CN1004357B - Catalist for catalytic cracking and cracking method using a kind of molecular sieve - Google Patents

Catalist for catalytic cracking and cracking method using a kind of molecular sieve Download PDF

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CN1004357B
CN1004357B CN85109362.0A CN85109362A CN1004357B CN 1004357 B CN1004357 B CN 1004357B CN 85109362 A CN85109362 A CN 85109362A CN 1004357 B CN1004357 B CN 1004357B
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sapo
molecular sieve
weight
aluminosilicophosphate
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CN85109362A (en
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里吉斯·约瑟夫·佩利特
彼得·凯文·库格林
马克·托马斯·斯坦尼尤利斯
加里·诺曼·朗
朱尔·安东尼·拉博
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Union Carbide Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates (SAPO compounds)

Abstract

Cracking catalysts containing silicoaluminophosphate molecular sieves are disclosed. Such catalysts are derived from specific silicoaluminophosphate molecular sieves of U.S. Pat. No. 4,440,871. The catalyst when used for the conversion of hydrocarbons provide product mixtures different from those obtained by use of aluminosilicates based catalysts.

Description

The cracking method of applying silicon aluminophosphate molecular sieve catalyzer
The present invention relates at United States Patent (USP) 4,440 cracking catalyst that the silicoaluminophosphamolecular molecular sieve by special of narration forms in 871.
Up to the present, the research of cracking catalyst generally is only limited to the preparation modified zeolite with as cracking catalyst, and its research also is only limited to the interaction of this zeolite with other inorganic oxide material.Following patent is the representative of the prior art aspect of research zeolite based cracking catalyst:
Application by being dispersed in the formed conversion catalyst of zeolite that contains in the silicon matrix has been disclosed in United States Patent (USP) 3,140, in 249 and 352,796.
At United States Patent (USP) 3,312, the application of adulterated matrix component is disclosed in 615, for example, a kind ofly comprise that (this inert powder may be α-Al for zeolite, a kind of inorganic oxide matrix and inert powder 2O 3) Application of Catalyst.At United States Patent (USP) 3,542, disclose in 670, comprise a kind of soft silica-aluminum oxide, add the catalyzer of aluminum oxide and a kind of zeolite respectively, and at United States Patent (USP) 3,428, disclose in 550 and comprised a kind of zeolite, the catalyzer of a kind of amorphous alumina hydrate and alumina monohydrate.
Have been found that and use low alkali metal content and unit cell diameter less than about 24.45
Figure 85109362_IMG2
Zeolite can improve the water vapor stability of Y zeolite and thermostability (see United States Patent (USP) 3,293,192 and issue patent 28 again, 629(United States Patent (USP) 3,402,996 issue patent again)).
In addition, United States Patent (USP) 3,591,488 disclose in 427 ℃ to 816 ℃ temperature range, can handle Hydrogen or ammonium type zeolite for water, perhaps then with positively charged ion the zeolite of this water vapor and water treatment be carried out cationic exchange again, this kind positively charged ion can be the rare earth metal positively charged ion.This method has increased the mol ratio of the silicon-dioxide and the aluminum oxide of zeolite, has also increased defect structure simultaneously.United States Patent (USP) 3,676,368 disclose a kind of hydrogen faujusite of rare earth ion exchanged of the 6-14% of containing rare-earth oxide.United States Patent (USP) 3,957, No. 623 disclose a kind of total amount that contains is 1-10%(weight) zeolite of the rare earth ion exchange of rare-earth oxide.United States Patent (USP) 3,607,043 to disclose a kind of preparation rare earth ion content be 0.3-10%(weight) the method for zeolite.
United States Patent (USP) 4,036,739 disclose hydrothermally stable and ammonia is stablized Y zeolite, and wherein the part sodium ion in the sodium Y zeolite is exchanged into ammonium ion (NH &lt;math><msup><mi></mi><msub><mi>+</mi></msup><mi>4</mi></msub></math> ), carry out steam roasting subsequently again, and carry out ion-exchange with ammonium again, make last sodium oxide content be lower than 1%(weight), will exchange product then again and carry out roasting, or according to United States Patent (USP) 3,781,199, with this zeolite with after a kind of refractory oxide mixes, carry out the roasting second time again.
Prior art discussed above is in the past and the representative of present fluid catalystic cracking (FCC) catalyst formulation.Recently at United States Patent (USP) 4,400, a class new catalyst is disclosed in 871.The catalyzer of this patent disclosure is the crystalline microporous silicoaluminophosphamolecular molecular sieve.Its application in cracking method is also disclosed.At United States Patent (USP) 4,440, in 871, use the cracking test of normal butane, to several aluminosilicophosphates (" SAPO "), estimate their catalytic cracking activity, and calculated first order reaction velocity constant value thus.Though all expressing, the first order reaction velocity constant of the aluminosilicophosphate that all are tested has catalytic activity, the still change between 0.2 to 7.4 of velocity constant value.The application of the mixture of a kind of silico-aluminate and special sial silicate is disclosed in and applies for simultaneously with the present invention and the common U.S. that transfers the possession of awaits the reply in the patent application (act on behalf of case number be 14697).
