JP2557599B2 - Catalytic composite composed of phosphorus, silicon, and aluminum oxide amorphous solid solution - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The catalyst of the present invention is an amorphous solid solution of phosphorus, silicic acid, and aluminum oxide. This catalyst can be prepared by mixing a hydrosol of alumina and silica with a phosphorus compound, gelling the mixture to form particles, and finally calcining to form an amorphous catalyst. Finally, it is possible to use this catalyst as it is or to disperse a metal on it and use it as a catalyst in various hydrocarbon conversion processes such as hydrocracking or alkylation.

[0002]

Alumina is a well known catalyst support and catalyst. It is also well known that the attributes of alumina can be changed by gelling together with silica to form a silica / alumina composite or incorporating phosphorus to form an alumina / phosphorus composite. Such modified aluminas are useful in catalyzing various hydrocarbon conversion processes such as hydrocracking, isomerization, and alkylation. Even in the prior art, there are several ways to prepare these materials as shown below.
U.S. Pat. No. 3,909,450 discloses a method of preparing an amorphous silica / alumina composition in which a sol of alumina and silica is mixed, gelled by the well-known oil drop method, and finally dried to form the composition. . The silica / alumina composition can also be prepared by eutectoid as described in US Pat. No. 3,274,124. U.S. Pat.No. 4,629,
717 and U.S. Pat. No. 4,727,209 describe a phosphorus modified alumina composite and a hydrocarbon conversion process using the composite. This complex is amorphous,
The molar ratio of phosphorus to aluminum is in the range 1: 1 to 1: 100 and the surface area is in the range 140-450 m ² / g. U.S. Pat. No. 4,760,040 discloses a hydrocarbon cracking catalyst made of crystalline aluminosilicate zeolite within a phosphorus-containing alumina matrix. Similarly, U.S. Pat.
No. 1 discloses a composition containing silica and alumina, which alumina is promoted by at least one element or compound selected from sodium, manganese, and phosphorus. In addition, U.S. Pat.
No. 621 describes a catalyst composed of an alumina-aluminum phosphate-silica matrix and amorphized by calcination at 500 ° C. for 16 hours. Japanese Patent Publication discloses a catalyst for purifying a hydrocarbon made of a carrier containing silica / alumina on which phosphoric acid is dispersed. Finally, Japanese Patent Laid-Open No. 60-18509 discloses P ₂ O ₅ and silica /
It discloses a catalyst that is a mixture of alumina.

In contrast to such prior art, catalytic compositions have been prepared which consist of an amorphous solid solution of phosphorus, aluminum and silicon oxide (hereinafter referred to as amorphous silica / alumina / phosphorus). In general, a solid solution simply means a solid phase containing multiple components. One type of solid solution is a substituted solid solution in which solute atoms or atomic groups are replaced by solvent atoms or atomic groups within the crystal structure. Substitution of one atom or group with another is possible only if the size of the substituting material does not change so much. Therefore, in this system, the phosphorus and silicon atoms are replaced, and the aluminum atoms occupy the place. Obviously, this differs from systems in which phosphoric acid or other phosphorus compounds are incorporated into alumina or silica / alumina substrates or supports. It also differs from JP 60-18509 in that there is no P ₂ O ₅ phase mixed with the silica / alumina powder. The properties of the present catalytic composition also differ from the hybrid materials described in the prior art. For example, the acidity of the catalyst depends on the amount of silica present in the composition, whereas in conventional catalysts it depends on the presence of free phosphorus on the catalyst. Also, the porosity of the catalyst is controlled by the polymer packing during gelation of the catalyst particles.

