CN1024504C - Cracking catalyst containing phosphate and hydrogen Y molecular sieve, and its preparation - Google Patents
Cracking catalyst containing phosphate and hydrogen Y molecular sieve, and its preparation Download PDFInfo
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- CN1024504C CN1024504C CN 91109945 CN91109945A CN1024504C CN 1024504 C CN1024504 C CN 1024504C CN 91109945 CN91109945 CN 91109945 CN 91109945 A CN91109945 A CN 91109945A CN 1024504 C CN1024504 C CN 1024504C
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Abstract
The present invention relates to a phosphorus containing faujasite type catalyst for the catalystic cracking of hydrocarbons, which is prepared from 4 to 50 wt% of zeolite, 0 to 80 wt% of clay, 5 to 95 wt% of high temperature resisting aluminium containing inorganic oxide and 0.05 to 4.0 wt% of phosphorus, wherein the zeolite is HY, HX, REHY and RFHX, and other types of zeolite can also be compounded. The catalyst is prepared from faujasite with the Na<+> pre-exchange degree of 0 to 90% or a mixture of the faujasite and other kinds of zeolite as a raw material matched with the clay and the high temperature resisting aluminium containing inorganic oxide as auxiliary materials by treating the raw material and the auxiliary materials after spray forming and ion exchange with a water solution of a phosphorus containing compound. The catalyst has the advantages of high activity stability, high abrasion resistance strength and high product selectivity.
Description
The invention relates to a kind of phosphorous faujasite-type Catalysts and its preparation method that is used for catalytic cracking of hydrocarbon.Specifically, be phosphorous, the faujasite-type Catalysts and its preparation method that contains or do not contain rare earth that is used for catalytic cracking of hydrocarbon about a kind of.
What propose the REHY zeolite the earliest is U.S. W.R.Grace company.USP3 has reported the result that REHY zeolitic cracking catalyst hydrothermal stability is investigated in 676,368: the content of rare earth (RE in zeolite
2O
3) when being lower than 7 weight %, its heat and the baked REY of the substandard CREY(of hydrothermal stability); And the selectivity of REHY is compared with CREY, C
3～C
4Total productive rate is higher, C
5The lower slightly coke selectivity of productive rate identical or good slightly.
The catalyst company of changing into of Japan has developed phosphorous faujasite to improve the heat endurance of zeolite.At JP62-212, y-type zeolite is handled with the phosphate radical and the simultaneous aqueous solution of ammonium ion in 219, obtains phosphorous NHY
4Zeolite, its sodium content is (with Na
2The O meter) be lower than 3 heavy %, phosphorus content is (with P
2O
5Meter) be 0.3～15 heavy %, this zeolite promptly got heat-staple P-contained Y-zeolite at 500～800 ℃ in 1～6 hour with steam treatment.At JP63-50, in 313, with Na
2O content is that 0.8 heavy %, lattice constant are that the HY of 2.447 nanometers is with phosphoric acid and NH
+ 4The aqueous solution handle half an hour down at 90 ℃, promptly get P after the drying
2O
5Content is the HY zeolite of 10.4 heavy %.
Nippon Oil Co., Ltd has developed the new matrix of a class as Cracking catalyst.At JP63-270, catalyst contains the LaHY of 15 heavy % in 545, and all the other 85 heavy % be " evenly matrix ", contain the Al of 20.9 weight % in this matrix
2O
3, the MgO of 4.1 heavy % and the imvite of 75 heavy %.This catalyst can improve conversion ratio and gasoline yield when producing gasoline and middle distillate with heavy oil.At JP63-270, in 546, catalyst contains the LaHY of 15 heavy %, contains the Al of 16.2 heavy % in the matrix of all the other 85 heavy %
2O
3, 3.2 heavy %MgO, 5.6 heavy % P
2O
5And the imvite of 75 heavy %.At JP63-278,553, catalyst still contains the LaHY of 15 heavy %, contains Al in the matrix of all the other 85 heavy %
2O
382 heavy %, MgO16.2 heavy %, P
2O
51.8 heavy %.
At USP4, handle by carclazyte with biphosphate ion or dihydrogen phosphite ion and ammonium salt thereof in 454,241, USP4,465,780, USP4,504,382 and transform the y-type zeolite catalyst made to improve the micro-activity of Cracking catalyst.
At USP, do 200～1000 meters on matrix duty factor surface with aluminum phosphate in 765,884 and USP4,873,211
2The y-type zeolite of/gram, in an embodiment load be contain 14.1 heavy % rare earths and 25 heavy % sodium, specific surface is 546 meters
2The REY zeolite of/gram is to improve the hydrothermal stability of Cracking catalyst.