The present invention relates to cracking catalyst and fluid catalystic cracking method.This type of catalyzer comprises a kind of United States Patent (USP) 4,440 that is disclosed in, the special silicoaluminophosphamolecular molecular sieve of a class in 871 and that have specific aperture, and its preferably uses simultaneously with at least a inorganic oxide that exists as binding agent and/or matrix components.
The present invention relates to the crude oil material catalytic cracking to produce lower boiling hydrocarbons.Method of the present invention is by with described raw material and United States Patent (USP) 4,440,871, in the special silicoaluminophosphamolecular molecular sieve of a disclosed class contact and implement.
The United States Patent (USP) 4 that on April 3rd, 1984 issued, 440871, the aluminosilicophosphate that the present invention uses has been described, this aluminosilicophosphate is characterised in that their calcined form, at pressure is that 500 mmhg, temperature are under 20 ℃ of conditions, and the adsorption rate of Trimethylmethane is at least 2%(weight).In another embodiment, the feature of this type of aluminosilicophosphate also is their calcined form, is 2.6 mmhg at pressure, and temperature is under 22 ℃ the condition, to the adsorption rate of triethylamine greater than 5%(weight).
The present invention relates to contain the new catalytic cracking catalyst of silicoaluminophosphamolecular molecular sieve, and their methods of in catalytic cracking process, using.Catalytic cracking catalyst of the present invention is to make by listing this paper United States Patent (USP) 4,440,871 disclosed novel aluminosilicophosphates as a reference in.
It is for ease of reference fully that this paper is called " SAPO " molecular sieve with applied aluminosilicophosphate among the present invention, and employed dummy suffix notation is consistent in this dummy suffix notation and the United States Patent (USP) 4,440,871.The catalyzer of the application SAPO that hereinafter will discuss is to contain United States Patent (USP) 4,440, certain silicon aluminium phosphate catalyst of 871, and generally always will use together with at least a inorganic oxide matrix component.
" SAPO " used herein speech is called " SAPO " molecular sieve in United States Patent (USP) 4,440871.Disclosed in the United States Patent (USP) 4,440871 " SAPO " molecular sieve is a microporous crystalline silico-alumino-phosphate, and the micropore on the molecular sieve is of uniform size, and its specific diameter is approximately greater than 3
Figure 85109362_IMG3
(dust), the basic experience chemical constitution of molecular sieve is when former synthesized form and anhydrous form:
mR：（Si xAl yP z）O 2
In the formula, at least a organic formwork agent that " R " representative exists in the crystals microcellular system; The numerical value of " m " is 0.02-0.03; " m " represents every mole of (Si xAl yP z) O 2The mole number of " R " that exists; " X ", " Y " and " Z " represent the molar fraction that exists with tetrahedral oxide compound of silicon, aluminium and phosphorus respectively, described molar fraction is at United States Patent (USP) the 4th, on the ternary diagram of Fig. 1 of 440, No. 871 by in the determined pentagonal compositing range of these 5 points of A, B, C, D and E.United States Patent (USP) 4,440,871 molecular sieve are also to have a kind of PO &lt;math><msup><mi></mi><msub><mi>+</mi></msup><mi>2</mi></msub></math> ，AlO &lt;math><msup><mi></mi><msub><mi>-</mi></msup><mi>2</mi></msub></math> And SiO 2The silicoaluminophosphamaterial material of the three-dimensional micropore network structure of tetrahedron element is a feature, and the basic experience chemical constitution of its anhydrous form is:
mR：（Si xA yP z）O 2
In the formula, at least a organic formwork agent that " R " representative exists in the crystals microcellular system; " m " represents every mole of (Si xA yP z) O 2The mole number of " R " that exists; The numerical value of " m " from 0 to 0.3; " X ", " Y " and " Z " represent the molar fraction of the silicon, aluminium and the phosphorus that partly exist with oxide compound respectively, described molar fraction be on the ternary diagram of Fig. 1 by in these 5 determined compositing ranges of point of A, B, C, D and E, described aluminosilicophosphate has a kind of X-ray powder diffraction figure of feature, under having at least, this kind diffractogram is listed in United States Patent (USP) the 4th, listed d-spacing in any one table in 440, No. 871 table I, III, V, VII, IX, X III, X XI, XX III or the XX V.In addition, the SAPO molecular sieve can be at the high roasting temperature that is enough to make at least a portion organic formwork agent of existing in crystallization internal capillary system to be removed.The SAPO that the present invention uses comprises SAPO-5, SAPO-11, SAPO-31, SAPO-37, SAPO-40 and SAPO-41.