[0004]

SUMMARY OF THE INVENTION The present invention is directed to a catalytic composition, a process for preparing the composition, and a process using the composition. Therefore,
One embodiment of the present invention is 5-50% by weight of Al ₂ O ₃ , 10
-Phosphorus containing 90% by weight of SiO ₂ and 5-40% by weight of P ₂ O ₅ ,
It is a catalytic composition composed of an amorphous solid solution of silicon and aluminum oxide. Another embodiment of the present invention is a process for preparing such a catalytic composition composed of an amorphous solid solution of phosphorus, silicon and aluminum oxide, the process comprising an alumina hydrosol,
It consists of preparing a mixture of silica hydrosol and a phosphorus compound, gelling the mixture to make particles, and calcination of the particles to obtain an amorphous solid solution of phosphorus, silicon and aluminum oxide. Another embodiment of the present invention is a process of contacting a hydrocarbon with a catalytic composite under hydrocarbon conversion conditions to obtain a hydroconverted product, wherein the catalytic composite is 5-50% by weight. Al
₂ O _3, phosphorous containing P ₂ O ₅ of 10-90% by weight of SiO ₂ and 5-40% by weight, and a silicon and aluminum oxide.

[0005]

In general, the compositions according to the invention are prepared by making a mixture of alumina sol, silica sol and a phosphorus compound. Alumina sols are well known in the art and are usually prepared by digesting in a strong acid such as hydrochloric acid at a reflux temperature in the range of 80 to 105 ° C. The aluminum to chlorine ratio in this sol ranges from 0.7: 1 to 1.5: 1 on a weight basis. Silica sols are well known in the art and are usually prepared by acidifying water glass. This mixture also contains a phosphorus compound. Typical phosphorus compounds that can be used in the present invention are H ₃ PO ₄ , H ₃ PO ₂ , H ₃ PO ₃ , and (NH ₄ ) H ₂ PO.
₄ , (NH ₄ ) ₂ HPO ₄ , K ₃ PO ₄ , K ₂ HPO ₄ , KH ₂ PO ₄ , Na ₃ PO ₄ , Na ₂ H
PO ₄ , NaH ₂ PO ₄ , PX ₃ , RPX ₂ , R ₂ PX, R ₃ P, X ₃ PO, (XO) ₃ P
O, (XO) ₃ P, R ₃ PO, R ₃ PS, RPO ₂ , RPS ₂ , RP (O) (OX) ₂ , RP
(S) (SX) ₂ , R ₂ P (O) OX, R ₂ P (S) SX, RP (OX) ₂ , RP (SX) ₂ , RO
P (OX) ₂ , RSP (SX) ₂ , (RS) ₂ PSP (SR) ₂ , and (RO) ₂ ROP (O
R) ₂ where R is an alkyl or aryl group such as a phenyl group and X is hydrogen, R or a halide. These compounds include RPH ₂ as monovalent, R ₂ PH as divalent, and R ₃ P such as butyl phosphate as trivalent, oxidized phosphine oxide R ₃ PO such as tributylphosphine oxide, and trivalent. Phosphine sulfide R ₃ PS, monovalent RP
(O) (OX) ₂ , and divalent R ₂ P (O) OX, phosphoric acids such as benzene phosphoric acid, corresponding sulfur derivatives such as RP (S) (SX) ₂ and R ₂ P (S) SX, Esters of phosphoric acid such as dialkyl phosphonates (RO) ₂ P (O) H, dialkyl alkyl phosphonates (RO) ₂ P (O) R, and alkyl dialkyl-phosphonates (RO) P (O) R ₂ ; phosphinic acids such as diethylphosphinic acid R ₂ POX, monovalent (RO) P (OX) ₂ , divalent (RO) ₂ POX, and trivalent (RO) ₃ P, Included are phosphites and their esters, such as monopropyl esters, alkyl dialkyl phosphites (RO) PR ₂ and dialkyl alkyl phosphites (RO) ₂ PR esters. (RS) ₂ P (S)
H, (RS) ₂ P (S) R, (RS) P (S) R ₂ , R ₂ PSX, (RS) P (SX) ₂ , (RS)
Corresponding sulfur derivatives including ₂ PSX, (RS) ₃ P, (RS) PR ₂ and (RS) ₂ PR can also be used. Examples of phosphoric acid esters include pyrophosphites such as trimethyl phosphite, triethyl phosphite, diisopropyl phosphite, butyl phosphite, and tetraethyl pyrophosphite. The alkyl groups of the compounds mentioned above preferably contain 1-4 carbon atoms. Other suitable phosphorus-containing compounds include ammonium hydrogen phosphate, phosphorus trichloride, bromide, and iodide, alkylphosphoric acid chloride (RO) PCl ₂ , dialkylphosphoric acid chloride (RO) ₂ PCl, dialkylphosphorous acid chloride R. _{There are 2} PCl, dialkylphosphono chloride (RO) (R) P (O) Cl, dialkylphosphino chloride R ₂ P (O) Cl and RP (O) Cl ₂ . Applicable corresponding sulfur derivatives include (RS) PCl ₂ , (RS) ₂ PCl, (RS) (R) P
(S) Cl and R ₂ P (S) Cl are included. Preferred phosphorus compounds are phosphoric acid, phosphorous acid and ammonium phosphate. The three components of this mixture may be combined into a sub-mixture prior to making the mixture. That is, the phosphorus compound may be added to the alumina sol to obtain the phosphorus-modified alumina described in the cited US Pat. No. 4,629,717 or US Pat. No. 4,727,209. Once the phosphorus modified alumina sol is prepared, it is combined with acidified water glass, ie silica sol, and treated as described herein. Another method is to use a phosphorus compound to acidify the water glass, and phosphorus-modified silica.
The process of mixing the sol with the alumina sol and treating as described herein is included. Finally, the phosphorus compound can be added to the alumina / silica sol prepared by the process described in the cited US Pat. No. 3,909,450. Regardless of how a mixture of these three components is made, the mixture is
-50 wt% Al ₂ O ₃ , 10-90 wt% SiO ₂ , and 5-4
It must contain sufficient aluminum, silicon and phosphorus to provide a final product containing 0 wt% P ₂ O ₅ .

