CN1007991B - With the hydrogenolysis that contains the alumo-silicate molecular sieve catalyzer - Google Patents
With the hydrogenolysis that contains the alumo-silicate molecular sieve catalyzerInfo
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- CN1007991B CN1007991B CN 85109634 CN85109634A CN1007991B CN 1007991 B CN1007991 B CN 1007991B CN 85109634 CN85109634 CN 85109634 CN 85109634 A CN85109634 A CN 85109634A CN 1007991 B CN1007991 B CN 1007991B
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- sapo
- catalyst
- weight
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- hydrogen
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- 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
-
- 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)
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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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
Abstract
Disclose the hydrogenolysis of using the catalyzer that contains alumo-silicate, this alumo-silicate is from No. 4440871, United States Patent (USP), and it is characterised in that its calcinated form is at ℃ following oxygen of absorption at least 4% (weight) of dividing potential drop 100 torrs and temperature-186.
Description
The method that the present invention relates to comprise the hydrocracking catalyst of special alumo-silicate molecular sieve and use these hydrocracking catalysts.
The document of relevant this class catalyzer and application method thereof is considerable.In a large amount of patents of some technical task, find out that easily why some technical field so attracts people's interest.The for example application of some zeolite in hydrocracking catalyst.The representative of this field patent be with hydrocracking in use the relevant patent of ZSM-type zeolite, it comprises: No. 3894934, United States Patent (USP) (ZSM-5), No. 3871993 (ZSM-5, ZSM-11, ZSM-12 and ZSM-21), No. 3702886 (ZSM-5), No. 3758403 (ZSM-5 combines with zeolite Y) and No. 3972983 (ZSM-20).
Though the above-mentioned patent in hydrocracking catalyst aspect the application ZSM type zeolite is important, uses these zeolites and does not still have commercial significance so far.Coml occasion major part concentrates on and further improves the basic hydrocracking technology about zeolite Y that occurred No. 3130007, United States Patent (USP) (be disclosed in) in the hydrocracking field.
Developed hydrocracking catalyst in many aspects based on y-type zeolite.The method in the following patent of being disclosed in can be used as the explanation of the whole bag of tricks that has proposed:
United States Patent (USP) discloses " the overstable y-type zeolite silico-aluminate of synthetic " for No. 3293192 (referring to No. 3594331, United States Patent (USP), it discloses Z-14HS is zeolite Y), its preparation method be the low Y zeolite of calcining basic metal content, with the alkaline solution that contains ammonium or compounded amino salt with calcinate carry out continuous alkali exchange until alkali content less than 1%(weight), calcine gained exchange product then.
Though, developed Y type hydrocracking catalyst widely, almost also do not develop fully new, based on the hydrocracking catalyst of the new molecular sieve component of development.This paradox, promptly lacking new catalytic material (although sizable economic benefit is arranged) is because the emphasis of coml hydrocracking work is a zeolite Y.Therefore, patent documentation is also recommended improved zeolite Y.
Now zeolite Y and as catalyzer the application in hydrogenolysis gains public acceptance., the state of the art that relates to zeolite Y and the application in hydrocracking catalyst thereof also is limited to ion exchange technique, aluminium abstraction technique, catalyst preparation technology and in general by the secondary treatment method of removing aluminium in the zeolite Y.
The difference of hydrocracking catalyst of the present invention and prior art and preparation method thereof is to use one group of novel non-zeolite molecular sieve, and it can be used separately, also can combine use with habitual catalyzer in the hydrogenolysis.These new non-zeolite molecular sieves have particular performances, and it can obtain to be different from the resulting products distribution of the catalyzer of being made by zeolite aluminosilicate.
Fig. 1 is comparative catalyst (catalyst A) and the petroleum naphtha fraction productive rate of catalyzer of the present invention (catalyst B) and the graph of a relation of transformation efficiency.
Fig. 2 is similar to Fig. 1, has just described catalyzer C of the present invention.
Fig. 3 is the RON(research octane number (RON) of the petroleum naphtha fraction of catalyst A and catalyst B) with the graph of a relation of transformation efficiency.
Fig. 4 is similar to Fig. 3, and that just describe is catalyzer C.
Fig. 5 is the heavy petrol fraction productive rate of catalyst A and catalyzer C and the graph of a relation of transformation efficiency.
Fig. 6 is the heavy petrol fraction productive rate of catalyst A and catalyst B and the graph of a relation of transformation efficiency.
Fig. 7 is the C of catalyst A and catalyzer C
5Different/the direct ratio of hydrocarbon and the graph of a relation of transformation efficiency.
Fig. 8 is the C of catalyst A and catalyzer C
6Different/the direct ratio of hydrocarbon and the function relation figure of transformation efficiency.
Fig. 9 is the C of catalyst A and catalyst B
5Different/the direct ratio of hydrocarbon and the function relation figure of transformation efficiency.
Figure 10 is the C of catalyst A and catalyst B
6Different/just the ratio of hydrocarbon and the function relation figure of transformation efficiency.
Figure 11 is different/just the ratio and the carbonatoms purpose function relation figure of catalyst A and catalyst B.
Figure 12 is the C of catalyst A and catalyzer C
3The function relation figure of productive rate and transformation efficiency.
Figure 13 is the C of catalyst A and catalyst B
3The function relation figure of productive rate and transformation efficiency.
The present invention relates to the application process of hydrocracking catalyst and this catalyst. This catalyst comprises the non-zeolite molecular sieve that will talk about below at least a, at least a hydrogenation component and arbitrarily a kind of the hydrocracking hydrocarbon feed is had the particle of traditional hydrocracking catalyst of catalytic activity, for example contains traditional hydrocracking catalyst particle of the typical zeolite aluminosilicate of usually using in above-mentioned hydrocracking catalyst. This class alumo-silicate molecular sieve of using is in the present invention summarized and is disclosed in No. 4440871, the United States Patent (USP), they are members of such class alumo-silicate molecular sieve, be that its calcinated form is depressed at the branch of-186 ℃ of temperature and 100 torrs, have and adsorb at least 4%(weight) the supplementary features of oxygen. Traditional catalyst component (catalyst that for example contains zeolite aluminosilicate) is characterized by the hydrocracking catalyst component, such as so far tradition application in hydrogenolysis, contains catalyst of various forms of y-type zeolites etc. The unique point of Catalyst And Method of the present invention is to use special alumo-silicate molecular sieve as catalyst in technical process, can generate the product mixtures that can not obtain with traditional hydrocracking catalyst.
The present invention relates to use the hydroconversion process (seeing aftermentioned for details) of the catalyzer that contains at least a alumo-silicate molecular sieve.Method for hydrogen cracking is by cracking high boiling hydrocarbon raw material and the unsaturates hydrogenation that makes in the raw material, and high boiling hydrocarbon feed is converted into more lower boiling product.