SAPO catalyzer of the present invention is to use United States Patent (USP) 4,440,871 aluminosilicophosphate prepares, as mentioned above, the further feature of this catalyzer also is, its calcined form is 500 mmhg at pressure, temperature is under 20 ℃ of conditions, and the adsorption rate of Trimethylmethane is at least 2%(weight).In another embodiment, the above-mentioned feature of this SAPO also is its calcined form, is 2.6 mmhg at pressure, and temperature is under 22 ℃ of conditions, to the adsorption rate of triethylamine greater than 5%(weight).The above-mentioned CHARACTERISTICS IDENTIFICATION of employed in the present invention aluminosilicophosphate (SAPO) relates to a kind of characterization of adsorption and identifies, this kind characterization of adsorption identifies it is to handling through a kind of back is synthetic, for example fuse or chemical treatment, to remove most of because the SAPO of the template " R " that synthesis of molecular sieve just adds carries out.Though special SAPO of the present invention is with when its calcined form, to the adsorption rate of Trimethylmethane or triethylamine is feature, but the present invention also must comprise the SAPO that uses a kind of not roasting, this kind SAPO is that above-mentioned adsorption rate with its calcined form is a feature, because when under catalytic cracking condition, using the SAPO of this not calcined form in the method, this SAPO will be carried out roasting or hydrothermal treatment consists on the spot, so that have this specific adsorption rate to Trimethylmethane or triethylamine.Therefore, owing to there is template " R " to have (this kind template is owing to add during synthesis of molecular sieve), so SAPO will be processed into a kind of form that it is characterized in that the above-mentioned adsorption rate of Trimethylmethane on the spot, but the SAPO-11 of calcined form is to be feature with the above-mentioned adsorption rate to Trimethylmethane and triethylamine.Therefore, mention a kind of when having the SAPO of specific characterization of adsorption during at its calcined form, and do not mean that the SAPO that get rid of to use former synthesized form, and the SAPO of this synthesized form will have such characterization of adsorption when carrying out roasting, hydrothermal treatment consists or other processing (for example ion-exchange).
This paper uses " thermal treatment " speech and is illustrated in air or thermal bake-out and a kind of hydrothermal calcine (thermal bake-out under the situation that has water vapor to exist) under the situation that rare gas element (for example nitrogen) exists are arranged.Thermal treatment generally is to carry out one period more than 0.25 hour in the temperature more than 300 ℃, and when thermal treatment was a kind of hydrothermal treatment consists, then this kind processing generally was to have to be at least about the 20%(volume in air) water vapor situation about existing under carry out.The source of water vapor is unimportant, and it can provide from the water vapor source of outside, perhaps also can produce on the spot under the used Heating temperature of hydrothermal treatment consists.As mentioned above, also the SAPO of its former synthesized form this technological process can be used for,, when the SAPO with former synthesized form adds this process, a kind of hydrothermal treatment consists will be provided on the spot because under catalytic cracking condition.
Can also be by with silicoaluminophosphamolecular molecular sieve (being with or without in the presence of a kind of inorganic oxide matrix component) and at least a positively charged ion that can form hydrogen, for example NH &lt;math><msup><mi></mi><msub><mi>+</mi></msup><mi>4</mi></msub></math> , H +Contact with the solution of quaternary ammonium ion SAPO is carried out ion-exchange.It is generally acknowledged that selected SAPO can also comprise positively charged ion that is selected from II A family, III A family, III B family to VII B family and rare-earth cation and its hybrid ionic that is selected from cerium, lanthanum, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium.At present, not observing the rare-earth cation that exists with the SAPO molecular sieve is favourable to the activity of SAPO component.Though in some cases, their existence may be favourable, the essence of the relation between multivalence attitude positively charged ion and the SAPO catalyzer is still not fully aware of at present.Because ion-exchange, aluminosilicophosphate can contain at least a positively charged ion, for example, forms the positively charged ion of hydrogen, and this positively charged ion is different from those positively charged ions that just link with silicoaluminophosphamolecular molecular sieve at the beginning in synthetic.Owing to the positively charged ion that ion-exchange exists, press the starting weight of silicoaluminophosphamolecular molecular sieve and calculate, its significant quantity is preferably in 0.1%-20%(weight) between, and general significant quantity is in 0.5-10%(weight) between.
Certainly, thermal treatment noted earlier and ion-exchange can be carried out one or many by any order, and these changes all are within the scope of the present invention.