At USP4,977, disclose a kind of catalyst that is made of two kinds of particles in 122, a kind of particle wherein is the crystal metal silicate zeolite that loads on the nonzeolite inorganic oxide matrix, and this zeolite is the y-type zeolite of a.＜24.7A or the USY type zeolite of a.＜24.5A; Another kind of particle is the phosphorous Al that loads on the nonzeolite inorganic oxide matrix
2O
3, this phosphorous Al
2O
3Be with specific surface＞20 meter
2The Al of/gram
2O
3Contact with the alkali salt of phosphoric acid or phosphorous acid or its mixed acid and to form.Phosphorus content in the total catalyst is 0.04～2.0 heavy %, and it has higher scuff resistance.
EP358,261 disclose a kind of kaolinic FCC catalyst that comprises crystalline aluminosilicate and cross with sulfuric acid, phosphorous acid, acetic acid treatment, and this crystalline aluminosilicate is the X of X, Y, super stabilizing, the y-type zeolite of super stabilizing.
EP397 discloses in 183 and has a kind ofly loaded on P-contained Y-zeolite on the inorganic oxide matrix to improve the activity of Cracking catalyst.This P-contained Y-zeolite is to use Na
2O content is NaY, HY, the NH of 1～5 heavy %
4Y-type zeolite such as Y, USY be selected from H
3PO
4, (NH
4)
2HPO
4, NH
4H
2PO
4, NaH
2PO
4Phosphorous compound aqueous solution reaction, P on the reacted y-type zeolite
2O
5Content is 0.1～4.0 heavy %.
On the basis of above-mentioned prior art, one of purpose of the present invention provides a kind ofly to be had containing phosphorus and being selected from the zeolitic cracking catalyst of HY, HX, REHY, REHX of high-activity stable, high abrasion resistance strength.
Its preparation flow of Cracking catalyst that contains zeolite is broadly divided into two classes: a class is for exchanging flow process earlier, add matrix after zeolite exchange earlier soon or the modification again and remove spray drying forming (with or without the back roasting), as USP3,676,368, BP1,528,532, JP63-270 is reported in 546, JP63-278,553; Another kind of is back exchange flow process, be about to go again to exchange or modification after zeolite without exchange adds matrix elder generation spray drying forming, and as USP4,454,241, USP4,465,780, USP4,504,382, DS2,114,355, DL139, in 092, DL142,002, DL142,846 report.
Two of purpose of the present invention provides a kind of method that above-mentioned two flow process advantages are the phosphorous faujasite zeolite catalyst of one and the preparation simplified that collects.
Zeolite catalyst provided by the invention has following composition: 4～50 heavy %, the zeolite of best 5～45 heavy %; Natural or the artificial synthetic clay of 0～80 heavy %; 5～95 heavy %, the high temperature resistant aluminium inorganic oxide that contains of best 10～75 heavy %; 0.05～4.0 heavy %, the phosphorus of best 0.4～3.0 heavy %.
Said zeolite can be selected from one of HY, HX, REHY, REHX or two or more mixture wherein, also can be at least they one of with other zeolite: the mixture that is selected from one of USY, USREY, HZSM, modenite, L zeolite, β zeolite.Said clay is for Cracking catalyst matrix clay commonly used, as kaolin, halloysite, imvite, swollen notes soil etc.The said high temperature resistant aluminium inorganic oxide that contains is Al
2O
3, SiO
2Al
2O
3, Al
2O
3MgO, Al
2O
3CaO, Al
2O
3ZrO
2Deng or two kinds mixture wherein.
Zeolite catalyst provided by the invention makes by following method: wet colloid or slurries, clay and the high temperature resistant aluminium inorganic oxide precursor that contains of zeolite are mixed into glue in predetermined ratio, spray drying forming behind the homogeneous, carry out the ion-exchange post processing with the phosphorus-containing compound aqueous solution then, the microballoon after the exchange after filtration, be drying to obtain finished product.
Said zeolite is commutative Na
+Pre-exchange degree be 0～90% faujasite, they can be synthetic after only flush away mother liquor, NaY, NaX zeolite without any ion-exchange treatment, also can be through a HN
+ 4And/or RE
3+HNaY, HNaX, REHNaY, REHNaX, RENaY, RENaX zeolite behind exchange, the bakes to burn the article.Two or more mixture and the mixture of one of one of them and USY, USREY, HZSM, modenite, L zeolite, β zeolite at least in the also above-mentioned NaY of said zeolite, NaX, HXaY, HNaX, REHNaY, REHNaX, RENaY, the RENaX zeolite.
