CN1417117A - Combined zeolite comprising two kinds of modified Y-type zeolite - Google Patents
Combined zeolite comprising two kinds of modified Y-type zeolite Download PDFInfo
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Abstract
The combined zeolite comprises two kind sof modified Y-type zeolite, the first kind of 1-9 pts.wt. and the second kind in 9-1 pts.wt. The first kind of modified Y-type zeolite has crystallinity higher than 85%, specific surface area greater than 700 sq m/g, crystal cell parameter 2.420-2.445 nm, SiO2/Al2O3 ratio 8-18 and infrared acidity 0.6-1.6 mmol/g; and the second kind of modified Y-type zeolite has crystallinity higher than 90%, specific surface area greater than 750 sq m/g, crystal cell parameter 2.425-2.435 nm, SiO2/Al2O3 ratio 8-18 and infrared acidity 0.2-0.6 mmol/g. The combined zeolite may be compounded with refractory oxides, such as amorphous Si-Al or Al2O3 to constitute the carrier for hydrocarbon-converting hydrogenation catalyst with group VIB and/or group VIII metal as active component.
Description
1, technical field:
The present invention relates to a kind of zeolite, especially the acidic components, the particularly combined zeolite of forming by two kinds of modified Y zeolites used of Hydrocarban coversion catalysts.
2, background technology:
Heavy distillate is produced light ends oil by hydrocracking, and particularly it being transformed the output that increases rocket engine fuel and diesel oil is the major issue that current modernized refinery pays close attention to.
Improve wherein that the key of rocket engine fuel and diesel component ratio is to prepare suitable catalyzer in the isocrackate, be equipped with appropriate process again.
Hydrocracking catalyst is the dual-function catalyst with cracking and hydrogenation performance, its cracking performance is provided by carrier (comprising zeolite), hydrogenating function is provided by VIB and/or group VIII metal, and the active catalyzer different with selectivity formed in the different cooperations of hydrogenation performance and cracking performance.
Early stage carrier of hydrocracking catalyst is unformed SiO
2-Al
2O
3, beginning to add modified zeolite after the sixties, the current hydrocracking catalyst overwhelming majority contains modified zeolite, and is developed to two or more modified zeolite of use by a kind of modified zeolite.
United States Patent (USP) 4,925,546 and 4,980,328 provide two kinds of combined zeolites that overstable gamma zeolite is formed, the SiO of its first overstable gamma zeolite
2/ Al
2O
3Be 5～8, unit cell parameters is 2.4524nm～2.4667nm, the SiO of second overstable gamma zeolite
2/ Al
2O
3Be 8～20, unit cell parameters is 2.4343nm～2.4524nm.
United States Patent (USP) 4,661, the Y zeolite combination of 239 two kinds of hydrothermal treatment consists that provide, hydrothermal treatment consists Y zeolite unit cell parameters is 2.420nm～2.435nm, the Y zeolite difference of its first and second hydrothermal treatment consists modification only is that unit cell parameters differs 0.01nm at least.
Chinese patent 1050037A, the combination that 1017343B and 87103714 discloses two kinds of modified Y zeolites is used to prepare the hydrocracking catalyst of producing intermediate oil, two kinds of modified Y zeolite unit cell parameterss are all between 2.420nm～2.435, and both differ at least more than the 0.01nm, no specific targets.The steam treatment temperature that is provided in the example of these several pieces of patents is more than 732 ℃, have up to 788 ℃.Bigger in industrial enforcement difficulty.
3, summary of the invention:
The purpose of this invention is to provide a kind of combined zeolite of forming by two kinds of modified Y zeolites, make it be specially adapted to the acidic components of Hydrocarban coversion catalysts, being particularly useful for heavy hydrocarbons hydrocraking production rocket engine fuel and diesel oil is the process of main purpose product, thereby improves the selectivity of activity of such catalysts and rocket engine fuel and diesel oil.
Combined zeolite of the present invention comprises first modified Y zeolite and second modified Y zeolite, described first modified Y zeolite is 1: 9～9: 1 with the ratio of the weight content of second modified Y zeolite in described combined zeolite, the character of described first modified Y zeolite is: degree of crystallinity 〉=85%, specific surface area 〉=700m
2/ g, unit cell parameters 2.420nm～2.445nm, SiO
2/ Al
2O
3Than being 8～18, infrared acidity is 0.6mmol/g～1.6mmol/g; The character of described second modified Y zeolite is: degree of crystallinity 〉=90%, specific surface area 〉=750m
2/ g, unit cell parameters 2.425nm～2.435nm, SiO
2/ Al
2O
3Than being 8～18, infrared acidity is 0.2mmol/g～0.6mmol/g.