Ion-exchange is typically carried out, and prepares the slurry of silicon aluminium phosphate catalyst earlier, and promptly the catalyzer of each volume adds the water of 5-15 volume, adds a kind of selected cationic solution that contains afterwards again.Ion-exchange is carried out in room temperature usually, then the solution of gained is heated to approximately more than 50 ℃, and stirs 0.5-3 hour under this temperature.Then this mixture is filtered and washes with water to remove unnecessary negatively charged ion, these negatively charged ion are introduced owing to adding cationic salts solution.
Silicoaluminophosphamolecular molecular sieve generally will be used with at least a inorganic oxide matrix component, up to the present, inorganic oxide matrix component commonly used in the prescription of fluid catalytic cracking (FCC) catalyzer comprises: the inorganic catalyzed oxidation thing of amorphous, the silica/alumina that for example has catalytic activity, clay, silicon-dioxide, aluminum oxide, silica-alumina, silicon-dioxide-zirconium white, silica-magnesia, aluminum oxide one boron oxide, aluminum oxide one titanium dioxide etc., and their mixture.This matrix can be the form of colloidal sol, hydrogel or gel, and aluminum oxide normally, silicon-dioxide or silicon-dioxide one alumina component, for example Guan Yong silicon-dioxide one aluminum oxide cracking catalyst wherein has this catalyzer of several classes and composition thereof to have bought on market.Matrix itself may play a kind of katalysis, and for example to the viewed the sort of catalytic activity of silica/alumina, perhaps matrix itself may be inert basically.In some cases, this matrix can play the effect of a kind of " tackiness agent ", though in some cases may be with last catalyzer spraying drying or moulding and do not need tackiness agent.These substrate materials can be made the cogelled of a kind of silicon-dioxide and aluminum oxide, or make the aluminum oxide on the hydrogel that is deposited on a kind of premolding and preconditioning.Silicon-dioxide can be present in the matrix as a kind of main matrix components with solid form, and for example, the amount of silicon-dioxide is greatly about 5-40%(weight) between, and best be in about 10-30%(weight) between.Silicon-dioxide can also use with a kind of cogelled form, and its composition contains the 75%(weight of having an appointment) silicon-dioxide and about 25%(weight) aluminum oxide or contain the 87%(weight of having an appointment) silicon-dioxide and about 13%(weight) aluminum oxide.In final catalyst, typical inorganic oxide matrix component is in about 0-99%(weight) between, and best be in about 5-90%(weight) between (pressing total catalyst weight calculating).In final cracking catalyst, with aluminosilicophosphate, also can adopt other material, clay for example, carbon monoxide oxidation promotor etc., these also belong within the scope of the invention.
The representative of the matrix system that can use in the present invention, be disclosed in No. the 1315553rd, the british patent specification of publishing on May 2nd, 1973 and United States Patent (USP) No. 3446727 and No. 4086187 in, these patents are all listed reference of the present invention in.
As mentioned above, catalyzer of the present invention can use with a kind of matrix components, and this kind matrix components can be silicon-dioxide or alumina component.This alumina component can comprise the discrete particles of various aluminum oxide, for example, and pseudobochmite.The alumina particle of this discrete form has, and measures with the BET method, greater than about 20 square metres of every gram (rice 2/ gram) total surface area, and best be greater than 145 meters 2/ gram, for example, about 145-300 rice 2/ gram.The micro pore volume of alumina component is normally greater than 0.35 cubic centimetre/gram.The mean particle size of alumina particle generally is less than 10 microns, and best be less than 3 microns.The aluminum oxide component can be used alone as matrix or with the use that combines of other matrix components.The aluminum oxide component can be any aluminum oxide, and preferably moulding in advance, and make it be in that a kind of to make its surface-area and microvoid structure all be stable physical aspect, thereby in the time of in this aluminum oxide being added a kind of inorganic gel impure, that contain suitable abundant residues soluble salt, this soluble inorganic salt will can not change the surface and the microporous properties of aluminum oxide with measuring, also can not promote their chemical etchings to the preformed porous alumina that may change.For example, this aluminum oxide normally a kind of through suitable chemical reaction, slurries are aging, filter, dry, the part of salt residue is removed in washing, heating makes its volatile content drop to the weight less than 15%(then) the formed aluminum oxide in back.The amount of the alumina component that in the catalyzer finished product, exists, the total of pressing catalyzer can be to be about 5-95%(weight), and best be at 10-30%, in addition, in Preparation of Catalyst, can use a kind of aqueous solution or hydrogel of aluminum oxide, perhaps the hydrated aluminum oxide slurries.
