalyst is then returned to the cracking process and the catalyst is contacted with an antimony compound, characterized by the activity of the catalyst and the passivation of the metals deposited thereon, such as nickel, vanadium, and iron, in order to increase the activity of the catalyst and that an antimony compound of the formula shown in the figure is used, in which the substituents R are the same or different and represent hydrocarbon radicals with 1 to 18 carbon atoms, and the total number of carbon atoms in the molecule of this compound is 6 to 90. 2. Sipo-sób according to the substitutes. A compound according to claim 1, characterized in that an antimony compound of the formula shown in the drawing is used, wherein R represents alkyl radicals with 2 to 10 carbon atoms, optionally substituted cycloalkyl radicals with 5 or 6 carbon atoms, or optionally substituted phenyl radicals. 3. The method according to p. A compound according to claim 2, characterized in that an antimony compound of the formula shown in the drawing is used, in which R represent n-propyl or octyl radicals. 4. The method according to p. The method of claim 1, wherein the antimony compound is present in an antimony content of 6 to 21% by weight. 5. -5. The method according to p. The method of claim 1, wherein the antimony compound is used in an amount of 0.1-1.3% by weight of antimony with respect to the amount of the catalyst. 6. The method according to p. The process of claim 1, wherein the antimony compound is added to the cracked hydrocarbons. 7. The method according to p. The process according to claim 6, characterized in that the antimony compound is added to the hydrocarbons in an amount of 1-1500 parts of antimony per 1 million parts by weight of the hydrocarbons. 8. A method of reactivating the catalyst of the hydrocarbon cracking process, reduced by the deposition of metals such as nickel, vanadium and iron on the catalyst during cracking, by contacting the catalyst with an antimony compound by methods such as saturation. of the cracking catalyst with a solution of an antimony compound or the addition of this compound to hydrocarbons directed to the cracking process, characterized in that the antimony compound is a compound of the formula given in the figure, in which the R substituents are the same or different and represent hydrocarbon radicals with 1-18 carbon atoms, and the total number of carbon atoms in the molecule of this compound is 6-90. 9. The method according to p. The process according to claim 8, characterized in that an antimony compound of the formula shown in the figure is used, wherein R represents alkyl radicals with 2-10 carbon atoms, optionally substituted cycloalkyl radicals with 5-6 carbon atoms or optionally substituted phenyl radicals. 10. The method according to claim 9, characterized in that an antimony compound of the formula shown in the drawing is used, in which the R substituents represent n-propyl or octyl radicals. 11. The method according to p. The process as claimed in claim 8, wherein the antimony compound has an antimony content of 6 to 21% by weight. 12. The method according to p. 8. A method according to claim 8, characterized in that the antimony compound is used in an amount of 0.1-1.3% by weight of antimony in relation to the amount of usator. 10 1S 20 25 30 36 40 45 50 105 505 Rx 0 R / 0 l / p-s- 5b