The said high temperature resistant aluminium inorganic oxide precursor that contains is aluminium colloidal sol, plan thin water aluminium glue, silica-alumina gel and Al
2O
3MgO, Al
2O
3CaO, Al
2O
3ZrO
2Isocolloid system or two kinds mixture wherein.
Said phosphorus-containing compound is the water soluble compound of phosphorus, comprising: orthophosphoric acid, phosphorous acid, phosphoric anhydride, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), ammonium phosphite, aluminum phosphate etc. are best with phosphoric acid and ammonium salt thereof wherein.The consumption of phosphorus-containing compound solution is 1～15 times of catalyst butt weight of moulding, and concentration is counted 0.001～17.5 heavy % with phosphorus content, is preferably 0.02～12.0 heavy %.Pressure during ion-exchange is 0～6 MPa, and is the most convenient with normal pressure; Temperature is 5～99 ℃, best 10～96 ℃; Be 1～180 minute swap time, best 2～100 minutes.This ion-exchange can once be carried out, and also can carry out several times so that the phosphorus on the catalyst reaches predetermined amount.The catalyst of spray shaping can first eccysis solubility salt before carrying out ion-exchange, also can not wash and directly carries out ion-exchange.
Cracking catalyst provided by the invention has the advantage that activity stability is good, scuff resistance is high, product selectivity is good.Method for preparing catalyst provided by the invention is because the Na on the employed zeolite
+Pre-exchange degree can be 0～90%, therefore saved traditional repeatedly exchange one calcining process to zeolite, shorten and simplified the Preparation of catalysts flow process; In addition, adopt phosphorus exchange post processing to substitute traditional washing procedure, both reached and removed water soluble salt and (comprise Na
+) purpose, improved activity of such catalysts stability and abrasion strength resistance again, but do not made the flow process complexity.
Following example will be made further instruction to Catalysts and its preparation method provided by the invention.
Example 1
With NaY(SiO
2/ Al
2O
3=5, Na
2The heavy % of O14) with 1.49 heavy %RECl
3Solution is according to zeolite: RECl
3The weight ratio of solution=1: 15 2 hour promptly gets Na in 550 ℃ of roastings 85 ± 5 ℃ of following ion-exchanges 30 minutes behind the filtration drying
+Pre-exchange degree is 60% RENaY.
2 kilograms of (butt) kaolin (China Kaolin Co., Ltd's industrial products, solid content＞75%) with 6.7 liters of water purification pulps, are stirred and add boehmite (Shandong Aluminum Plant's industrial products, Al after 1 hour
2O
380 heavy %) 400 grams are (with Al
2O
3Meter), stirs the above-mentioned RENaY527 gram of adding (butt) after 1 hour, stir 2 hours spray drying formings of homogeneous.
With the catalyst of moulding and 15 times to stem-based catalyst, phosphorus concentration is phosphoric acid (commercially available technical grade) aqueous solution of 0.065 heavy %, and regulate slurries pH to 3.5～4.5 with the ammoniacal liquor (commercially available chemical pure) of 16 heavy %, stirred 30 minutes down at 60 ℃, filter cake after the filtration repeats phosphorus by above-mentioned condition and handles once, again in 110～120 ℃ of dryings 2 hours, promptly get phosphorous REHY type zeolite catalyst provided by the invention, note is made A.
Listed the selective data of every instrumental analysis data, anti-active micro-data and the heavy oil micro anti-evaluation of this catalyst in the table 1.Na wherein
2O is that atomic absorption spectrum records RE
2O
3For the X-ray fluorescent records, P is that phosphorus molybdenum vanadium colorimetric method records Cl
-For the normal electrode method records, specific surface is N
2The adsorption capacity method records, and pore volume is proposed standard TC promulgated by the ministries or commissions of the Central Government, and 014-77 water droplet method records, and wear rate is the U.S. Jersey of a Davison company index.Anti-active micro-data is to be that 235～337 ℃ light oil is a raw material with boiling range, records at 460 ℃ of following fixed bed reactions, and catalyst is 5 grams through 100% water vapour 800 ℃ of processing, loading amounts in advance.The little live data of heavy oil be 482 ℃, during weight space velocity 16
-1Condition under fixed bed reaction record, the catalyst loading amount is 4 grams.The related properties of used heavy oil feedstock have been listed in the table 2.
Below in each example analytical method all therewith example with.