The next step in the process of preparing the composites of the present invention involves gelling the mixture described above. One such method is to combine a gelling agent with the mixture described above, and then combine the combined mixture prepared in the above procedure with oil heated to an elevated temperature to cause gelation with formation of spherical particles. Includes procedures to disperse in a bath or tower. Gelling agents that can be used in this process are hexamethylene tetramine, urea, or mixtures thereof. The gelling agent releases ammonia at the elevated temperatures that fix or convert the hydrosol spheres to the hydrogel spheres. These balls are then continuously removed from the oil bath,
It is usually subjected to special aging and drying treatments in oil and ammoniacal solutions to further improve its physical properties. The resulting aged, gelled particles are washed and dried at relatively low temperatures in the range of 93 ° C to 149 ° C (200-300 ° F), and then 454 ° C to 704 ° C (85 ° C).
It is calcined at a temperature of 0-1300 ° F) for 1-20 hours. This gives an amorphous solid solution of phosphorus, silicon and aluminum oxide. It is also possible to gel the mixture of aluminum, phosphorus and silicon components by spray drying the mixture or by adding a gelling agent to the mixture followed by spray drying. Spray drying is usually 10 at atmospheric pressure (101.3kPa)
It is conducted at temperatures from 0 ° C to 760 ° C (212 ° F-1400 ° F). The porous structure of the spray dried material need not, of course, be the same as the porous structure of the oblate spheroidal material made by the oil drop method.

The composite of the present invention is characterized as a solid solution of phosphorus, aluminum and silicon oxide. This means that the composite does not contain separate phases of alumina, silica, and phosphorus oxides. The composite may best be described as an alumina matrix substituted with phosphorus and silicon atoms. The fact that it is amorphous means that it has only short distance arrangements and not long distance arrangements associated with crystalline molecular sieves containing silicon, aluminum and phosphorus. There is. Furthermore, as mentioned above, the acidity of the complex depends on the amount of silica present in the complex,
Therefore, its acidity can be controlled by varying the amount of silica in the final complex. The composite also has pores with an average diameter of 30-300 angstroms, pore volume of the order of 0.35-0.75 cc / g, and surface area of 200-420 m ² / g.