The ratio of the weight of described two kinds of modified Y zeolites in combined zeolite is preferably: first modified Y zeolite/second modified Y zeolite=8/2～6/4.
The character of first modified Y zeolite of the present invention is preferably: degree of crystallinity 90%～105%, specific surface area 750～850m
2/ g, unit cell parameters 2.435nm～2.440nm, SiO
2/ Al
2O
3Than being 11～15, infrared acidity is 0.8mmol/g～1.2mmol/g.
The character of second modified Y zeolite of the present invention is preferably: degree of crystallinity 95%～110%, specific surface area 780～870m
2/ g, unit cell parameters 2.430nm～2.435nm, SiO
2/ Al
2O
3Than being that 11～15 infrared acidity are 0.3mmol/g～0.5mmol/g.
Two kinds of modified Y zeolites disclosed by the invention are feedstock production with the NaY zeolite all, and the character of NaY zeolite is generally should be: SiO
2/ Al
2O
3Than being 4.5～5.5, preferably 5.0～5.2, unit cell parameters is 2.450nm～2.480nm, 2.460nm～2.470nm preferably, degree of crystallinity is greater than 90%, more preferably greater than 95%.Described NaY zeolite can be with reference to United States Patent (USP) 3,130, disclosed method preparation in 007.
The preparation method of described first modified Y zeolite comprises: (1) contacts NaY zeolite raw material and carries out the ammonium exchange with ammonium salt solution, make it become NH
4The NaY zeolite, the exchange after-filtration, several, the Na in zeolite are carried out in exchange and filtration repeatedly
2O content is reduced to below 3%; (2) NH that (1) step clearing house is got
4The NaY zeolite carries out high-temperature water thermal treatment, and treatment temp is 500 ℃～700 ℃, and keeping steam partial pressure in the stove during hydrothermal treatment consists is 0.03MPa～0.15MPa, and the treatment time is 0.5hr～10.0hr; (3) with the sample of (2) step after the hydrothermal treatment consists with containing NH
4 +And H
+Solution-treated, the weight ratio of zeolite and solution is 1: 2～15, the temperature of processing is 50 ℃～120 ℃, the time of processing is 0.2hr～5.0hr, the number of times of processing is 1 to 5 time, H in the solution
+Concentration be 0.02N～0.20N, NH
4 +Concentration be 0.5N～3.0N, filter after each solution-treated, last solution-treated after filtering, filter cake washs with water purification, the filter cake after the washing promptly becomes described first modified Y zeolite after drying.
Used ammonium salt solution can be that the mineral acid salt of ammonium is (as NH in the exchange of above-mentioned ammonium
4NO
3, NH
4Cl, NH
4SO
4And NH
4CO
3Deng) solution or organic acid salt be (as NH
4Ac etc.) solution, the exchange temperature is generally 50～120 ℃, and preferably 85～100 ℃, the Na in the zeolite that last ammonium exchange obtains
2O content is preferably reduced to below 2.3%.
Described high-temperature water thermal treatment one is to the NH that (1) step clearing house can be got
4The NaY zeolite places in the outer hot inner pressed hydrothermal treatment consists stove and carries out high-temperature water thermal treatment with the water vapor that himself was produced.Preferably 550 ℃～650 ℃ of treatment temps keep preferably 0.05MPa～0.10MPa of steam partial pressure in the stove during hydrothermal treatment consists, the treatment time is 1.0hr～5.0hr preferably.
Zeolite sample after the described processing is with containing NH
4 +And H
+Solution-treated, the weight ratio of zeolite and solution is preferably 1: 5～10, preferably 80 ℃～100 ℃ of the temperature of solution-treated, the time of solution-treated is 0.5hr～2.0hr preferably, the number of times of solution-treated preferably 2～3 times, H in the solution
+Concentration 0.06N～0.15N preferably, NH
4 +Concentration 1.0N～2.0N preferably, the negatively charged ion in the solution can be Cl
-, NO
3 -, SO
4 2-, CO
3 2-, Ac
-Or its mixture.Filter after described each solution-treated, last solution-treated after filtering, filter cake washs with water purification, the filter cake after the washing generally can be under 100 ℃～130 ℃ conditions dry 8hr～16hr.