Comparative Examples 1
Prepare catalyst by the method described in the example 1, but the back exchanges use NH when handling
4The commercially available chemical pure of Cl() replaces phosphoric acid.This not phosphorous comparative catalyst note is made B, and the relevant data of analyzing are listed in table 1.Can find out from table 1 data: it is high scuff resistance, activity stability and better choice than catalyst B that catalyst A has comparison.(see Table 1, table 2)
Example 2
With NaY RECl
3-NH
4The Cl mixed solution mixes according to 1: 10 weight ratio, at 85 ± 5 ℃ of following ion-exchanges 30 minutes, RECl in this mixed solution
3Concentration be 1.4 heavy %, NH
4The concentration of Cl is 2.7 heavy %, promptly gets Na in 2 hours in 500 ℃ of roastings behind the filtration drying
+Pre-exchange degree is 68% REHNaY.
20 gram kaolin are added to SiO
2Content is in 1 premium on currency glass (water glass plant, Tianjin industrial products, modulus 2.9～3.3) solution of 60 grams per liters, stirs to add 0.4 liter of Al down again
2O
3Content is aluminum sulfate (commercially available technical grade) solution of 80 grams per liters, and the aging ammoniacal liquor that adds 0.25 liter of 16 heavy % after 15 minutes filters making beating and promptly gets Al
2O
3Content is the semi-synthetic sial carrier slurries of 28 heavy %.Part by weight according to carrier and zeolite is 82: 18 above-mentioned REHNaY of adding, spray drying forming behind the stirring homogeneous.
Be respectively at 45 ℃, pH to the water purification of stem-based catalyst under 4～5,7～8 the condition with 25 times and carry out pre-wash twice, filter, with 15 times to stem-based catalyst, phosphorus concentration is that ammonium phosphite (commercially available chemical pure) solution of 0.001 heavy % exchange twice of processing after 55 ℃, each 8 minutes, filter, be drying to obtain phosphorous REHY type zeolite catalyst C provided by the invention.
Listed the selective data of every instrumental analysis data, anti-active micro-data and the heavy oil micro anti-evaluation of this catalyst in the table 3.
Comparative Examples 2
Press USP3,676,368(=BP1,415,527) described in requirement prepare zeolite: RE before the roasting
3+And/or NH
+ 4The zeolite Na of exchange
2The heavy % in O＜4.0; NH after the roasting
+ 4Exchange makes Na
2The heavy % in O＜0.5.
With the NaY zeolite through a RECl
3Exchange, (NH once
4)
2SO
4(commercially available chemical pure) exchange, 540 ℃ of roastings 3 hours, secondary (NH
4)
2SO
4Exchange obtains Na
2O content 0.29 heavy %, RE
2O
3The RENH of content 6 heavy %
4Y.Press example 2 described Preparation of catalysts methods again, but handle without exchange behind the phosphorus, make not phosphorous contrast REHY type zeolite catalyst D, the relevant data of analyzing are listed in table 3.
Can be found out by table 3 data: catalyst C has comparison than much higher scuff resistance of catalyst D and lower gas yield.(seeing Table 3)
Example 3
By the NH of 100 gram NaY with 2 liters 0.15 mole
4The consumption of Cl solution exchanges 1 hour with NaY down at 55 ± 5 ℃, and the filter cake after the filtration promptly got Na in 2 hours 550 ℃ of roastings
+Pre-exchange degree is 69% NHaY.Its sodium content is (with Na
2The O meter) be 4.7 heavy %, the differential thermal fail temperature is 985 ℃, and specific surface is 850 meters
2/ gram.
In 300 gram kaolin slurries (the kaolin solid content is 30 heavy %), add boehmite 30 grams (with Al
2O
3Meter), stirs the above-mentioned HNaY80 gram of adding (butt) after 1 hour, stir 2 hours spray drying formings of homogeneous.
With the catalyst of moulding and 15 times to stem-based catalyst, phosphorus concentration is ammonium dihydrogen phosphate (ADP) (commercially available chemical pure) aqueous solution of 0.04 heavy %, exchange 2 hours down at 40 ℃, filter cake after the filtration repeats phosphorus by above-mentioned condition and handles once, promptly gets phosphorous HY type zeolite catalyst E provided by the invention after the drying.
Listed the selective data of every instrumental analysis data, anti-active micro-data and the heavy oil micro anti-evaluation of this catalyst in the table 4.
Comparative Examples 3
Press JP62-212,219 embodiment, 2 described methods, by NaY through PO
3+ 4-NH
+ 4Mixed liquor exchange, air roasting, NH
4 +Exchange, steam roasting are prepared phosphorous HY zeolite, its Na
+Pre-exchange degree is 95%, and sodium content is (with Na
2The O meter) be 0.75 heavy %, P content is 0.25 heavy %, and the differential thermal fail temperature is 1007 ℃, and specific surface is 824 meters
2/ gram.