The condition for validity of (seeing: zeolite chemistry and catalysis, Jule A.Rabo, American Chemical Society, the 13rd chapter, 171 special topics (1976)) hydrogenolysis and enforcement thereof in this technical field has belonged to altogether to be known, and knows that they have several frequently seen type.Two kinds of types that are very familiar to are a segment type and two segment types.In a segment type (Unicracking-JHC or damp western hydrocracking) method, raw material wants pre-treatment to remove nearly all sulphur and nitrogen, for example realizes desulfurization and denitrogenation with hydrofinisher.Make the streams hydrocracking then in reactor in the presence of catalyzer, single-pass conversion is 40% to 70%.Unconverted hydrocarbon can recirculation after gas washing removes deammoniation and fractionation separates to go out converted product, until whole conversions.Two-stage method (Unicracking-JHC) is developed, and second section application that it provides is from the input charging as fractionation plant of the effluent of a segment type hydrogenolysis (by behind the washer of ammonia) and second hydrocracking reactor.Unconverted raw material so in the second hydrocracking reactor recirculation until whole conversions.Because in fact the catalyzer in second hydrocracking reactor works in the environment of no ammonia, therefore the transformation efficiency in this reactor can maintain higher level, 60-80% for example, and usually can under the temperature lower than first section reactor, transform.
Have been found that the products distribution that obtains when using products distribution that special alumo-silicate molecular sieve forms and not using above-mentioned alumo-silicate molecular sieve is different.Catalyzer of the present invention can use separately, also can with under effective hydrocracking condition, have active general hydrocracking catalyst and be used in combination.So far, the hydrocracking catalyst of prior art need be stood some loss in order to make specific process variable or product property (as octane value) reach optimizing.For example, when the application zeolite aluminosilicate is catalyst based, observe the improvement that improves the gasoline octane rating of the product that is indicated by isoparaffin and n-paraffin ratio, be accompanied by the decline of gasoline yield and feed stock conversion.As the index of high-octane rating product, therefore, increasing or descending of it is used as the index of gasoline product octane value to the ratio of different chain hydrocarbon and n-paraffin always.With respect to n-paraffin, the increase of isoparaffin amount is not obvious, the reduction of gasoline yield and feed stock conversion, even also not obvious increase is arranged, this commercial be crucial.The increase of (product contains at least 5 carbon atoms, and boiling point is lower than 185) isoparaffin and n-paraffin ratio is a particularly important in the petroleum naphtha fraction, because this fraction is generally no longer treated to improve its octane value.
The alumo-silicate molecular sieve of using among the present invention is selected from that class alumo-silicate molecular sieve that is disclosed in No. 4440871, the United States Patent (USP), and they be its calcinated form can also depress at-186 ℃ of temperature, 100 torr branches be adsorbed to few 4%(weight) the sort of alumo-silicate molecular sieve of oxygen.The essential characteristic of alumo-silicate calcinated form is to adsorb 2%(weight at least under 20 ℃ of temperature and dividing potential drop 500 torrs) Trimethylmethane.At the non-zeolite molecular sieve of this application, it is characterized in that preferably satisfying one of above-mentioned absorption index, its feature is that also their calcinated form adsorbs triethylamine under 22 ℃ of temperature, dividing potential drop 2.6 torrs amount is zero to less than 5%, preferably less than 3%(weight).
Alumo-silicate molecular sieve with feature of above-mentioned absorption index is selected from the alumo-silicate class that is disclosed in No. 4440871, the United States Patent (USP), is hereby incorporated by; To be described below simultaneously.The alumo-silicate molecular sieve that No. 4440871, United States Patent (USP) is the alumo-silicate of microporous crystalline, and its hole is uniformly, and has the specific diameter greater than about 3 dusts, and the basic experiment chemical constitution of its synthetic state and anhydrous form is:
mR：（Si
XAl
YP
Z）O
2
Wherein " R " represents at least a organic formwork agent that is present in the intracrystalline hole system; " m " represents every mole of (Si
XAl
YP
Z) O
2The mole number that has " R ", " m " value from 0.02 to 0.3; " X " " Y " and " Z " represent the molar fraction of the silicon, aluminium and the phosphorus that exist with tetrahedral oxide respectively, and described molar fraction must drop on by in the pentagonal compositing range that ABCD and E point are determined on the ternary diagram of the accompanying drawing 1 of No. 4440871, United States Patent (USP).The SAPO molecular sieve that No. 4440871, United States Patent (USP) also is known as has PO
+ 2, AlO
- 2And SiO
2The alumo-silicate of the three-dimensional microporous framework structure of tetrahedron element, its basic experiment chemical constitution when anhydrous form is:
mR：（Si
xAl
yP
z）O
2，
Wherein " R " representative is present at least a organic formwork agent in the crystal inner pore system; " m " represents every mole of (Si
xAl
yP
z) O
2The mole number that has " R ", " m " are worth from zero to 0.3; " X " " Y " and " Z " represent the molar fraction of the silicon, aluminium and the phosphorus that exist with oxide compound part (oxide moiety) respectively, above-mentioned molar fraction drops on by in the compositing range that A, B, C, D and E point limit on the ternary diagram of Fig. 1, above-mentioned alumo-silicate has the X-ray powder diffraction figure of feature, and this figure contains the d spacing of expression in any one table of table I, III, V, VII, IX, XII, X VII, X XI, XX III or XX V of No. 4440871, United States Patent (USP) below at least.In addition, such crystalline aluminium silicophosphate can be at sufficiently high temperature lower calcination, to remove some organic formwork agent at least that is present in the crystal inner pore system.
The alumo-silicate that No. 4440871, United States Patent (USP), usually be called " SAPO-n " in the text, as one type, promptly as " SAPO-n ", wherein n is the integer of a kind of specific SAPO of expression, has reported the preparation of specific SAPO in No. 4440871, the United States Patent (USP).Therefore catalyzer of the present invention will be called the catalyzer that contains " SAPO ", contain one or more SAPO of No. 4440871, United States Patent (USP) in the catalyzer with expression, catalyzer of the present invention has above-mentioned adsorb oxygen, adsorb isobutane and the characteristic of absorption triethylamine under conditions suitable simultaneously.Applicable SAPO class includes, but is not limited among the present invention: SAPO-11, SAPO-17, SAPO-31, SAPO-33, SAPO-34, SAPO-35, SAPO-40, SAPO-41, SAPO-44 and its mixture.
The above-mentioned feature of the SAPO that uses among the present invention is relevant with the adsorpting characteristic of SAPO, and this SAPO is through synthesizing aftertreatment (for example calcining or chemical treatment) to remove the quite most of template " R " that exists owing to synthetic.Although specific herein SAPO is relevant with the characterization of adsorption of its calcinated form to the adsorpting characteristic of oxygen, Trimethylmethane or triethylamine, but the present invention also comprises the SAPO that uses non-incinerating or improvement certainly, these SAPO have above-mentioned adsorpting characteristic at its calcinated form or improved form since the non-incinerating SAPO that uses under effective hydrocracking condition in the inventive method will be calcined on the spot or hydrothermal treatment consists to make it to have one or more characterization of adsorptions in oxygen, Trimethylmethane and the triethylamine.So SAPO can become the form with above-mentioned characterization of adsorption at on-the-spot disposal, this also is a scope of the present invention.For example, though the calcinated form of SAPO-11 has the characteristic of adsorb isobutane, the SAPO-11 of synthetic form, because the template " R " of existence when synthetic is arranged, so there is not the characteristic of above-mentioned adsorb isobutane.Therefore, when talking about its calcinated form and have the SAPO of specific characterization of adsorption, be not the SAPO that does not use former synthetic form, the latter can have above-mentioned characterization of adsorption after former ground warp calcining, hydrothermal treatment consists and/or other processing (as: with the ion-exchange of suitable atoms).