The preparation of second modified Y zeolite can be carried out as follows: first modified Y zeolite is carried out hydrothermal treatment consists once more by the condition of the first modified Y zeolite hydrothermal treatment consists, be second modified Y zeolite after the processing.
Generally two kinds of modified Y zeolites can be mixed being used in the catalyzer, its blending ratio is: first modified Y zeolite/second modified Y zeolite=9/1 is to 1/9, and preferably 8/2 to 6/4.
Utilize two kinds of modified Y zeolites of the present invention as acidic components, be equipped with porous, inorganic refractory oxide matrix such as SiO
2-Al
2O
3, Al
2O
3Form support of the catalyst, combine with group vib and/or VIII family hydrogenation metal in the element periodic table of elements again and form catalyzer, this catalyzer can be used for the hydrocarbons hydrogenation conversion catalyst, its composition is generally: the weight percent with catalyzer is a benchmark, comprise: described combined zeolite of the present invention accounts for 10%-45%, the porous, inorganic refractory oxide accounts for 25%-65%, and the hydrogenation active metals component accounts for 15%-35% in oxide compound.
When the above-mentioned catalyzer of concrete preparation, promptly can earlier first modified Y zeolite of the present invention and second modified Y zeolite be prepared into combined zeolite earlier according to ratio of the present invention, composite with other necessary component again, make described catalyzer, also described first modified Y zeolite, second modified Y zeolite and porous refractory oxide can be mixed together and make carrier earlier, utilize the impregnating method that the hydrogenation activity component is loaded on the carrier again, make described catalyzer.In a word, as long as the finally ratio requirement according to the invention of made each component of catalyzer, the present invention does not limit the addition sequence and the adding method of each component.
Porous, inorganic refractory oxide of the present invention generally can be aluminum oxide and/or siliceous aluminum oxide, and described hydrogenation active metals component is generally can be group vib and/or group VIII metal component.
This catalyzer is applicable to the hydroconversion reactions of hydro carbons, is specially adapted to hydrocracking, hydro-upgrading, hydrotreatment of heavy hydrocarbon etc.
Two kinds of modified Y zeolites combination provided by the present invention is used for heavy hydrocarbons hydrocraking catalyst, can make this catalyzer demonstrate excellent activity, high rocket engine fuel and diesel oil selectivity.4, embodiment:
Embodiment 1
With 1000g SiO
2/ Al
2O
3Than being 5.0, unit cell parameters is 2.468nm, and degree of crystallinity is that 97% NaY zeolite adds 8L and contains 800g NH
4NO
3Solution in, be warming up to 95 ℃, stirred 1 hour, dope filtration, repetitive operation 2 times, filter cake is used deionized water wash at last, analyzes Na in the filter cake of washing back this moment
2The weight content of O is 2.3%.
Filter cake is placed the hydrothermal treatment consists stove of hot inner pressed outward, temperature is risen to 660 ℃, steam partial pressure is 0.07Mpa in the control stove, carries out hydrothermal treatment consists 2 hours, and telegram in reply is lowered the temperature naturally.
Zeolite sample after the hydrothermal treatment consists adds 0.15N HNO
3, contain 1.0N NH
4NO
3Solution 10L in, the weight ratio of zeolite and solution is 1: 8, stirs under 90 ℃ of conditions 1 hour, filters, repeat again 1 time, washing, 110 ℃ dry 4 hours down, obtain the first modified Y zeolite sample 1, its physico-chemical property is as follows:
Degree of crystallinity 92%;
Specific surface area 780m
2/ g;
Unit cell parameters 2.438nm
SiO
2/ Al
2O
3Than being 13.2
Infrared acidity is 1.06mmol/g
Embodiment 2
With 800g SiO
2/ Al
2O
3Than being 5.0, unit cell parameters is 2.468nm, and degree of crystallinity is that 97% NaY zeolite adds 8L and contains 960g NH
4NO
3Solution in, be warming up to 90 ℃, stirred 1 hour, dope filtration, repetitive operation 2 times, filter cake is used deionized water wash at last, analyzes Na in the filter cake of washing back this moment
2The weight content of O is 1.9%.
Filter cake is placed the hydrothermal treatment consists stove of hot inner pressed outward, temperature is risen to 620 ℃, steam partial pressure is 0.12Mpa in the control stove, carries out hydrothermal treatment consists 3 hours, and telegram in reply is lowered the temperature naturally.