Make the contrast HY-P zeolite catalyst F of same carrier by the prescription of example 3 described catalyst.Relevant analysis data are listed in table 4.
Can be found out by table 4 data: the anti-wear performance of catalyst E and activity stability obviously are better than comparative catalyst F.(seeing Table 4)
Example 4
NaY is weighed %, PH with 1.4
3RECl
3Solution is according to zeolite: RECl
3The weight ratio of solution=1: 15 1 hour promptly gets Na in 550 ℃ of roastings 85 ± 5 ℃ of exchanges 20 minutes down behind the filtration drying
+Pre-exchange degree is 63% REHNaY.Its sodium content is (with Na
2The O meter) be 4.8 heavy %, content of rare earth is (with RE
2O
3Meter) be 12 heavy %, the differential thermal fail temperature is 977 ℃, and specific surface is 841 meters
2/ gram.
Carrier and this REHNaY with example 1 make the catalyst that zeolite content 18 weighs %, carry out the back exchange processing of phosphorus again according to example 3 described conditions, make phosphorous REHY type zeolite catalyst G provided by the invention.
Every instrumental analysis data of this catalyst have been listed in the table 5, the selective data of anti-active micro-data and heavy oil micro anti-evaluation.
Comparative Examples 4
Press JP63-270, the method for preparing catalyst that provides in 546 examples 1 is with containing Na
2O 0.8 heavy %, RE
2O
3The REHY zeolite of 12 heavy % is made the REHY type zeolite catalyst H that contains the semi-synthetic carrier of Al-Mg-P of zeolite content 18 heavy %.Relevant analysis data are listed in table 5.
Can be found out by table 5 data: the anti-wear performance of catalyst G, activity stability and selectivity all obviously are better than comparative catalyst H.(seeing Table 5)
Example 5
With NaY RECl
3-NH
4The Cl mixed solution mixes according to 1: 10 weight ratio, at 85 ± 5 ℃ of following ion-exchanges 40 minutes, RECl in this mixed solution
3Concentration be 0.7 heavy %, NH
4The concentration of Cl is 8.6 heavy %, promptly gets Na in 1 hour in 650 ℃ of roastings behind the filtration drying
+Pre-exchange degree is 60% REHNaY.Its sodium content is (with Na
2The O meter) be 5.8 heavy %, content of rare earth is (with RE
2O
3Meter) be 2.5 heavy %, the differential thermal fail temperature is 980 ℃, and specific surface is 900 meters
2/ gram.
Carrier and this REHNaY with example 1 make the catalyst that zeolite content 25 weighs %.With the catalyst of moulding and 10 times to stem-based catalyst, phosphorus concentration is ammonium phosphate (commercially available chemical pure) aqueous solution of 0.01 heavy %, and to regulate slurries pH respectively with hydrochloric acid be 4～5 and 3～4, the back exchange is handled twice under 85 ℃, each 3 minutes, filtration drying promptly got phosphorous REHY type zeolite catalyst J provided by the invention.
Listed its relevant performance analysis data in the table 6.(seeing Table 6)
Example 6
At SiO
2Content is to stir in the 0.8 premium on currency glass solution of 60 grams per liters to add 0.33 liter of Al down
2O
3Content is the aluminum sulfate solution of 80 grams per liters, and the aging ammoniacal liquor that adds 38 milliliter of 16 heavy % after 15 minutes filters making beating and promptly gets Al
2O
3Content is the sial carrier slurries of 25 heavy %.Part by weight according to carrier and zeolite is 82: 18 adding example 4 prepared REHNaY, spray drying forming behind the stirring homogeneous.
Be respectively at 50 ℃, pH to the water purification of stem-based catalyst under 4～5 and 8～9 the condition with 35 times and carry out twice washing, filter the back with 5 times to stem-based catalyst, phosphorus concentration is that the ammonium phosphate solution of 0.01 heavy % exchanges processing 3 minutes after 90 ℃, filter, again with 1 times to stem-based catalyst, phosphorus concentration is that the ammonium dihydrogen phosphate aqueous solution of 12 heavy % exchanges after 15 ℃ and handled 160 minutes, filtration drying promptly gets phosphorous REHY type zeolite catalyst K provided by the invention.