Can see that as top discussion this class SAPO can obtain to use traditional products distribution that hydrocracking catalyst did not have.So far, the hydrocracking catalyst of prior art (containing zeolite) in order to reach the optimizing of special process variable or product property (for example octane value of gasoline product), always is accompanied by the decline of gasoline yield and/or transformation efficiency usually.Use catalyzer of the present invention and can reduce these losses.People wish that the ratio of isoparaffin and n-paraffin in the gasoline product increases, because this expression is the product of higher octane.
Except the octane value that has improved above-mentioned gasoline product, the improvement of octane value also might be used base metal catalysts in technology, and in the past, need obtain the high-octane rating product with noble metal catalyst.Because base metal catalysts more can tolerate pollutent, organic compounds containing sulfur in the charging usually, therefore, the invention provides the more resistant to pollution catalyzer (in the past, will follow loss of octane number with base metal catalysts) that does not have loss of octane number.When the SAPO that uses with the present invention when noble metal catalyst used, the present invention can further improve the isoparaffin content of gasoline product.
Catalyzer of the present invention can with traditional use of hydrocracking catalyst, also can be optionally and application of zeolite aluminosilicate component.The zeolite aluminosilicate component of this class catalyzer can be any silico-aluminate that was used as the hydrocracking catalyst component in the past, for example various forms of zeolite Y.As the hydrocracking catalyst component, the representative of disclosed zeolite aluminosilicate so far is that zeolite Y (comprises the stable zeolite Y of water vapor, as overstable zeolite Y), X zeolite, zeolite beta (No. 3308069, United States Patent (USP)), zeolite KZ-20(United States Patent (USP) 3445727), No. 3415736, zeolite ZSM-3(United States Patent (USP)), faujusite (faujasite), LZ-10(English Patent 2014970, June 9 nineteen eighty-two), ZSM type zeolite, erionite, mordenite, offretite, chabazite, FU-1-type zeolite, NU-type zeolite and composition thereof.Usually with Na
2O content is less than about 1%(weight) traditional cracking catalyst for well.
Think that herein applicable y-type zeolite includes, but is not limited to those disclosed zeolite Y component in following United States Patent (USP), the patent No. is: 3130007,3835032,3830725,3293192,3449070,3839539,3867310,3929620,3929621,3933983,4058484,4085069,4175059,4192778,3676368,3595611,3594331,3536521,3293192,3966643,3966882 and 3957623.
The another kind of zeolite catalyst of Ying Yonging is " LZ-210 " herein, and it has done to introduce in E, P, C can be for reference.The publication that publish June 29 nineteen eighty-three also is incorporated herein by reference for No. 82211.In one embodiment, the mol ratio of silicon oxide and aluminum oxide is between about 7 to about 11, is preferably in about 8 to about 10.The hydrocracking catalyst that contains LZ-210 is disclosed in serial No. 490951 of common unsettled U.S. of submitting to May 2 nineteen eighty-three, is incorporated herein by reference in the lump at this, and this LZ-210 can be used as optional, traditional hydrocracking component at this.
Term " ZSM-type " zeolite at those zeolites that are used to refer to use buzz word " ZSM-n " name in the art, is an integer at this " n " usually.ZSM type silico-aluminate includes, but is not limited to: ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other similar material.
ZSM-5 has detailed introduction in No. 3702886, United States Patent (USP) and Re29948 number.All specification sheetss of these patents, especially wherein the X-ray diffractogram of disclosed ZSM-5 is hereby incorporated by.
United States Patent (USP) has been introduced ZSM-11 No. 3709979.The X-ray diffractogram of this specification sheets, especially ZSM-11 is hereby incorporated by.
United States Patent (USP) has been described ZSM-12 No. 3832449.Specification sheets and wherein disclosed X-ray diffractogram are hereby incorporated by.
United States Patent (USP) has been described ZSM-23 No. 4076842.The detailed description of the X-ray diffractogram of its whole contents and disclosed zeolite is hereby incorporated by.
United States Patent (USP) has been introduced ZSM-35 No. 4016245.The specification sheets and the X-ray diffractogram thereof of this zeolite are hereby incorporated by.
United States Patent (USP) has been mentioned ZSM-38 No. 4046859 especially.The specification sheets of this zeolite and characteristic X-ray diffractogram thereof are incorporated herein by reference.
United States Patent (USP) has described ZSM-48 in greater detail No. 4423021.The specification sheets of this zeolite and characteristic X-ray diffractogram thereof also are hereby incorporated by.In addition, No. 4061724, crystalline silicate such as Silicalite(United States Patent (USP)) can with use of SAPO of the present invention.
Catalyzer of the present invention comprises the SAPO of at least a above-mentioned sign, a kind of hydrogenation catalyst (component) and one or more traditional hydrocracking catalyst components random, that comprise zeolite aluminosilicate component and hydrogenation/cracking component (as nickelous sulfide, tungsten sulfide or the like).The products distribution that the relative quantity of SAPO component and traditional hydrocracking component (if any) will depend on the hydrocarbon feed of selection at least in part and therefrom want to obtain, but in all cases, use the SAPO of at least a significant quantity.When using traditional hydrocracking catalyst (THC) component, THC is generally about 1: 10 to about 500: 1 with the relative weight ratio of SAPO, wishes at about 1: 10 to about 200: 1, and is better between about 1: 2 and about 50: 1, is preferably about 1: 1 to about 20: 1.
SAPO and THC(are if any) can carry out ion-exchange, dipping and/or occlusion and/or thermal treatment with the positively charged ion of selecting, these processing are carried out after can or joining them in one or more inorganic oxide matrix components individually or simultaneously before or after mixing mutually.When SAPO used ion-exchange, it preferably and the positively charged ion that is made of hydrogen (NH for example
+ 4, H
+, quaternary ammonium cation or the like) exchange.It partly is the positively charged ion (hydrogen-forming cation) that is made of hydrogen that the positively charged ion of SAPO preferably has at least.
If SAPO and THC(are the words that have) ion-exchange, dipping and/or occlusion can be undertaken by its cationic solution with a selection is contacted, THC or SAPO can be through Overheating Treatment, positively charged ion is selected from ammonium, II A family, III A family, the III B positively charged ion to VII B family and rare earth, and rare-earth cation is selected from Ce, La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and its mixture.The definite character of rare-earth cation and SAPO mutual relationship and they are to containing the SAPO activity of such catalysts and/or optionally influencing also not fully aware of at present.Because ion-exchange and/or dipping, positively charged ion (for example rare-earth cation) might replace at least a portion and be present in positively charged ion among SAPO and/or the THC at first.The significant quantity that positively charged ion can exist is by the weight of initial SAPO and/or THC, for about 0.1% to about 20%(weight), be generally about 0.5% to about 10%(weight).
Hydrocracking catalyst of the present invention contains the hydrogenation catalyst (component) that is generally used in hydrocracking catalyst significant quantity, at least a.The hydrogenation component generally is selected from the hydrogenation catalyst of being made up of the metal of one or more VI families and VIII family, comprises the salt, complex compound and the solution that contain above-mentioned metal.Hydrogenation catalyst preferably is selected from by at least a that form or by at least a metal of forming, salt and its complex compound in Ni, Mo, Co, W, Ti, Cr and its mixture in Pt, Pd, Rh, Ir and its mixture.