Zeolite sample after the hydrothermal treatment consists adds and contains 0.08N HNO
3, contain 1.0N NH
4NO
3Solution 8L in, zeolite is 1: 8 with the ratio of the weight of solution, stirs under 90 ℃ of conditions 2 hours, filters, and repeats 2 times again, washing, drying obtain the first modified Y zeolite sample 2.The physico-chemical property of sample 2 is as follows:
Degree of crystallinity 96%;
Specific surface area 803m
2/ g;
Unit cell parameters 2.439nm
SiO
2/ Al
2O
3Than being 13.8
Infrared acidity is 1.01mmol/g
Embodiment 3
Sample 1400g among the embodiment 1 is placed outer hot inner pressed hydrothermal treatment consists stove, be warming up to 650 ℃, steam partial pressure is 0.08Mpa in the control stove, handles 2 hours, and the product that obtains after the cooling is the second modified Y zeolite sample 3.The character of sample 3 is listed as follows:
Degree of crystallinity 100%;
Specific surface area 816m
2/ g;
Unit cell parameters 2.432nm
SiO
2/ Al
2O
3Than being 13.1
Infrared acidity is 0.38mmol/g
Embodiment 4
Sample 1400g among the embodiment 2 is placed outer hot inner pressed hydrothermal treatment consists stove, be warming up to 630 ℃, steam partial pressure is 0.10Mpa in the control stove, handles 3 hours, and the product that obtains after the cooling is the second modified Y zeolite sample 4.The character of sample 4 is listed as follows:
Degree of crystallinity 97%;
Specific surface area 786m
2/ g;
Unit cell parameters 2.432nm
SiO
2/ Al
2O
3Than being 13.6
Infrared acidity is 0.41mmol/g
Embodiment 5
The first modified Y zeolite sample 1 is mixed with the second modified Y zeolite sample, 3 according to the form below part by weight, measure its character.
Table 1
| Sample number into spectrum | Mix 1 | Mix 2 | Mix 3 | Mix 4 | Mix 5 | Mix 6 |
| The first modification sample 1 | ?80 | ?75 | ?70 | ?65 | ?60 | ?50 |
| The second modification sample 3 | ?20 | ?25 | ?30 | ?35 | ?40 | ?50 |
| SiO 2/Al 2O 3 | ?13.2 | ?13.1 | ?13.2 | ?13.1 | ?13.1 | ?13.1 |
| Infrared acidity mmol/g | ?0.90 | ?0.86 | ?0.84 | ?0.81 | ?0.76 | ?0.70 |
Embodiment 6
The first modified Y zeolite sample 2 is mixed with the second modified Y zeolite sample, 4 according to the form below part by weight, measure its character.
Table 2
| Sample number into spectrum | Mix 7 | Mix 8 | Mix 9 | Mix 10 | Mix 11 | Mix 12 |
| The first modification sample 2 | ????80 | ????75 | ????70 | ????65 | ????60 | ????50 |
| The second modification sample 4 | ????20 | ????25 | ????30 | ????35 | ????40 | ????50 |
| SiO 2/Al 2O 3 | ????13.8 | ????13.6 | ????13.7 | ????13.7 | ????13.6 | ????13.7 |
| Meleic acid mmol/g | ????0.91 | ????0.84 | ????0.82 | ????0.79 | ????0.77 | ????0.71 |
Embodiment 7
The sample that is mixed by different ratios by the first modified Y zeolite sample 1 and the second modified Y zeolite sample 3 that is provided among the embodiment 5 is provided is mixed 1～mixed 6 each 30g, respectively with the unformed SiO of 60g
2-Al
2O
3(SiO wherein
2Weight content be 37%) mix, add the little porous aluminum oxide of 10 grams (pore volume 0.3～0.5ml/g) as tackiness agent moulding make carrier, make with pickling process and contain NiO 5.8%, WO
322.3% catalyst A, B, C, D, E, F.Catalyst A---F and reference catalyst (HC-16) composition is listed in table 3.
Table 3
| Catalyst chemical is formed, m% | ??A | ???B | ???C | ???D | ???E | ???F | The reference agent |
| ??????WO 3 | ?22.9 | ??21.8 | ??22.4 | ??22.5 | ??21.9 | ??22.1 | ???17.77 * |
| ??????NiO | ?5.7 | ??6.1 | ??5.8 | ??6.2 | ??5.9 | ??6.0 | ???5.24 |
| ??????Si 2O | ?34.7 | ??34.2 | ??35.1 | ??34.5 | ??35.2 | ??34.5 | ???10.3 |
| ??????Al 2O 3 | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
*Analytical results is MoO
3Data.