The amorphous composites according to the invention can be used on their own to catalyze various hydrocarbon conversion processes, or
It is also possible to use it as a support for dispersing the catalytic metal. The metals particularly active in the performance of hydrocarbon conversion processes such as hydrocracking, isomerization, and alkylation are Group VIB and Group VIII metals,
It is a combination or a mixture of them. Group VIB metals are chromium, molybdenum, and tungsten,
Group VIII metals are iron, cobalt, nickel, ruthenium, rhodium, osmium, iridium and platinum. Of these metals, molybdenum, tungsten, nickel, cobalt, and mixtures of these metals are preferred. Particularly preferred is a catalyst containing nickel and tungsten. The concentration of these metals varies considerably with each metal in the range of 0.1-20% by weight of the support. In particular, when the metals are nickel and tungsten, nickel is present in the range 0.1-3 wt% and tungsten is present in the range 1-20 wt%. These metals can be dispersed by a well-known means such as impregnating a support with decomposable salts of the metals and then calcining. Representative examples of degradable salts that can be used are chromium chloride, chromium bromide, chromium nitrate, ammonium paramolibendate, ammonium metatungstate,
Iron chloride, iron bromide, iron nitrate, cobalt chloride, cobalt bromide, cobalt nitrate, nickel chloride, nickel bromide, nickel nitrate, ruthenium tetrachloride, rhodium trichloride, rhodium nitrate, palladium acid, palladium chloride, palladium nitrate, Osmium tetrachloride, iridium tetrachloride, chloroplatinic acid, and platinum tetrachloride. Impregnation techniques that can be used in metal dispersion include dipping, evaporation and vacuum impregnation. One preferred method of impregnation involves the use of steam jacket rotary dryers. Amorphous composite is impregnation solution and /
Alternatively, the composite is spun in a dispersant containing the desired ingredients contained within the dryer and is internally rotated by the rotary motion of the dryer. Evaporation of the solution in contact with the rotating complex is promoted by applying steam to the dryer jacket. The resulting catalytic composite is dried and then calcined at a temperature of 450-700 ° C. to decompose its metal salt into a metal oxide. In some cases, it is desirable to sulfurize the resulting catalytic composite, which can be done by a number of techniques known in the art. For example, after the one or more metals are dispersed on the support, the resulting catalyst composite is
It can be sulfided by contacting the catalyst with a sulfur-containing compound including hydrogen sulfide, carbon disulfide, mercaptans, disulfides, and the like. Conditions for sulfurizing the catalytic composite include temperatures in the range of 20 ° C to 200 ° C and 101.3 ° C.
It includes temperatures in the range of -1480 kPa (atmospheric pressure -200 psig). Sulfidation can be done in batch mode or continuous mode, but continuous mode is preferred.

The amorphous composite according to the present invention can be used as a hydrocarbon conversion catalyst as it is or after dispersing a catalytic metal thereon. Hydrocarbon conversion processes are well known in the prior art and include cracking, hydrocracking, isomerization, alkylation, polymerization, reforming, hydrogenation, dehydrogenation, transalkylation of both aromatic compounds and isoparaffins. Reaction, dealkylation, hydration, dehydration, hydrotreatment, hydrodenitrification, hydrodesulfurization, methanation,
And the Syngas shift process. The specific reaction conditions and raw material types that can be used in these processes are well known in the prior art. For example, US Pat. No. 4,310,440 and US Pat.
No. 71 discloses the conditions of the process described above.
Of the processes listed above, the amorphous composites of the present invention are particularly suitable for hydrocracking, cracking, and alkylation (especially aromatics alkylation).