As what recognized in the art, precious metal and base metal generally shall not be applied in the same catalyst system of hydrocracking catalyst, though this situation and being not precluded within outside the scope of the present invention.Be meant the metal of elementary state or oxide compound, sulfide, halogenide, carboxylate salt or the like other form about the metal of tool catalytic activity.
The existence of the hydrogenation catalyst of significant quantity makes hydrocracking catalyst have hydrogenating function.When hydrogenation catalyst is precious metal, its amount is generally about 0.05% to about 1.5%, this is by the total weight of the catalyzer that comprises the matrix weight that THC, tackiness agent maybe may exist, (below will discuss), but also may use the significant quantity that exceeds this scope.Although can use weight above 1.5%() significant quantity,, the recommended significant quantity of hydrogenation component is about 0.3% to about 1.2%(weight).(represent) that when hydrogenation catalyst is base metal the significant quantity of non-noble metal oxide usually will be for about 1.0% to about 30%(weight with oxide compound) or more (based on the gross weights of catalyzer), also can use though exceed the significant quantity of this scope.
The last form of the hydrogenation component of hydrocracking catalyst can be a metal oxide still in this not strict restriction, and metallic sulfide or other have the form of catalytic activity.Because sulphur generally is present in the pending hydrocarbon feed, therefore since the actual form of some hydrogenation component of situ reaction probably to small part be sulfide.
When being used as the hydrogenation component by precious metal, catalyzer activates in air usually, reduces in nitrogen atmosphere then.When using base metal, catalyzer is also handled with sulphur compound usually.
There are many methods to join the hydrogenation component in total catalyst composition.They can be added in SAPO component, the THC component (if any), can be added in any other metal oxide component, also can be added in its mixture.In selectable method, a plurality of hydrogenation components (two or more) can join in the composition of catalyzer with powder type.They can add by grinding altogether, dipping, ion-exchange or occlusion, thereby one or more hydrogenation components can join among SAPO and/or the THC.For example, before composition is at last by calcining, by with common grinding, dipping or the precipitation of the composition of catalyzer each component or its each component, metallic sulfide, metal oxide or its water-soluble salt can be added wherein.In the method that selection can be provided, the method by the aqueous solution, alcoholic solution, hydrocarbon solution or other non-aqueous solution with soluble compounds or its precursor flood can join these components in the Manufactured particle.When the hydrogenation component is base metal, dipping or to grind altogether be the method for recommending, and when making the hydrogenation component with precious metal, ion-exchange techniques is better.
Though the hydrogenation component can be with oxide form and SAPO and/or THC(if having) component mixes, and it is not common situation.They generally add with metal-salt, and this metal-salt can thermal transition become corresponding oxide compound in oxidizing atmosphere, perhaps be reduced into metal with hydrogen or other reductive agent.As mentioned above, body (as dithiocarbonic anhydride, hydrogen sulfide, hydrocarbon mercaptan, elementary sulfur or the like) reaction of giving of composition and sulphur can reach sulfuration.Above-mentioned oxidation or sulfidation are generally carried out on catalyst composition; this catalyst composition partly dry (on demand), compressing tablet, granulation, push with tackiness agent or matrix; or be shaped with other method; and at last more than 600 °F, general at the temperature lower calcination more than 800.
In the art, as you know, hydrocracking catalyst generally uses with a kind of binder substance, perhaps resembles common theory, uses with inorganic oxide matrix, and this inorganic oxide matrix can be an inert, also can be catalytic activity.For example adaptable inorganic matrix has silicon oxide, aluminum oxide, silica-alumina, silicon oxide-zirconium white, silicon oxide-magnesium oxide, zirconium white-boron oxide, aluminium oxide-titanium oxide or the like and composition thereof.Inorganic oxide not necessarily often uses, if use, its amount is for about 5% to about 95%(weight), be preferably about 10% to about 80%(weight), the total weight of pressing hydrocracking catalyst.
The term relevant " crude oil material " with hydrogenolysis, be meant an any crude oil material or a part wherein at this, it comprise by the various stock oils of common oil field or offshore oil field exploitation by first, secondary or tertiary recovery whole crude and by the plurality of raw materials oil of gained." crude oil material " also can obtain " synthetic crude " from coal, shale oil, Tar sands and pitch earth.Crude oil material can be original oil (straight run), also can be the synthetics through fusion.Because in many hydrocracking operations, sodium-chlor is a kind of poisonous substance as everybody knows, therefore above-mentioned crude oil material is wanted desalination before use usually.In addition, the various components that term " crude oil material " also comprises crude oil (up to the present, the crude oil component is generally as raw material or possible charging) and comprise cut gas oil, heavy vacuum gas oil, vacuum gas oil, normal pressure and decompression residual oil, synthetic crude, fine coal, surpass the fraction of gasoline boiling range that these cuts generally comprise and contain greater than the compound of about 11 carbon atoms and their mixture.
In method for hydrogen cracking, the general boiling point of the hydrocarbon feed of the hydroeracking unit of packing into surpasses 300 °F, and is better between about 400 °F to 1200 °F, is preferably between about 400 °F to about 900 °F.The hydrocarbon charging can be obtained by above-mentioned many sources, comprises fractionation, hydrocracking, pyrolysis method of catalytic cracking method, pyrogenic process, crude oil or the like.So that gasoline output when reaching maximum value, the full boiling point of industrial general raw material is not more than about 800 °F at present when implementing hydrogenolysis.In general, boiling range from about 300 to 800 catalytic cracking light cycle oil or straight-run light gas oil or its mixture as raw material.Material can be in hydrofinisher pre-treatment to reach hydrodenitrification and/or hydrogenating desulfurization.The sulfur-bearing scope that exists with hydrogen sulfide in the charging can be up to 0.1 to 3%(weight); Nitrogen content in the ammonia form can be up to 4000ppm or more.Temperature, space velocity and other process variable can control to and can compensate nitrogen to the active influence of hydrocracking catalyst.In the hydrocracking reaction district, raw material contacts with hydrocracking catalyst in the presence of the compound of hydrogenous gas and/or generation hydrogen.In hydrocracking process, hydrogen is consumed, and excessive hydrogen generally is retained in reaction zone.It is comparatively favourable that the ratio of hydrogen that uses and oil (charging) is at least 1000 standard cubic foot hydrogen/every barrel of charging (SCFB), also can preferably use about 4000 to 12000SCFB up to 20000 SCFB.Generally operate under high temperature and high pressure in the hydrocracking reaction district.Total hydrocracking pressure be generally about 400 to about 4000 pounds/square inch (gauge pressures) (Psig), be preferably about 500 to 2000psig.Hydrocracking reaction is thermopositive reaction, and temperature is along the direction of catalyst bed and raise.Therefore the temperature in hydrocracking reaction district can be than low 10 to 40 of temperature out.Hydrocracking catalyst bed medial temperature is about 450 °F to 800 °F, depends on whether there is NH
3Aging conditions with catalyzer.In hour liquid space velocity (LHSV) be generally 0.2 to 5 feed volume/catalyst volume hour, be preferably 0.25 to 4LHSV.
Following example can be used for illustrating the application of hydrocracking catalyst of the present invention and method, but is not limited to these examples.
Experimental procedure
Prepare hydrocracking catalyst by the method for introducing in the following example, and test its effectiveness as hydrocracking catalyst.These catalyzer are used as hydrocracking catalyst in first section hydrocracking.