Listed its relevant performance analysis data in the table 7.(seeing Table 7)
Example 7
The catalyst sample of example 2 gained spray shapings is respectively at 65 ℃, pH to the water purification of stem-based catalyst under 4～5 and 7～8 the condition with 30 times carries out twice washing, filter, with 8 times to stem-based catalyst weight, phosphorus concentration is that the phosphate aqueous solution of 0.001 heavy % mixes with it, and regulate slurries pH3.0～5.0 with the ammoniacal liquor of 16 heavy %, the back exchange is handled twice under 60 ℃, each 15 minutes, filtration drying promptly got phosphorous REHY type zeolite catalyst L provided by the invention.
Listed its relevant performance analysis data in the table 8.(seeing Table 8)
Example 8
Carrier and Na with example 1
+Pre-exchange degree is the catalyst that 0 NaY makes zeolite content 40 heavy %, with 15 times to stem-based catalyst, phosphorus concentration is that the ammonium phosphate solution of 0.01 heavy % exchanges after 50 ℃ and handles 5 times, each 10 minutes, filter, be drying to obtain phosphorous HY type zeolite catalyst M provided by the invention.
Listed its relevant performance analysis data in the table 9.(seeing Table 9)
Example 9
According to example 1 described method for preparing catalyst, when the preparation catalyst slurry, add 30 catalyst subsidiary factory of gram HZSM-5(Qilu Petrochemical company industrial products again, solid content＞98%), the microspherical catalyst that makes is handled according to the back exchange that example 1 described method is carried out phosphorus equally, can make the composite zeolite catalyst N of phosphorous and REHY provided by the invention.
Listed its relevant performance analysis data in the table 10.(seeing Table 10)
Example 10
In example 1 described preparation process, the RENaY addition is 480 grams, adds the super steady Y that DASY(hydro-thermal method dealuminzation is made, wherein Na simultaneously again
2The heavy % of O0.8, lattice constant 2.448 nanometers, 830 meters of specific surfaces
2/ gram, 1018 ℃ of differential thermal fail temperatures) 320 grams carry out spray drying forming and back exchange is handled according to example 1 described method, can make the composite zeolite catalyst O of phosphorous and REHY provided by the invention.
Listed its relevant performance analysis data in the table 11.(seeing Table 11)
Table 1
Catalyst A B
Back exchange Solution H
3PO
4NH
4Cl
Chemical composition, heavy %
Na
2O 0.27 0.20
P 1.0 /
RE
2O
32.8 2.8
Cl
-0.1 0.4
Specific surface, rice
2/ gram 172 179
Pore volume, milliliter/gram 0.28 0.30
Wear rate is during %
-11.6 2.8
Micro-activity, heavy %
800 ℃/4: 74 74
800 ℃/17: 56 38
The little oil of heavy oil, heavy %
Gas 11.5 13.4
Gasoline 56.7 55.2
Light diesel fuel 18.5 17.8
Coke 2.2 2.4
Conversion ratio 70.4 71.0
Table 2
20 ℃ of density, gram per centimeter
30.8652
Viscosity: millimeter
2/ second, 50 ℃ 14.58
100℃ 4.37
Asphalitine, heavy %
C
5Insoluble matter 0.60
C
7Insoluble matter 0.026
Carbon residue, heavy % 0.04
Total sulfur, heavy % 0.42
Boiling range, ℃ initial boiling point 227
Heavy % 5 274
10 289
20 322
30 347
40 373
50 389
60 401
70 417
80 431
90 446
95 458
Do 475
Table 3
Catalyst C D
Used zeolite Na
2The heavy % 4.4 0.29 of O
RE
2O
3Heavy % 7.0 6.0
Chemical composition, heavy %
Na
2O 0.20 0.15
RE
2O
31.30 1.10
Al
2O
332.0 32.0
P 1.3 /
Specific surface, rice
2/ gram 256 263
Pore volume, milliliter/gram 0.51 0.51
Wear rate is during %
-12.3 5.5
Micro-activity, heavy %
800 ℃/4: 74 74
800 ℃/17: 56 59
The little oil of heavy oil, heavy %
Gas 12.4 15.7
Gasoline 53.0 53.7
Light diesel fuel 19.3 18.6
Coke 2.4 2.5
Conversion ratio 67.8 71.9
Table 4
Catalyst E F
Chemical composition, heavy %
Na
2O 0.30 0.34
Al
2O
349.5 49.7