The conditions for hydrocracking are usually 400 ° F to 1 ° C.
200 ° F (204-649 ° C), preferably 600-950 ° F (316
Includes temperatures in the range of -510 ° C. The reaction pressure ranges from atmospheric pressure (101.3 kPa) to 3,500 psig (24234 kPa), preferably 200-3000 psig (1480-20786 kPa). The contact time is usually 0.1 hr ~ ¹ -15 hr ~ ¹ , preferably 0.2 to 3
Equivalent to liquid hourly space velocity (LHSV) in the range of hr ~ ¹ . Hydrogen circulation rate is 1,000-50,00 per barrel of raw material
0 standard cubic feet (scf), preferably in the range of 2,000-30,000 scf (355-5,333 standard m ³ / m ³ ) per barrel of feed. Suitable hydrotreating conditions are generally within the hydrotreating conditions described above. The effluent from the reaction zone is usually removed from the catalyst bed, subjected to partial concentration and vapor-liquid separation, and then fractionated to recover its various components. Hydrogen and, if desired, some or all of the unreacted heavy material is refluxed to the reactor.
It is also possible to send unreacted material to the second reactor using a two-step flow. The catalyst according to the invention can be used in only one stage of such a process,
It can be used in both reactor stages.

Catalytic cracking processes are preferably carried out with these compositions using feedstocks such as gas oil, heavy naphtha, deasphalted crude oil residuum, the most important desired product of which is gasoline. . 850-1100 ° F
A temperature range of 0.5-10 hr- ¹ LHSV value and a pressure condition of 101.3-446.1 kPa (0-50 psig) are suitable. Alkylation of aromatics aromatics (C ₆ -
C _12), includes a process for making a linear alkyl substituted aromatic compounds, especially by reacting benzene with monoolefins. This process uses a range of 5: 1 to 30: 1 aromatics: olefins (eg benzene: olefins).
Ratio, LHSV of 0.3-6 hr ~ ¹ , temperature of 100-250 ° C, and pressure of 1480-6996 kPa (200-1000 psig). More detailed information about the device can be found in US Pat. No. 4,870,222, which is incorporated herein by reference.

[0012]

EXAMPLES Example 1 Several compositions were made containing phosphorus, silicon and aluminum, or only silicon and aluminum. The following procedure was used to prepare these samples. Metallic aluminum with a Al: Cl weight ratio of 0.88 (Al: 12.5 wt%) and polymeric alumina chloride hydroxy was cooked in dilute hydrochloric acid at a temperature of 102 ° C. to form a hydrosol. Thereafter, the amount of phosphoric acid calculated to bring the phosphorus content of each calcined spherical particle to the specified value other than the particles used as a control was added to the hydrosol. In each experiment, the appropriate amount of water was added to maintain the alumina and aluminum phosphate solids content in the 25-30% range. Each phosphorus-containing hydrosol was then cooled and mixed with an aqueous solution of hexamethylene tetraamide (HMT) to form a hydrosol having a HMT: Cl molar ratio of 0.4. Cl: Na molar ratio 1.10
Acidified water glass was prepared by adding concentrated HCl to diluted water glass so that the SiO ₂ concentration was 11%. The phosphorus-containing alumina sol was then added to the acidified water glass to form an acidic solution containing phosphorus, alumina and silica hydrosol. The hydrosol was formed into spherical hydrogel particles by discharging the hydrosol as droplets into a dropping tower containing an oil suspension medium at a temperature of 95 ° C. The spherical hydrogel particles were aged at a temperature of 100 ° C. for 19 hours with a portion of gas oil. After the aging treatment, the spherical particles were washed with water at a temperature of 95 ° C and then dried at a temperature of 120 ° C for 2 hours. Finally, the amorphous silica / alumina / phosphate spherical particles were calcined at a temperature of 650 ° C. for 2 hours in the presence of (3% H ₂ O) humid air. Table 1 shows the attributes of the spherical particles produced by the procedure described above.

[0013]

[Table 1]

Example 2 The spherical particles prepared in Example 1 were impregnated with nickel and tungsten salts to prepare a hydrocracking catalyst. Appropriate amounts of ammonium metatungstate and nickel nitrate were dissolved in pure water and placed in a stream jacket rotary dryer. To this solution was added 120 grams of the desired spherical particles described in Example 1, the mixture was spun at room temperature for 30 minutes, then steamed on a rotary drier to completely evaporate excess water. The resulting Ni / W catalyst particles were calcined for 1 hour at 240 ° C and then for 2 hours at 565 ° C. During this calcination, 1
Air was blown through the calcination furnace at a rate of 0.056 m ³ (1.5 cubic feet) per hour. The composition of the finally prepared catalyst is shown in Table 2.