With hydrocarbon feed (the gas oil feedstocks boiling range about 332 °F to about 853 °F (ASTM methods of test D-2887), and contain the sulphur of the 5000ppm that has an appointment and the nitrogen of 2000ppm) contact with the catalyzer of selecting for use and estimate the catalyzer of selecting for use in the hydrocracking.The density of raw material is 0.8341 gram per centimeter at 60 °F
3The nitrogen (with the TERTIARY BUTYL AMINE form) of the sulphur of 0.5 weight % (with the thiophene form) and 0.2 weight % is joined in the raw material, make raw material contain sulphur and nitrogen, wherein, weight % is based on the gross weight of raw material.The about 1450psig of pressure, temperature about 685 °F to about 709 and the little hourly space velocity of LHSV(liquid) carry out hydrocracking process about 1.7 times.It is about 8000 standard cubic foots/every barrel of hydrocarbon feed that hydrogen is introduced ratio.
The raw material selected for use introduced carry out the hydrocracking experiment in the stainless steel reactor that axial temperature meter jack is arranged.The thermocouple monitoring of temperature in the reactor in the jack.Catalyzer is the extrudate form, is loaded in the reactor, and mixes so that the local superheating position of reactor reaches minimum with quartzy small pieces.
The hydrocarbon feed that uses in the following example is a kind of gas oil, its IBP(initial boiling point) be 332 °F, the FBP(full boiling point) be 853 °F, api gravity (American Petroleum Institute's api gravity index) is 37.9.Total nitrogen content is less than 0.1%(weight in the raw material).The chemical analysis results of raw material is:
Percent by volume
Aromatic substance total amount 24.7
Monocyclic aromatics 19.0
Bicyclic aromatic compound 3.1
Three cyclophane compounds of group 1.2
Percent by volume
Fourth Ring aromatic substance 0.6
Five rings aromatic substance 0.8
Saturates total amount 75.4
Comparative catalyst (catalyst A) and as follows by the preparation method of two kinds of catalyzer of the present invention (catalyst B and catalyzer C).Except as otherwise noted, all weight is by anhydrous calculating.
With LZ-210(zeolite aluminosilicate) the preparation catalyst A.LZ-210 is by No. 82211 preparations of disclosed E.P.C. publication, its SiO
2With Al
2O
3Than being 9.0, this LZ-210 handled 1 hour in 600 ℃ 100% water vapor, and with every pound of NH
4NO
3(with 10%(weight) aqueous solution provides) ratio of 1 pound of LZ-210 refluxed 1 hour, to carry out the ammonium exchange.Mix 140 gram LZ-210 and 60 gram pseudo-boehmite aluminum oxide (with 4.2 milliliters of concentrated nitric acid peptizations in 60 ml waters), pulverized this mixture then 10 minutes, catalyst A is shaped.Mixture is configured as 1/16 inch extrudate, and drying is 10 hours under 100 ℃, calcines 2 hours in 500 ℃ of air again.Calcining under 500 ℃ is a proceed step by step, earlier with more than one hour catalyzer is heated to 220 ℃, then 220 ℃ of following heatable catalysts 1.5 hours, with more than one hour catalyzer is warmed up to 500 ℃ from 220 ℃ again, at last 500 ℃ times heating 2 hours.With incinerating extrudate and Ni(NO
3)
26H
2O and ammonium metatungstate solution mix, and make the hole of incinerating extrudate obtain filling, the dry again mixture that obtains.The catalyst A that makes at last contains the various oxide compounds of following weight percentage: 5%NiO, 20%WO
3, 52.5% LZ-210 and 22.5% aluminum oxide.NiO and WO in the catalyst A
3Chemical analysis results be NiO 4.7 weight % and WO
320.8 weight %.
In the preparation of hydrocracking catalyst, catalyst B is with SAPO-11 and LZ-210 preparation.According to the routine 17(of No. 4440871, United States Patent (USP) be dissolution time be 24 hours) preparation SAPO-11, and use with former synthetic form.The LZ-210 that uses in LZ-210 zeolite and the catalyst A is identical.Grind the LZ-210 zeolite aluminosilicate that 15.0 gram SAPO-11 and 105 grams are used in catalyst A, prepare catalyst B.Will be at 100 centimetres
3(c.c) contain 42.4 gram ammonium metawolframates and 33.93 gram Ni(NO in the water
3)
26H
2The solution of O adds in SAPO-11 and the LZ-210 mixture.Pseudo-boehmite aluminum oxide (30.0 gram, be dissolved in 60 ml waters with 4.2 milliliters of concentrated nitric acid epoxy glues) is added in the said mixture, and extruding obtains mixture, the extrudate size is 1/16 inch again.Extrudate is dry and resemble under 500 ℃ to the catalyst A narration and calcine.The catalyst B that makes contains the various oxide compounds of following weight percentage: 5.0%NiO, 20%WO
3, 52.5%LZ-210,7.5%SAPO-11 and 15%Al
2O
3NiO and WO in the catalyst B
3The chemical analysis value be: NiO 4%(weight) and WO
316%(weight).
Use SAPO-34 and LZ-210 and prepare catalyzer C with the preparation catalyzer.Method by 32 to 38 narrations of the example in No. 4440871, the United States Patent (USP) prepares SAPO-34.The LZ-210 that LZ-210 uses when being the preparation catalyst A through identical steam-treated and ammonium exchange.Catalyzer C can make by mixing 25.08 gram SAPO-34 and 175 gram LZ-210.This mixture was ground 15 minutes, and add that 53.8 grams use in catalyst B, through the aluminum oxide of above-mentioned peptization.The mixture that obtains was mixed 15 minutes.In mixture, add entry again, the formation mixture of can extruding, the extrudate size is 1/16 inch.With its mix with 53 centimetres
3Contain 19.39 gram Ni(NO in the water
3)
26H
2The solution of O and 24.2 gram ammonium tungstates is full of the hole of incinerating extrudate.Dry then extrudate and resembling under 500 ℃ is above-mentionedly calcined described catalyst A.The weight percentage that the catalyzer C that makes contains various oxide compounds is as follows: 5%NiO, 20%WO
3, 52.5% LZ-210,7.5% SAPO-34 and 15% aluminum oxide.Among the catalyzer C to NiO and WO
3The chemical analysis value be: NiO 4.99%(weight) and WO
320.32%(weight).