Can use the shaping of catalyst technology of standard to form the finished product of catalyzer in the mixture of one or more silicoaluminophosphamolecular molecular sieves and one or more inorganic matrix components, these technology comprise, spraying drying is granulated extrusion molding and other suitable ordinary method.In the preparation catalyzer, the spraying drying step is a preferable methods, and this step is well-known in the art.When catalyzer is made extruding pelletizing and behind air drying, then usually with its pulverizing and be sized to granularity less than 150 microns.
The catalyzer that contains SAPO can prepare with the method for any routine.A kind of method that adopts silica-alumina and porous aluminum oxide to prepare this kind catalyzer is that water glass and a kind of alum liquor are reacted, to form a kind of water-setting rubber cement of silica/alumina, and then it is the gel slurry of gained is aging, to obtain required micropore character, filtration to be removing a large amount of external and undesirable sodium ion and sulfate ions, and then makes slurry in water.This aluminum oxide can be under suitable condition, by sodium aluminate solution and alum liquor are reacted, that slurries are aging to obtain the required micropore character of aluminum oxide, filtration, drying, to make slurry to remove sodium ion and sulfate ion and dryly to make the content of its volatile matter be reduced to 15%(weight in water again) prepare.This aluminum oxide can be made slurry in water then, and mix with a kind of impure silica-alumina water-setting rubber cement with proper amt.Just the SAPO molecular sieve component can be added in this kind mixture then.Each component of using sufficient amount provides required last composition.Then the mixture that obtains is filtered, remove the external soluble salt of partly staying wherein.To cross filterable mixture drying subsequently to prepare dried solid.Then more this dried solid is made slurries in water, and washing is to there not being unwanted soluble salt in fact.Then with the catalyzer drying, to residual moisture content less than about 15%(weight).This kind catalyzer generally will could use after roasting, but also can roasting on the spot in process under the catalytic cracking condition.
Carry out catalytic cracking with catalyzer of the present invention, can be under effective catalytic cracking condition, catalyst cracking method by any routine carries out, and suitable catalysis is split condition and comprised: temperature range is between about 204 ℃ to 871 ℃, preferably between 371 ℃ to 871 ℃; Pressure range is from being lower than 1 barometric point to several normal atmosphere, and typical pressure is between about 7 kilogram force/square centimeters at an about normal atmosphere (1.03 kilogram force/square centimeter).This process can implemented in the array apparatus down: fixed bed, moving-bed, ebullated bed, pulpous state reactor, pipeline reactor, riser reactor or fluidized-bed.Catalyzer of the present invention can be used for transforming any habitual hydrocarbon feed used in catalytic cracking, that is to say, catalyzer of the present invention can be used for cracked naphtha, gas oil and the residual oil with high metal contamination thing content.Catalyzer of the present invention, be particularly suitable for the cracking of the hydro carbons in the gas oil boiling range, just, be suitable for will be under a normal atmosphere boiling range be raw gasline 216 ℃ to 982 ℃ hydrocarbon oils cracking, produce and not only have boiling point, but also can produce the product of octane value with raising compared with beginning raw material low product.
This paper use " crude oil material " speech represent any from general oil field or offshore oilfield once, secondary, or the full fraction crude oil exploited of tertiary oil recovery and the raw material of producing with these crude oil." crude oil material " can comprise any full fraction " synthetic crude " (" syncrude "), for example those crude oil that can produce from coal, shale oil, Tar sands and pitch.This kind crude oil can be direct-distilled, perhaps produces by synthesizing by mixing.But generally preferably at first with crude oil desalting, because well-known sodium-chlor is a kind of poisonous substances for the catalyzer of most of cracking operations.In addition, also use " crude oil material " speech to comprise the integral part of crude oil, these integral parts of crude oil are generally as catalytically cracked material or its potential raw material, with comprise: for example, oil, synthetic crude (producing) are looked in fraction gas oil, heavy vacuum gas oil, normal pressure or decompression from shale oil, Tar sands, coal, from hydroeracking unit, hydrotreater, coker, pyrolytic process, and the raw material of high boiling point FCC product recycle fraction production; And boiling point is higher than the various cuts of conventional full boiling point of gasoline boiling range scope, and these cuts generally comprise and contain above compound of 11 carbon atoms and their mixture.
In addition, this catalyzer can be used for the FCC(fluid catalytic cracking effectively) process.Wherein, a kind of carbon-hydrogen micromolecular compound (CHFC) is mixed use with crude oil material.This process this paper is referred to as the FCC-CHFC process.
This paper uses " carbon-hydrogen micromolecular compound " speech, represents carbon atom number than the material that the material in the gasoline boiling range scope lacks, and to be preferably those carbon atom quantities be 5 or be less than 5 material, and these materials can be included into following any class:
A) hydrogen-rich molecule, promptly hydrogen % content is in 13.0-25.0%(weight) molecule of scope, these molecules comprise light paraffins, i.e. CH 4, C 2H 6, C 3H 8And other material.