It is that raw material is estimated that catalyst A, B, C, D, E, F and reference catalyst (HC-16) subtract three-way distillate with Iran, and Iran subtracts three-way distillate character and is listed in the table below:
Table 4
| Density, g/cm3 | ????0.9151 |
| Boiling range, ℃ | ????254～545 |
| Sulphur, % | ????1.67 |
| Nitrogen, w% | ????0.1944 |
Catalyst A, B, C, D, E, F and the reference catalyst evaluation result on small-sized hydroeracking unit is listed in the table below:
Table 5
| Cracking catalyst | A | ?B | ?C | ?D | ?E | ?F | The reference agent |
| Reaction pressure (always), MPa | ????????????????????????????????15.7 | ||||||
| Volume space velocity, h -1 | ????????????????????????????????1.21 | ||||||
| Hydrogen to oil volume ratio | ????????????????????????????????1150 | ||||||
| The treated oil nitrogen content, μ g/g | ????????????????????????????????～23 | ||||||
| Temperature of reaction, ℃ | 373 | ?375 | ?378 | ?381 | ?384 | ?389 | ?390 |
| 〉=350 ℃ of transformation efficiencys, w% | 73.0 | ?75.1 | ?74.2 | ?74.8 | ?73.3 | ?74.5 | ?75 |
| Middle distillates oil selectivity, w% | 71.8 | ?73.7 | ?74.9 | ?76.6 | ?77.1 | ?77.9 | ?74.8 |
Embodiment 8
Sample among the embodiment 6 mixes 7～mixed 12 each 50g, respectively with the unformed SiO of 150g
2-Al
2O
3Mixing adds the tackiness agent moulding and makes carrier, makes with pickling process to contain NiO 6.2%, WO
321.7% catalyzer G, H, I, J, K, L.Catalyzer G---L and reference catalyst (HC-16) composition is listed in table 6.
Table 6
| Catalyst chemical is formed, m% | ????G | ????H | ????I | ???J | ???K | ???L | The reference agent |
| ????WO 3 | ??21.4 | ??21.7 | ??22.3 | ??23.0 | ??21.9 | ??21.3 | ???17.77 * |
| ????NiO | ??6.3 | ??6.1 | ??5.8 | ??6.0 | ??5.9 | ??6.2 | ???5.24 |
| ????Si 2O | ??35.1 | ??34.9 | ??35.2 | ??34.2 | ??35.0 | ??35.6 | ???10.3 |
| ????Al 2O 3 | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
*Analytical results is MoO
3Data.
It is that raw material is estimated that catalyzer G, H, I, J, K, L and reference catalyst subtract three-way distillate with Iran, and Iran subtracts three-way distillate character with example 7.Catalyzer G, H, I, J, K, L and reference catalyst (HC-16) evaluation result on small-sized hydroeracking unit is listed in table 7:
Table 7
| Cracking catalyst | ?G | ??H | ??I | ??J | ??K | ??L | The reference agent |
| Reaction pressure (always), MPa | ????????????????????????????????15.7 | ||||||
| Volume space velocity, h -1 | ????????????????????????????????1.21 | ||||||
| Hydrogen to oil volume ratio | ????????????????????????????????1150 | ||||||
| The treated oil nitrogen content, μ g/g | ????????????????????????????????～21 | ||||||
| Temperature of reaction, ℃ | 374 | ?377 | ?378.5 | ?382 | ?385 | ?389 | ???390 |
| 〉=350 ℃ of transformation efficiencys, w% | 73.5 | ?74.9 | ?73.8 | ?74.2 | ?73.1 | ?74.4 | ???75 |
| Middle distillates oil selectivity, w% | 72.5 | ?77.4 | ?74.8 | ?77.6 | ?77.8 | ?79.4 | ???74.5 |
Claims (10)
1, a kind of combined zeolite of forming by two kinds of modified Y zeolites, comprise the-modified Y zeolite and second modified Y zeolite, described first modified Y zeolite is 1: 9～9: 1 with the ratio of the weight content of second modified Y zeolite in described combined zeolite, the character of described first modified Y zeolite is: degree of crystallinity 〉=85%, specific surface area 〉=700m
2/ g, unit cell parameters 2.420nm～2.445nm, SiO
2/ Al
2O
3Than being 8～18, infrared acidity is 0.6mmol/g～1.6mmol/g; The character of described second modified Y zeolite is: degree of crystallinity 〉=90%, specific surface area 〉=750m
2/ g, unit cell parameters 2.425nm～2.435nm, SiO
2/ Al
2O
3Than being 8～18, infrared acidity is 0.2mmol/g～0.6mmol/g.