Example 4 to 6
Example 1 to 3(catalyst A, B and C) the middle catalyzer for preparing, a series of transformation efficiency (Table A of face, B and C as follows) is estimated by above-mentioned step as hydrocracking catalyst.Analyze various products, and adopt ASTM report " the pinking feature of pure hydro carbons ", technology discloses the octane value of listing in No. 225 (1958), utilizes C
5And C
6The volume averaging value of product is calculated the MON(motor-method octane number of petroleum naphtha) and the RON(research octane number (RON)).The compound that utilization records in the petroleum naphtha fraction calculates MON and RON, and it comprises following component: 2-methylbutane, Skellysolve A, 2, the 3-dimethylbutane, 2-methylpentane, 3-methylpentane, normal hexane, methylcyclopentane, 2,4-dimethylbutane, hexanaphthene and benzene." transformation efficiency " is that material changes into the weight percentage that boiling point is lower than 420 products.In Table A, B and C, reported following product (being expressed as the weight percentage of raw material): " %C
1To C
4"=contain 1 to 4 carbon atom product; " %C
3"=contain three carbon atoms product; " %C
5185 of to "=containing the product of at least 5 carbon atoms, boiling point is lower than 185 °F; " C185-420 "=product boiling point is from 185 °F to 420 °F; " C
5420 of to "=at least 5 carbon atoms of product, boiling point is lower than 420 °F.C
5, C
6, C
7, C
8And C
9Product be reported in below.Every kind of situation is measured following product: " C
5"=Skellysolve A and 2-methylbutane; " C
6"=normal hexane, 2,3-dimethylbutane, 2-methylpentane and 3-methylpentane; " C
7"=normal heptane, 2-methyl hexane, 3-methyl hexane and 2, the 4-dimethylpentane; " C
8"=octane, 2,2,4-dimethylhexane, 2,3-dimethylhexane, 2-methylheptane, 3,4-dimethylhexane and 3-methylheptane; " C
9"=positive nonane, 2,4-dimethyl heptane, 2,6-dimethyl heptane, 2,5-dimethyl heptane, 4-methyloctane, 2-methyloctane and 3-methyloctane.Above-mentioned product is base in weight.Measure various products with the simulation distil of describing in the ASTM test method(s) 2887.
The products distribution that will obtain with catalyst A compare with the products distribution of utilizing catalyst B and C to obtain, illustrate, when similar transformation efficiency, obtain petroleum naphtha fraction (C by catalyzer of the present invention
5185 of to) octane value has improvement.In addition, for catalyst B and C, C
5And C
6Different/positive the ratio of hydrocarbon has raising.Because isoparaffin has higher octane value, so the product that obtains with catalyst B and C has improved the octane value that calculates.
The data of Table A, B and C are plotted on Fig. 1 to 13, these data declarations in hydrogenolysis, use the benefit that catalyzer of the present invention obtained.Fig. 1 and 2 is petroleum naphtha productive rate (C
5-185 °F) with transformation efficiency concern aspect, the comparison diagram of catalyst A, B and catalyzer C.Compare with using the resulting product of comparative catalyst A, catalyst B and catalyzer C generate petroleum naphtha product similar or higher yields.Fig. 3 and Fig. 4 have compared the calculating RON(research octane number (RON) of the petroleum naphtha fraction that obtains with catalyst A, B and C).Compare with the petroleum naphtha fraction that produces with catalyst A, catalyst B and C produce the petroleum naphtha fraction of higher RON value.Fig. 5 is at heavy petrol fraction (C
5420 of to) fasten the pass of productive rate and transformation efficiency, the comparison diagram of catalyst A and catalyzer C, and shown that comparative catalyst generates more heavy petrol product.The attach most importance to aspect that concerns of gasoline fraction productive rate and transformation efficiency of Fig. 6, the comparison diagram of catalyst A and catalyst B.Surprised is, applications catalyst B, and heavy petrol fraction productive rate and comparative catalyst A are similar, and the RON of petroleum naphtha fraction is improved.Fig. 7,8,9 and 10 has compared the C that produces with catalyst A, B and C
5And C
6Different/the direct ratio of hydro carbons.In each case, compare with the product that is produced by catalyst A, the product that catalyst B and C produce all has higher different/direct ratio.Figure 11 is by C
5, C
6, C
7, C
8And C
9Different/the direct ratio of hydrocarbon and the funtcional relationship of carbonatoms are to the comparison diagram of catalyst A and catalyst B.The product that applications catalyst B obtains demonstrates C
5, C
6, C
7, C
8And C
9Therefore different/direct ratio that the hydrocarbon tool is higher has shown the product of higher octane value.Figure 12 and 13 is for catalyst A, B and C, its C
3The graph of a relation of product productive rate and transformation efficiency.With comparison shows that of catalyst A, the C of catalyzer C
3Product slightly increases, and the C of catalyst B
3The productive rate of product is similar to catalyst A.
The above results explanation applications catalyst B and catalyzer C have improved the RON of petroleum naphtha fraction, have increased C
5To C
9Different/the direct ratio of product and the productive rate of petroleum naphtha and heavy petrol fraction are constant substantially or increase arranged.Therefore, application contains the of the same race catalyzer of the catalyzer of SAPO than no SAPO component, and the octane value of resulting petroleum naphtha fraction increases.These results also show, catalyst B (containing SAPO-11) contains SAPO-34 being better than catalyzer C(aspect the octane value that improves the petroleum naphtha product), and do not have the gasoline yield loss.The characteristics of SAPO-11 are adsorb isobutane and SAPO-34 does not have this characteristic, and therefore, SAPO-11 belongs to recommend the SAPO that uses in catalyzer of the present invention.
Example 7
Use SAPO-11 and prepare catalyzer, with the hydrocracking that catalyzer of the present invention is described and the functional performance of dewaxing.The method of describing by the example 18 of No. 4440871, United States Patent (USP) prepares SAPO-11, is last di-n-propylamine and Al
2O
3Mol ratio be 1.0 to 1.The concrete preparation process of catalyzer is: 150 gram SAPO-11 are mixed to form extrudable mixture (slurry) with the water of 100 gram Kelvin (Kaiser) intermediate density aluminum oxide and q.s.This mixture is squeezed into 1/16 inch extrudate and 100 ℃ of air dryings 16 hours.Then extrudate was calcined 2 hours in 480 ℃ of air.Again with extrudate (153 gram) with contain 40.0 gram Ni(NO
3)
2, 6H
2150 milliliters of aqueous solution (filling up hole) of O and 48.8 gram ammonium metawolframates.Then mixture was calcined 2 hours down 100 ℃ of following dryings 16 hours and at 480 ℃.The catalyzer that makes contains (being expressed as oxide weight percentage ratio): 5%NiO, 23%WO
3, 36%SAPO-11 and 36% Al
2O
3NiO and WO
3The chemical analysis value be: NiO 5.4% and WO
323.0%.
Be in total pressure that 2000psig, liquid hourly space velocity (LHSV) are 1, hydrogen flow rate is the 10000SCFB(standard cubic feet per barrel) be to contact with hydrogen by the raw material of selecting for use under about 700 to 840 condition to estimate this catalyzer with temperature.Collect and estimate boiling point and be lower than 600 product, and provide conversion values according to these products.The raw material of using in the present embodiment is a kind of vacuum gas oil, its IBP(initial boiling point) be 560 °F, the FBP(full boiling point) be 1148 °F (both determine with ASTM methods of test D-2887), api gravity is 22.3, pour point is greater than 95 °F.The physics and the chemical property of raw material are as follows:
Weight percentage
Paraffinic hydrocarbons 24.1
Weight percentage
Mononaphthene 9.5
Polynaphthene 8.7
Monocyclic aromatics 13.3
Bicyclic aromatic compound 9.3
Three cyclophane compounds of group 4.3
Fourth Ring aromatic substance 2.7
Five rings aromatic substance 0.7
Collect reactor effluent, and change into the umber of the charging (by weight) that boiling point is lower than 600 products with determination of simulated distillation.Transformation efficiency is expressed as feedstock conversion and becomes boiling point to be lower than the weight percentage of 600 products.During collecting, keep the effluent liquid temperature at about 130 °F, by the pour point of ASTM methods of test D-97-66 assaying reaction device effluent liquid.