B) its chemical structure molecule of allowing or help carbon-hydrogen small molecules to transform all can be used.These molecules comprise CH 3OH, other lower boiling alcohol, ethanol for example, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol etc., fatty ether, for example dme and other oxygenatedchemicals (acetal, aldehyde, ketone).
C) above-mentioned (a) or (b) the secondary reaction product of the material in the class, these products are carbon-hydrogen micromolecular compounds itself, or the hydrogen that transmits, these products comprise alkene, naphthenic hydrocarbon or alkane.
D) material that structurally or chemically is equivalent to (c) class, particularly alkene etc., and
E) (a) class to (d) class material whole or the composition of any material wherein.
It is preferred that carbon-the hydrogen micromolecular compound is methyl alcohol, dme and C 2-C 5Alkene, and be most preferred with methyl alcohol, dme wherein.
In addition, it is generally acknowledged that the FCC-CHFC process relates to combination reaction, these are reflected at sulphur, oxygen, nitrogen and the metal contamination object space face removed in whole crude oil or its heavy hydrocarbon part and are commonly considered as effectively, are effective to small part.
The operation of FCC-CHFC type method is generally being implemented under the following condition: temperature arrives in about 760 ℃ scope at 204 ℃, and normally in 371 ℃ to 649 ℃ scope; Pressure is selected to the scope up to tens kilogram force/square centimeters being lower than 1 normal atmosphere, but usually less than 14 kilogram force/square centimeters.Preferred condition comprises: temperature at 427 ℃ to about 621 ℃ scope; Pressure is in normal pressure to 7 kilogram force/square centimeter or higher pressure range.
Carbon-hydrogen micromolecular compound so just can provide to technological process with the most frequently used any method as long as be to exist when it contacts with catalystic material, and it is suitable promptly generating on the spot.
In preferably operating the FCC-CHFC process, the hydrocarbon raw material of methyl alcohol with a kind of gas oil type used.The weight percentage of the methyl alcohol in the hydrocarbon feed in feeding cracking or conversion operation can have bigger variation, can select to being about in 25% the scope being about 1%, and the weight calculating of pressing raw material, it approximately is between 5% to 20% that this ratio preferably remains on.But, this percentage ratio can change, and concrete percentage ratio is then determined in the scarce hydrogen situation of high-molecular weight hydrocarbon charging, the amount of sulphur, nitrogen and oxygen in the oil plant, the amount of polycyclic aromatic hydrocarbon, the type of catalyst system therefor and required transformation efficiency.Preferably will avoid providing in charging any a large amount of or remarkable excessive methyl alcohol, because under certain conditions, methyl alcohol has the trend of self interreaction.
Be preferably, the FCC-CHFC process is under low pressure used a kind of fluidized catalyst system, and does not need high pressure hydrogen.This fluidized catalyst system promotes quite cheap carbon-hydrogen micromolecular compound to contact expeditiously with heavy difficult cracking is intermolecular in the presence of the high surface area cracking catalyst.Reacting to each other of intermolecular hydrogen conversion, for example methylation reaction and catalytic cracking reaction carry out in the presence of the fluidized catalyst particle, and play diffusion/mass transfer control action kou and/or problem that heat transfer caused are reduced to minimum level.
The quite cheap carbon-hydrogen micromolecular compound that is easy in the petroleum refinery provide can be provided the FCC-CHFC process, for example, light gas fraction, light olefin, lower boiling liquid flow or the like, and especially can use methyl alcohol, methyl alcohol be a kind of no matter be as a kind of transportable product from the foreign natural gas conversion process, or quantitatively all be easy to provide as a kind of product by large-scale coal, shale oil or Tar sands gasification.The FCC-CHFC process also can be utilized carbon monoxide (using with water or such " contributor " of methyl alcohol), this kind gas is easy to be provided by the stack gas (or other unburnt process) that the refinery produces, or by coal, shale oil, Tar sands gasify to be provided.Carbon-hydrogen micromolecular compound can also carry out high efficiency circulation.
Example below implementing is for the present invention is described, rather than in order to limit the present invention.
Example 1
Prepare two kinds of catalyzer, according to the activity test of ASTM methods of test D-3907(microreactor) estimate its performance.These two kinds of catalyzer prepare with non-zeolite molecular sieve SAPO-5 and zeolite L Z-210.SAPO-5 is according to United States Patent (USP) 4,440,871 method preparation, and behind air roasting, just use.LZ-210(SiO 2With Al 2O 3Ratio be 9.0) then be according to the method preparation of No. the 82.211st, E.P.C publication.