P 1.0 0.1
Specific surface, rice
2/ gram 229 265
Wear rate is during %
-17.5 18
Micro-activity, heavy %
800 ℃/4: 76 69
800 ℃/17: 55 35
The little oil of heavy oil, heavy %
Gas 14.1 13.3
Gasoline 54.8 53.6
Light diesel fuel 19.6 19.8
Coke 2.0 2.0
Conversion ratio 70.9 69.1
Table 5
Catalyst G H
Chemical composition, heavy %
Na
2O 0.20 0.19
Al
2O
345.0 44.0
RE
2O
32.1 2.2
MgO / 3.1
P 1.0 1.6
Specific surface, rice
2/ gram 180 190
Wear rate is during %
-12.2＞10
Micro-activity, heavy %
800 ℃/4: 74 32
800 ℃/17: 49/
The little oil of heavy oil, heavy %
Gas 11.4 15.8
Gasoline 56.7 51.2
Light diesel fuel 17.8 16.3
Coke 2.2 3.1
Conversion ratio 70.3 70.1
Table 6
Chemical composition, heavy %
Al
2O
344.8
Na
2O 0.27
RE
2O
30.6
P 1.04
Specific surface, rice
2/ gram 198
Wear rate is during %
-12.3
Micro-activity, heavy %
800 ℃/4: 65
800 ℃/17: 48
The little oil of heavy oil, heavy %
Gas 14.6
Gasoline 57.6
Light diesel fuel 17.5
Coke 2.3
Conversion ratio 74.5
Table 7
Chemical composition, heavy %
Al
2O
327.3
Na
2O 0.23
RE
2O
31.6
P 3.7
Specific surface, rice
2/ gram 276
Wear rate is during %
-11.3
Micro-activity, heavy %
800 ℃/4: 48
800 ℃/17: 36
The little oil of heavy oil, heavy %
Gas 13.5
Gasoline 49.8
Light diesel fuel 23.0
Coke 2.1
Conversion ratio 65.0
Table 8
Chemical composition, heavy %
Al
2O
330.3
Na
2O 0.24
RE
2O
32.4
P 0.1
Specific surface, rice
2/ gram 260
Wear rate is during %
-16.0
Micro-activity, heavy %
800 ℃/4: 78
800 ℃/17: 38
The little oil of heavy oil, heavy %
Gas 14.7
Gasoline 53.4
Light diesel fuel 18.1
Coke 2.4
Conversion ratio 70.5
Table 9
Chemical composition, heavy %
Al
2O
343.5
Na
2O 0.30
P 1.8
Specific surface, rice
2/ gram 219
Wear rate is during %
-1
Micro-activity, heavy %
800 ℃/4: 75
800 ℃/17: 53
The little oil of heavy oil, heavy %
Gas 13.8
Gasoline 53.8
Light diesel fuel 19.2
Coke 2.1
Conversion ratio 68.7
Table 10
Chemical composition, heavy %
Al
2O
347.3
Na
2O 0.21
RE
2O
32.7
P 0.9
Specific surface, rice
2/ gram 197
Wear rate is during %
-12.0
Micro-activity, heavy %
800 ℃/4: 76
800 ℃/17: 50
The little oil of heavy oil, heavy %
Gas 17.6
Gasoline 50.0
Light diesel fuel 17.0
Coke 2.3
Conversion ratio 69.9
Table 11
Chemical composition, heavy %
Al
2O
345.0
Na
2O 0.20
RE
2O
32.1
P 0.90
Specific surface, rice
2/ gram 210
Wear rate is during %
-12.3
Micro-activity, heavy %
800 ℃/4: 77
800 ℃/17: 50
The little oil of heavy oil, heavy %
Gas 13.7
Gasoline 58.6
Light diesel fuel 18.3
Coke 2.3
Conversion ratio 74.6
Claims (10)
1, a kind of cracking hydrocarbon faujasite zeolite catalyst is characterized in that:
(1) it by 4～50 heavy % be selected from one of HY, HX, REHY, REHX or wherein two or more mixture or the mixture of one of them and other zeolite, the natural or artificial synthetic clay of 0～80 heavy %, the high temperature resistant phosphorus that contains aluminium inorganic oxide and 0.05～4.0 heavy % of 5～95 heavy % are formed;
(2) being prepared as follows of it: with Na
+Mixture, clay and the high temperature resistant aluminium inorganic oxide precursor that contains of the faujasite of pre-exchange degree 0～90% or it and other zeolite are mixed into glue by predetermined ratio, spray drying forming behind the homogeneous, through or without washing, carry out one or many ion-exchange post processing with the phosphorus-containing compound aqueous solution, filtration, drying.
2, according to the described catalyst of claim 1, it is characterized in that said catalyst in (1) by 5～45 heavy % be selected from one of HY, HX, REHY, REHX or wherein two or more mixture or one of them and the mixture of other zeolite, the natural or artificial synthetic clay of 0～80 heavy %, the high temperature resistant phosphorus that contains aluminium inorganic oxide and 0.4～3.0 heavy % of 10～75 heavy % form.