Transformation efficiency and pour point are as follows:
Temperature (°F) the transformation efficiency pour point (°F)
700 7.52 85
724 9.84 80
749 17.95 70
769 30.06 55
788 41.60 25
797 36.64 35
788 29.89 40
788 33.74 45
807 43.64 30
Temperature (°F) the transformation efficiency pour point (°F)
821 45.12 30
822 45.50 30
840 56.88 20
The feedstock conversion of above-mentioned data declaration higher in the presence of hydrogen becomes more lower boiling product, illustrates that also above-mentioned product compares with starting raw material and have lower pour point.
Claims (31)
1, the method of processing crude oil material in the presence of hydrogen, it is characterized in that, it is 450 °F to 800 °F that this method is included in medial temperature, pressure is under the condition of 400psig to 4000psig, crude oil material with 400 to 1200 of boiling ranges, contact with conversion catalyst with hydrogen, the liquid hourly space velocity of hydrocracking is 0.2-5 feed volume/catalyst volume hour, hydrogen is 1 to the ratio of crude oil material, 000-20,000 standard cubic foot/every barrel of crude oil material, above-mentioned conversion catalyst comprises the alumo-silicate molecular sieve SAPO of No. 4440871 disclosed nonzeolites of at least a United States Patent (USP), at least a pt that is selected from, pd, Rh, Ru, Ni, W, Mo, Co, Ti, hydrogenation component in Cr and its mixture, and the activated traditional hydrocracking catalyst THC that chooses any one kind of them, the weight ratio of THC and SAPO is 1: 10 to 500: 1, contain at least a inorganic oxide matrix component in addition, above-mentioned SAPO is characterised in that, the oxygen of its calcinated form absorption at least 4% (weight) when dividing potential drop 100 torrs and temperature-186 ℃.
2, the method of processing crude oil material in the presence of hydrogen, it is characterized in that, it is 450 °F to 800 °F that this method is included in medial temperature, pressure is under the condition of 400psig to 4000psig, crude oil material with 400 to 1200 of boiling ranges, contact with conversion catalyst with hydrogen, the liquid hourly space velocity of hydrocracking is 0.2-5 feed volume/catalyst volume hour, hydrogen is 1 to the ratio of crude oil material, 000-20,000 standard cubic foot/every barrel of crude oil material, above-mentioned conversion catalyst comprises the alumo-silicate molecular sieve SAPO of No. 4440871 disclosed nonzeolites of at least a United States Patent (USP), at least a pt that is selected from, pd, Rh, Ru, Ni, W, Mo, Co, Ti, hydrogenation component in Cr and its mixture, and the activated traditional hydrocracking catalyst THC that chooses any one kind of them, the weight ratio of THC and SAPO is 1: 10 to 500: 1, contain at least a inorganic oxide matrix component in addition, above-mentioned SAPO is characterised in that, its calcinated form adsorbs 2%(weight at least when 20 ℃ of dividing potential drop 500 torrs and temperature) Trimethylmethane.
3, in the presence of hydrogen and a kind of conversion catalyst, the processing boiling point is higher than the crude oil material of petroleum naphtha fraction, in the method that produces light gasoline fraction, it is characterized in that, the process conditions that this improvement comprises is 450 to 800 of medial temperatures, under the condition of pressure 400psig to 4000psig, the crude oil material that boiling range is higher than petroleum naphtha, contact with conversion catalyst with hydrogen, the liquid hourly space velocity of hydrocracking is 0.2-5 feed volume/catalyst volume hour, hydrogen is 1 to the ratio of crude oil material, 000-20,000 standard cubic foot/every barrel of crude oil material, above-mentioned conversion catalyst comprises the alumo-silicate molecular sieve SAPO of No. 4440871 disclosed nonzeolites of at least a United States Patent (USP), at least a Pt that is selected from, Pd, Rh, Ru, Ni, W, Mo, Co, Ti, hydrogenation component in Cr and its mixture, and the activated traditional hydrocracking catalyst THC that chooses any one kind of them, the weight ratio of THC and SAPO is 1: 10 to 500: 1, contain at least a inorganic oxide matrix component in addition, above-mentioned SAPO is characterised in that, its calcinated form adsorbs 4%(weight at least when dividing potential drop 100 torrs and temperature-186 ℃) oxygen.
4, by the method for claim 3, wherein another feature of SAPO is that its calcinated form adsorbs 2%(weight at least when 20 ℃ of dividing potential drop 500 torrs and temperature) Trimethylmethane.
5, by claim 1 or 2 or 3 or 4 method, wherein SAPO is characterised in that its calcinated form under the condition of 22 ℃ of dividing potential drop 2.6 torrs and temperature, and absorption zero is to less than 5%(weight) triethylamine.
6, by the method for claim 5, wherein the adsorptive capacity of triethylamine is less than 3%(weight).
7, by the method for claim 1 or 2 or 3 or 4, wherein the weight ratio of THC and SAPO is 1: 2 to 50: 1.
8, by the method for claim 7, wherein the weight ratio of THC and SAPO is 1: 1 to 20: 1.
9, by the method for claim 1 or 2 or 3 or 4, wherein the inorganic oxide components amount is 5% to a 95%(weight of above-mentioned total catalyst weight).
10, according to the method for claim 1 or 2 or 3 or 4, wherein the above-mentioned THC component in the conversion catalyst is a zeolite aluminosilicate, and contains to be selected from by ammonium, II A family, III A family, II B family to VII B family, Ce, La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and its mixture and constituted the positively charged ion in a group.
11, by the method for claim 1 or 2 or 3 or 4, wherein the positively charged ion of SAPO to small part is to exist with the form that is made of (hydrogen-forming) hydrogen.
12, by the method for claim 11, be NH wherein by the cationic form that hydrogen constitutes
+ 4Or H
+
13, by the method for claim 10, wherein zeolite aluminosilicate contains 0.1% to 20%(weight) polyvalent cation.
14, by the method for claim 9, wherein the inorganic oxide matrix component is selected from clay, silicon oxide, aluminum oxide, silica-alumina, silicon oxide-zirconium white, silicon oxide-magnesium oxide, aluminum oxide-boron oxide, aluminium oxide-titanium oxide and its mixture.
15, by the method for claim 1 or 2 or 3 or 4, wherein SAPO is selected from SAPO-5, SAPO-11, SAPO-17, SAPO-31, SAPO-34, SAPO-35, SAPO-40, SAPO-41, SAPO-44 and its mixture.
16, by the method for claim 15, wherein SAPO is SAPO-11.
17, by the method for claim 15, wherein SAPO is SAPO-17.
18, by the method for claim 15, wherein SAPO is SAPO-31.
19, by the method for claim 15, wherein SAPO is SAPO-34.
20, by the method for claim 15, wherein SAPO is SAPO-40.
21, by the method for claim 15, wherein SAPO is SAPO-41.
22, by the method for claim 1 or 2 or 3 or 4, wherein crude oil material is selected from cut gas oil, heavy vacuum gas oil, vacuum gas oil, atmospheric resids, decompression residual oil, synthetic crude, fine coal and its mixture.
23, press the method for claim 1 or 2 or 3 or 4, wherein THC contains at least a zeolite aluminosilicate, and the latter is selected from zeolite Y, overstable zeolite Y, X zeolite, zeolite beta, zeolite KZ-20, faujusite, LZ-210, LZ-10, ZSM type zeolite and its mixture.