Behind preparation SAPO-5, it in 100% water vapor, was handled 2 hours down at 760 ℃, with the influence of simulation practical application in cracking process.Then the LZ-210 component is carried out the LZ-210 that rare earth ion exchanged provides rare earth exchanged, wherein contains 9.9%(weight) rare earth ion (representing) with oxide compound.This rare earth ion exchanged is with a kind of 46.0%(of containing weight) the rare-earth chloride solution of rare earth element carry out, this rare earth component is with consisting of that oxide form is represented: 60.0% lanthanum (La 2O 3), 21.5% neodymium (Nd 2O 3), 10.0% cerium (CeO 2), 7.5% praseodymium (Pr 6O 11) and other rare earth element of about 1.0%.
The matrix of SAPO-5 and LZ-210 is with 90%(weight) silica/alumina, (sold by the Davison branch of W.P.Grace company, its commercial trade mark is Msub/110) and 10%(weight) the micro-crystal fiber extrusion aid be mixed and made into.This mixture is squeezed into 0.16 centimetre pelletizing, and about 16 hours at 110 ℃ air drying, and then under 760 ℃ in 100% water vapor deactivation 2 hours.At last the material of this water vapor deactivation is pulverized, and be sized to the particle of 60 to 200 orders (USS).
Respectively with 15%(weight) material of being selected and 85%(weight) matrix mix and prepare SAPO-5 and LZ-210 catalyzer.Before the preparation catalyzer, earlier LZ-210 was carried out the water vapor deactivation 2 hours at 760 ℃ in 100% water vapor.Then with the roasting 3 hours in 590 ℃ air of the mixture of finished catalyst.According to ASTM methods of test D-3907 and with ASTM methods of test D-3907, in a routine tests, each catalyzer is estimated through following 4 modifications.First modification is that the full boiling point that is defined as the product of gasoline products is 222 ℃.Second modification is that stripping is to carry out under 30 ml/min 23-27 minute behind the nitrogen of catalyzer.The 3rd modification is that transformation efficiency is the transformation efficiency of measuring, rather than the standard conversion of ASTM methods of test.The 4th modification be, used raw material has 24.0 ° api gravity and 179 ℃ initial boiling point (IBP) in test method, 581 ℃ full boiling point (fbp) and 11.8 UOP k-factor.
" transformation efficiency %(weight) " be the weight percentage transformation efficiency that records." gasoline %(weight) " be C 5Hydrocarbon to boiling point is lower than the weight percentage of 222 ℃ the hydrocarbon of hydrocarbon in product." gas %(weight) " is that those boiling points in product are lower than C 4The weight percentage of hydrocarbon of boiling point, weight percentage with charging represents, " coking %(weight) " be after carrying out the back stripping by ASTM methods of test D-2907, stay the weight percentage of the resistates on the used catalyst, represent with the percentage ratio of charging." C 4S%(weight) " be the weight percentage of Trimethylmethane, normal butane and butylene in the product.The The above results of representing for percentage ratio by weight below:
Catalyzer
SAPO-5 LZ-210
Transformation efficiency %(weight) 57.7 57.2
Gasoline %(weight) 37.2 41.4
Gas %(weight) 6.6 5.5
Coking %(weight) 3.9 3.1
C 4S%(weight) 10.0 7.33
Above result proves that SAPO-5 is active cracking catalyst, can provide in fact and the identical transformation efficiency of LZ-210 catalyzer that contains aluminosilicate zeolite, but provide different products distribution.
Example 2
In the cracking operation, use a kind of gas oil feedstocks of heavy vacuum gas oil that comprises to carry out the FCC-CHFC process.The characteristics of this vacuum gas oil are that api gravity (15.6 ℃) is 20.7, and molecular-weight average is about 400 ± 10, and boiling spread is between 371 ℃-593 ℃.Carbon-hydrogen micromolecular compound is a methyl alcohol, and its amount is a 10%(weight).Catalyzer contains SAPO-5, after being heated to about 538 ℃ ± 7 ℃, feeds in the riser tube FCC apparatus.Owing to added methyl alcohol, hydrocarbon product just has the selectivity of raising to motor spirit (hydrocarbon) product, the hydrocarbon fuel existence of the boiling spread that it is characterized in that wherein having boiling point to be lower than gas-oil feed.

Claims (18)

1, the cracking crude oil material is to produce the method for low boiling hydrocarbon, this method comprises and will be selected from the described crude oil material of raw gasline, cut gas oil, vacuum residuum, long residuum, synthetic crude and composition thereof or the boiling point hydrocarbon raw material at 216 ℃ to 982 ℃, temperature be 371 ℃ to 871 ℃ and pressure be 1.03 kilogram forces/centimetre 2To 7 kilogram forces/centimetre 2Condition under, contact with the catalyzer that comprises at least a silicoaluminophosphamolecular molecular sieve, this kind molecular sieve is characterised in that its calcined form, is that 500 mmhg, temperature are under 20 ℃ the condition at pressure, and the adsorption rate of Trimethylmethane is at least 2%(weight); With contain 0 to 99%(weight) inorganic oxide matrix.