2,, it is characterized in that described first modified Y zeolite and the ratio of the weight content of second modified Y zeolite in described combined zeolite are 8/2～6/4 according to the described combined zeolite of claim 1.
3, according to the described combined zeolite of claim 1, the character that it is characterized in that described first modified Y zeolite is degree of crystallinity 90%～105%, specific surface area 750～850m
2/ g, unit cell parameters 2.435nm～2.440nm, SiO
2/ Al
2O
3Than being 11～15, infrared acidity is 0.8mmol/g～1.2mmol/g.
4, according to the described combined zeolite of claim 1, it is characterized in that the character of described second modified Y zeolite is: degree of crystallinity 95%～110%, specific surface area 780～870m
2/ g, unit cell parameters 2.430nm～2.435nm, SiO
2/ Al
2O
3Than being that 11～15 infrared acidity are 0.3mmol/g～0.5mmol/g.
5, according to the described combined zeolite of claim 1, it is characterized in that described first modified Y zeolite and second modified Y zeolite are that raw material carries out modification and obtains with the NaY zeolite all, described NaY zeolite raw material properties is SiO
2/ Al
2O
3Than being 4.5～5.5, unit cell parameters is 2.450nm～2.480nm, and degree of crystallinity is greater than 90%.
6, according to the described combined zeolite of claim 1, it is characterized in that the preparation method of described first modified Y zeolite comprises: (1) contacts NaY zeolite raw material and carries out the ammonium exchange with ammonium salt solution, make it become NH
4The NaY zeolite, the exchange after-filtration, several, the Na in zeolite are carried out in exchange and filtration repeatedly
2O content is reduced to below 3%; (2) NH that (1) step clearing house is got
4The NaY zeolite carries out high-temperature water thermal treatment, and treatment temp is 500 ℃～700 ℃, and keeping steam partial pressure in the stove during hydrothermal treatment consists is 0.03MPa～0.15MPa, and the treatment time is 0.5hr～10.0hr; (3) with the sample of (2) step after the hydrothermal treatment consists with containing NH
4 +And H
+Solution-treated, the weight ratio of zeolite and solution is 1: 2～15, the temperature of processing is 50 ℃～120, the time of processing is 0.2hr～5.0hr, the number of times of processing is 1 to 5 time, H in the solution
+Concentration be 0.02N～0.20N, NH
4 +Concentration be 0.5N～3.0N, filter after each solution-treated, last solution-treated after filtering, filter cake washs with water purification, the filter cake after the washing promptly becomes described first modified Y zeolite after drying.
7, according to the described combined zeolite of claim 1, it is characterized in that the preparation method of described second modified Y zeolite comprises: (1) contacts NaY zeolite raw material and carries out the ammonium exchange with ammonium salt solution, make it become NH
4The NaY zeolite, the exchange after-filtration, several, the Na in zeolite are carried out in exchange and filtration repeatedly
2O content is reduced to below 3%; (2) NH that (1) step clearing house is got
4The NaY zeolite carries out high-temperature water thermal treatment, and treatment temp is 500 ℃～700 ℃, and keeping steam partial pressure in the stove during hydrothermal treatment consists is 0.03MPa～0.15MPa, and the treatment time is 0.5hr～10.0hr; (3) with the sample of (2) step after the hydrothermal treatment consists with containing NH
4 +And H
+Solution-treated, the weight ratio of zeolite and solution is 1: 2～15, the temperature of processing is 50 ℃～120, the time of processing is 0.2hr～5.0hr, the number of times of processing is 1 to 5 time, H in the solution
+Concentration be 0.02N～0.20N, NH
4 +Concentration be 0.5N～3.0N, filter after each solution-treated, last solution-treated after filtering, filter cake washs with water purification, the filter cake after the washing carries out drying; (4) the dried zeolite of (3) step gained is carried out high-temperature water thermal treatment, treatment temp is 500 ℃～700 ℃, keeping steam partial pressure in the stove during hydrothermal treatment consists is 0.03MPa～0.15MPa, and the treatment time is 0.5hr～10.0hr, promptly gets described second modified Y zeolite after the processing.