24, the method for claim 23, wherein zeolite aluminosilicate is selected from zeolite Y, overstable zeolite Y, zeolite beta, zeolite KZ-20, faujusite, LZ-210, LZ-10, ZSM-5 and its mixture.
25, according to the method for claim 1 or 2 or 3 or 4, metal wherein is selected from Pt, Pd, Rh, Ru and its mixture, and its amount is a 0.05%(weight) to 1.5%(weight).
26, by the method for claim 1 or 2 or 3 or 4, wherein metal is selected from Ni, W, Mc, Co, Ti, Cr and its mixture, and its amount is a 1.0%(weight) to 30%(weight).
27, press the method for claim 1 or 2 or 3 or 4, wherein the hydrocracking condition of this method comprises, the boiling range of hydrocarbon charging is between 400 °F and 900 °F, hydrogen is 4000-12000 standard cubic feet per barrel crude oil material with the ratio of charging, operation total pressure 500-2000psig, medial temperature 450-800 °F, liquid hourly space velocity (LHSV) is 0.2-5 feed volume/catalyst volume hour.
28, by the method for claim 27, hydrotreatment has been passed through in charging wherein.
29, by the method for claim 27, charging is wherein handled through hydrogenating desulfurization.
30, by the method for claim 27, wherein the boiling range of hydrocarbon charging is between 300 °F and 800 °F.
31, by the method for claim 1 or 2 or 3 or 4, wherein the boiling range of hydrocarbon charging is between 400 °F and 900 °F.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US68294684A | 1984-12-18 | 1984-12-18 | |
| US682,946 | 1984-12-18 |
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|---|---|
| CN85109634A CN85109634A (en) | 1986-06-10 |
| CN1007991B true CN1007991B (en) | 1990-05-16 |
Family
ID=24741900
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| CN 85109634 Expired CN1007991B (en) | 1984-12-18 | 1985-12-17 | With the hydrogenolysis that contains the alumo-silicate molecular sieve catalyzer |
| CN 89100867 Pending CN1034679A (en) | 1984-12-18 | 1989-02-16 | The catalyzer that contains alumo-silicate molecular sieve |
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| EP (1) | EP0207133A1 (en) |
| JP (1) | JPS62501426A (en) |
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| US4724066A (en) * | 1985-01-22 | 1988-02-09 | Mobil Oil Corporation | Composites of microporous aluminum phosphates and zeolites and conversions over these catalysts |
| US4741820A (en) * | 1986-03-27 | 1988-05-03 | Union Carbide Corporation | Reforming/dehydrocyclization catalysts and processes |
| US4695368A (en) * | 1986-07-31 | 1987-09-22 | Union Oil Company Of California | Process for producing high octane gasoline |
| US4859312A (en) * | 1987-01-12 | 1989-08-22 | Chevron Research Company | Process for making middle distillates using a silicoaluminophosphate molecular sieve |
| US5139647A (en) * | 1989-08-14 | 1992-08-18 | Chevron Research And Technology Company | Process for preparing low pour middle distillates and lube oil using a catalyst containing a silicoaluminophosphate molecular sieve |
| RU2082748C1 (en) * | 1993-09-29 | 1997-06-27 | Институт катализа им.Г.К.Борескова СО РАН | Method of producing liquid motor fuels |
| CN1048429C (en) * | 1994-02-05 | 2000-01-19 | 中国科学院大连化学物理研究所 | Method of synthesizing aluminosilico-phosphate molecular sieve using double template agent |
| RO114524B1 (en) | 1997-10-02 | 1999-05-28 | Sc Zecasin Sa | Process for producing olefins with low molecular mass by fluidized bed catalytic conversion of methanol |
| CN1122637C (en) * | 2001-08-29 | 2003-10-01 | 复旦大学 | Method for synthesizing new-type beryllium phosphate molecular sieve by using concentrated amine system |
| CN100448536C (en) * | 2005-06-27 | 2009-01-07 | 中国科学院大连化学物理研究所 | Hydroisomerization catalyst and its preparation method |
| CN101757929B (en) * | 2008-12-24 | 2012-01-25 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| EP2526166A2 (en) * | 2010-01-21 | 2012-11-28 | Shell Oil Company | Hydrocarbon composition |
| US8679319B2 (en) | 2010-01-21 | 2014-03-25 | Shell Oil Company | Hydrocarbon composition |
| EP2526169A2 (en) | 2010-01-21 | 2012-11-28 | Shell Oil Company | Process for cracking a hydrocarbon- containing feed |
| US8562818B2 (en) | 2010-01-21 | 2013-10-22 | Shell Oil Company | Hydrocarbon composition |
| EP2526173A2 (en) | 2010-01-21 | 2012-11-28 | Shell Oil Company | Process for cracking a hydrocarbon-containing feed |
| CN109806907A (en) * | 2017-11-20 | 2019-05-28 | 中国石油天然气股份有限公司 | Support type Pt/TiO2/ ZSM-5 molecular sieve catalyst and the preparation method and application thereof |
| CN108851966A (en) * | 2018-04-24 | 2018-11-23 | 浙江绍兴苏泊尔生活电器有限公司 | Electric pressure cooker and cooking method |
| US11779909B2 (en) | 2018-12-13 | 2023-10-10 | China Petroleum & Chemical Corporation | Hydrocracking catalyst, preparation method therefor and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1506429A (en) * | 1975-05-13 | 1978-04-05 | Union Carbide Corp | Catalyst for hydrocarbon processes and process for preparing same |
| US4440871A (en) * | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
| IT1157983B (en) * | 1982-12-23 | 1987-02-18 | Fiat Auto Spa | KINEMATIC DEVICE FOR THE CONTROL OF A VALVE OF AN ENDOTHERMAL MOTOR |
| ATE27827T1 (en) * | 1983-05-02 | 1987-07-15 | Union Carbide Corp | CATALYST AND PROCESS FOR HYDROCRACKING. |
| US4512875A (en) * | 1983-05-02 | 1985-04-23 | Union Carbide Corporation | Cracking of crude oils with carbon-hydrogen fragmentation compounds over non-zeolitic catalysts |
-
1985
- 1985-12-17 AU AU53076/86A patent/AU5307686A/en not_active Abandoned
- 1985-12-17 JP JP50030185A patent/JPS62501426A/en active Pending
- 1985-12-17 CN CN 85109634 patent/CN1007991B/en not_active Expired
- 1985-12-17 EP EP19860900501 patent/EP0207133A1/en not_active Withdrawn
- 1985-12-17 WO PCT/US1985/002476 patent/WO1986003694A1/en not_active Application Discontinuation
-
1986
- 1986-08-18 FI FI863335A patent/FI863335A/en not_active Application Discontinuation
-
1989
- 1989-02-16 CN CN 89100867 patent/CN1034679A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| AU5307686A (en) | 1986-07-22 |
| CN1034679A (en) | 1989-08-16 |
| WO1986003694A1 (en) | 1986-07-03 |
| FI863335A0 (en) | 1986-08-18 |
| EP0207133A1 (en) | 1987-01-07 |
| FI863335A (en) | 1986-08-18 |
| JPS62501426A (en) | 1987-06-11 |
| CN85109634A (en) | 1986-06-10 |
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