2, according to the process of claim 1 wherein that described silicoaluminophosphamolecular molecular sieve is further characterized in that its calcined form, be 2.6 mmhg at pressure, temperature is under 22 ℃ the condition, to the adsorption rate of triethylamine greater than 5%(weight).
3, according to the process of claim 1 wherein that described silicoaluminophosphamolecular molecular sieve contains 0.1 to 20%(weight) at least a following positively charged ion: the H that is selected from +, &lt;math><msup><mi>NH</mi><msub><mi>+</mi></msup><mi>4</mi></msub></math> , II A family, III A family, III B family be to VII B family, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium and its mixture.
4, be hydrogen ion or the positively charged ion that forms hydrogen according to the process of claim 1 wherein that positively charged ion in the described silicoaluminophosphamolecular molecular sieve has a part at least.
5, according to the method for claim 4, the positively charged ion of wherein said formation hydrogen is that to be selected from be H at least +With
Figure 85109362_IMG1
In a kind of positively charged ion.
6, according to the method for claim 4, wherein this silicoaluminophosphamolecular molecular sieve is to be selected from SAPO-5, SAPO-11, SAPO-31, SAPO-37, SAPO-40, SAPO-41 and composition thereof.
7, according to the method for claim 6, wherein this aluminosilicophosphate is SAPO-5.
8, according to the method for claim 6, wherein this aluminosilicophosphate is SAPO-11.
9, according to the method for claim 6, wherein this aluminosilicophosphate is SAPO-31.
10, according to the method for claim 6, wherein this aluminosilicophosphate is SAPO-40
11, according to the method for claim 6, wherein this aluminosilicophosphate is SAPO-41.
12, according to the method for claim 1, wherein said aluminosilicophosphate is a kind of microporous crystalline silico-alumino-phosphate, its micropore is of uniform size and has approximately greater than the specific diameter of 3 dusts that the basic experience chemical constitution of this kind sial microcosmic salt when former synthesized form and anhydrous form is:
mR：（Si xAl yP z）O 2
" R " is illustrated at least a organic formwork agent that exists in the crystals microcellular system in the formula; The numerical value of " m " is 0.02 to 0.03; " m " represents every mole of (Si xAl yP z) O 2The mole number of existing " R "; Molar fraction when " x ", " y ", " z " represent respectively that silicon, aluminium and phosphorus exist with tetrahedral oxide, the described mark that rubs be on the ternary diagram of Fig. 1 of No. the 4th, 440871, United States Patent (USP) by the determined pentagon compositing range of these 5 points of A, B, C, D and E in.
13, according to the process of claim 1 wherein to have a kind of PO by described silicoaluminophosphamolecular molecular sieve &lt;math><msup><mi></mi><msub><mi>+</mi></msup><mi>2</mi></msub></math> 、AlO &lt;math><msup><mi></mi><msub><mi>-</mi></msup><mi>2</mi></msub></math> And SiO 2The three-dimensional microporous framework structure of tetrahedron element, the basic experience chemical constitution of its anhydrous form is:
mR：（Si xAl yP z）O 2
" R " is illustrated at least a organic formwork agent that exists in the crystals microcellular system in the formula; " m " represents every mole of (Si xAl yP z) O 2The mole number of existing " R " also has by 0 to 0.03 numerical value; " x ", " y " and " z " represent the molar fraction of the silicon, aluminium and the phosphorus that exist with the oxide compound portion-form respectively, described molar fraction be on Fig. 1 ternary diagram by in these 5 determined compositing ranges of point of A, B, C, D and E, described aluminosilicophosphate has a kind of X-ray powder diffraction figure of feature, under having at least, this kind diffractogram is listed in United States Patent (USP) the 4th, listed d-spacing in any one table in 440, No. 871 table I, III, V, VII, IX, X III, X VII, X XI, X XII or the XX V.
14, according to the method for right 1, wherein said catalyzer comprises 5 to 95%(weight) at least a inorganic oxide matrix component that is selected from clay, silicon-dioxide, aluminum oxide, silica-alumina, silicon-dioxide-zirconium white, silica-magnesia, aluminum oxide-boron oxide and aluminum oxide-titanium dioxide.
CN85109362.0A 1984-11-27 1985-11-26 Catalist for catalytic cracking and cracking method using a kind of molecular sieve Expired CN1004357B (en)

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