3,, it is characterized in that said other zeolite is selected from one of USY, USREY, HZSM, modenite, L zeolite, β zeolite according to the described catalyst of claim 1.
4,, it is characterized in that said clay is Cracking catalyst matrix kaolin, halloysite, imvite, a bentonite commonly used in (1) according to the described catalyst of claim 1.
5,, it is characterized in that the said high temperature resistant aluminium inorganic oxide that contains is Al in (1) according to the described catalyst of claim 1
2O
3, SiO
2Al
2O
3, Al
2O
3MgO, Al
2O
3CaO, Al
2O
3ZrO
2
6,, it is characterized in that said Na in (2) according to the described catalyst of claim 1
+The faujasite of pre-exchange degree 0～90% is NaY, NaX, HNaY, HNaX, REHNaY, REHNaX, REHaY, RENaX or two or more mixture wherein.
7,, it is characterized in that the said high temperature resistant precursor that contains the aluminium inorganic oxide is an aluminium colloidal sol in (2), intend thin water aluminium glue, silica-alumina gel, Al according to the described catalyst of claim 1
2O
3MgO glue, Al
2O
3CaO glue, Al
2O
3ZrO
2Glue.
8,, it is characterized in that said phosphorus-containing compound is phosphoric acid, phosphorous acid, phosphoric anhydride, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), ammonium phosphite, aluminum phosphate in (2) according to the described catalyst of claim 1.
9, according to the described catalyst of claim 1, it is characterized in that said ion-exchange post-treatment condition is in (2): phosphorus solution weight is 1～15 times of catalyst butt weight, phosphorus solution concentration is counted 0.001～17.5 heavy % with phosphorus content, exchange pressure 0～6 MPa, 5～99 ℃ of exchange temperature, 1～180 minute swap time.
10, according to the described catalyst of claim 9, it is characterized in that wherein said phosphorus solution concentration counts 0.02～12.0 heavy % with phosphorus content, exchange was carried out 2～100 minutes under normal pressure, 10～96 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91109945 CN1024504C (en) | 1991-10-24 | 1991-10-24 | Cracking catalyst containing phosphate and hydrogen Y molecular sieve, and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91109945 CN1024504C (en) | 1991-10-24 | 1991-10-24 | Cracking catalyst containing phosphate and hydrogen Y molecular sieve, and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1062157A CN1062157A (en) | 1992-06-24 |
| CN1024504C true CN1024504C (en) | 1994-05-18 |
Family
ID=4910069
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91109945 Expired - Lifetime CN1024504C (en) | 1991-10-24 | 1991-10-24 | Cracking catalyst containing phosphate and hydrogen Y molecular sieve, and its preparation |
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| Country | Link |
|---|---|
| CN (1) | CN1024504C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100389171C (en) * | 2004-08-31 | 2008-05-21 | 中国石油化工股份有限公司 | Catalytic cracking adjuvant and its preparing method |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1048428C (en) * | 1994-07-15 | 2000-01-19 | 中国石油化工总公司 | Multi-zeolite catalyzer for preparation of low-carbon olefines |
| CN1053918C (en) * | 1994-08-22 | 2000-06-28 | 中国石油化工总公司 | Double zeolite catalyst for prepn. of low carbon olefine |
| CN1072030C (en) * | 1997-11-11 | 2001-10-03 | 中国石油化工总公司 | Phosphorus-contained octahedro zeolite hydrocarbons cracking catalyst and preparation method therefor |
| US6884744B2 (en) * | 2001-04-13 | 2005-04-26 | W. R. Grace & Co.-Conn. | Zeolite based catalyst of ultra-high kinetic conversion activity |
| CN1311906C (en) * | 2004-07-29 | 2007-04-25 | 中国石油化工股份有限公司 | Cracking catalyst for hydrocarbon and preparation method |
| CN1322924C (en) * | 2004-07-29 | 2007-06-27 | 中国石油化工股份有限公司 | Cracking catalyst for hydrocarbon and preparation method |
| CN101670295B (en) * | 2008-09-11 | 2012-08-01 | 中国石油化工股份有限公司 | Preparation method of cracking catalyst |
| CN106927483B (en) * | 2015-12-29 | 2019-09-03 | 中国石油天然气股份有限公司 | Preparation method of modified Y-type molecular sieve |
-
1991
- 1991-10-24 CN CN 91109945 patent/CN1024504C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100389171C (en) * | 2004-08-31 | 2008-05-21 | 中国石油化工股份有限公司 | Catalytic cracking adjuvant and its preparing method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1062157A (en) | 1992-06-24 |
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