[0015]

[Table 2]

Example 3 The catalyst prepared in Example 2 was tested in a pilot plant using a crude oil, Light Arabian VGO, with the following attributes. Specific gravity 0.9206 @ 60 ° F or relative density at 15 ° C Initial boiling point 354 ° C (670 ° F) 10% 443 ° C (830 ° F) 20% 454 ° C (849 ° F) 30% 460 ° C (860 ° F) 40% 471 ° C (879 ° F) 50% 482 ° C (900 ° F) 60% 492 ° C (917 ° F) 70% 501 ° C (933 ° F) 80% 513 ° C (955 ° F) 90% 526 ° C ( 979 ° F) Final boiling point 553 ° C (1027 ° F) Each catalyst was tested under the following test conditions. Test conditions Plant pressure 13891kPa (2000psig) LHSV 1.0hr ~ ¹ CFR * 1.0 Recycle H ₂ 1780m ³ / m ³ (10,000SCFB _FF ) * combined feed ratio = (feed + recycle) / feed Each of the tested catalysts Table 3 shows the activity results of

[0017]

[Table 3] The test results shown in Table 3 are silica / alumina /
The advantages of catalysts made with phosphorus solid solution supports are clearly demonstrated. This is evidenced by the low deactivation rate of the phosphorus-containing composition and the high yield of kerosene.

[0018]

EFFECT OF THE INVENTION The catalytic composite of the present invention comprising an amorphous solid solution of phosphorus, silicon and aluminum oxide can be used as itself or as a carrier for a catalytically active metal to hydrocrack, isomerize, alkylate a hydrocarbon. It is a new and useful catalyst used for chemical conversion.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C10G 47/12 9547-4H C10G 47/12 49/04 9547-4H 49/04 // C07B 61 / 00 300 C07B 61/00 300

Claims (10)

(57) [Claims] 1. 5 to 50% by weight of Al ₂ O ₃ , 10 to 90% by weight of S
iO _2, and phosphorous containing P ₂ O ₅ 5-40% by weight, silicon, and hydrocarbon conversion process for the catalytic complex consists of amorphous solid solution of aluminum oxide. 2. The composite has pores with an average diameter of 30 to about 200 angstroms and a surface area of 200-about 420 m ² / g.
The composite of claim 1, wherein the pore volume is 0.35-0.75 cc / g. 3. The group VIB of the periodic table on which the complex is formed.
7. The composite of claim 1 having dispersed therein one or more metals selected from the group consisting of and VIII metals and mixtures thereof. 4. The Group VIB metal of the mixture is tungsten and is present in a concentration of 1-20% by weight of the composite, and the Group VIII metal of the mixture is nickel and 0.1-3% by weight of the composite. The complex of claim 3 present in a concentration. 5. A mixture of alumina hydrosol, silica hydrosol and phosphorus compound is prepared, the mixture is gelled to form particles, and the particles are formed to form phosphorus, silicon, and aluminum oxides. A process for preparing a catalytic composition according to claim 1 or 2, comprising a step of baking. 6. A gelling step combines the mixture with a gelling agent and disperses the combined mixture in an oil bath under conditions necessary to gel the oil droplets into particles, such as phosphorus, silicon. , And the process of claim 7 performed by calcining the particles to obtain spheres composed of an amorphous solid solution of aluminum oxide. 7. The process according to claim 5, wherein the gelling agent is hexaethylenetetramine or urea. 8. The process of claim 5, wherein said gelling step is performed by spray drying the mixture. 9. A hydrocarbon conversion process comprising contacting a hydrocarbon with a catalytic composition according to any one of claims 1 to 4 under hydrocarbon conversion conditions. 10. The process of claim 9 wherein said hydrocarbon conversion process is hydrocracking or alkylation.