8, a kind of hydrocracking catalyst is a benchmark with the weight percent of catalyzer, and comprising: the described combined zeolite of claim 1 accounts for 10%-45%, and inorganic refractory oxide accounts for 25%-65%, and the hydrogenation active metals component accounts for 15%-35% in oxide compound.
9,, it is characterized in that described inorganic refractory oxide is aluminum oxide or siliceous aluminum oxide according to the described hydrocracking catalyst of claim 7.
10,, it is characterized in that described hydrogenation active metals component is group vib and/or group VIII metal component according to the described hydrocracking catalyst of claim 7.
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|---|---|---|---|
| CN 01133376 CN1221473C (en) | 2001-10-30 | 2001-10-30 | Combined zeolite comprising two kinds of modified Y-type zeolite |
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|---|---|---|---|
| CN 01133376 CN1221473C (en) | 2001-10-30 | 2001-10-30 | Combined zeolite comprising two kinds of modified Y-type zeolite |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102463131A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN103191775A (en) * | 2012-01-06 | 2013-07-10 | 中国石油化工股份有限公司 | Preparation method of hydrocracking catalyst |
| CN103191774A (en) * | 2012-01-06 | 2013-07-10 | 中国石油化工股份有限公司 | Method for preparing hydrocracking catalyst |
| CN103773482A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Hydrocracking method used for producing high-quality chemical raw materials |
| CN104923291A (en) * | 2014-03-21 | 2015-09-23 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation and application thereof |
| CN105457671A (en) * | 2014-09-11 | 2016-04-06 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof, and hydrocracking reaction method |
| CN105457672A (en) * | 2014-09-11 | 2016-04-06 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof, and hydrocracking reaction method |
| CN106672995A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Modified Y-type molecular sieve and preparation method thereof |
| GB2546614B (en) * | 2014-12-01 | 2019-02-13 | China Petroleum & Chem Corp | H-Y Molecular sieve, and preparation methods thereof, hydrocracking catalyst, and hydrocracking method |
-
2001
- 2001-10-30 CN CN 01133376 patent/CN1221473C/en not_active Expired - Lifetime
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102463131A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN102463131B (en) * | 2010-11-04 | 2014-07-23 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN103191775A (en) * | 2012-01-06 | 2013-07-10 | 中国石油化工股份有限公司 | Preparation method of hydrocracking catalyst |
| CN103191774A (en) * | 2012-01-06 | 2013-07-10 | 中国石油化工股份有限公司 | Method for preparing hydrocracking catalyst |
| CN103773482A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Hydrocracking method used for producing high-quality chemical raw materials |
| CN103773482B (en) * | 2012-10-24 | 2015-09-02 | 中国石油化工股份有限公司 | A kind of method for hydrogen cracking producing high-quality industrial chemicals |
| CN104923291B (en) * | 2014-03-21 | 2018-07-31 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and its preparation and application |
| CN104923291A (en) * | 2014-03-21 | 2015-09-23 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation and application thereof |
| CN105457671A (en) * | 2014-09-11 | 2016-04-06 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof, and hydrocracking reaction method |
| CN105457672A (en) * | 2014-09-11 | 2016-04-06 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof, and hydrocracking reaction method |
| CN105457671B (en) * | 2014-09-11 | 2017-12-22 | 中国石油化工股份有限公司 | The method of hydrocracking catalyst and preparation method thereof and hydrocracking reaction |
| CN105457672B (en) * | 2014-09-11 | 2018-01-05 | 中国石油化工股份有限公司 | The method of hydrocracking catalyst and preparation method thereof and hydrocracking reaction |
| GB2546614B (en) * | 2014-12-01 | 2019-02-13 | China Petroleum & Chem Corp | H-Y Molecular sieve, and preparation methods thereof, hydrocracking catalyst, and hydrocracking method |
| US10525452B2 (en) | 2014-12-01 | 2020-01-07 | China Petroleum & Chemical Corporation | Na-Y molecular sieve, H-Y molecular sieve, and preparation methods thereof, hydrocracking catalyst, and hydrocracking method |
| CN106672995A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Modified Y-type molecular sieve and preparation method thereof |
| CN106672995B (en) * | 2015-11-09 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of Modified Zeolite Y and preparation method thereof |
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