CN1112245C - Composite zeolite and its preparing process - Google Patents
Composite zeolite and its preparing process Download PDFInfo
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- CN1112245C CN1112245C CN 00123139 CN00123139A CN1112245C CN 1112245 C CN1112245 C CN 1112245C CN 00123139 CN00123139 CN 00123139 CN 00123139 A CN00123139 A CN 00123139A CN 1112245 C CN1112245 C CN 1112245C
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- zeolite
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- sio
- combined zeolite
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- 239000010457 zeolite Substances 0.000 title claims abstract description 166
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 158
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 157
- 238000000034 method Methods 0.000 title description 11
- 239000002131 composite material Substances 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000009415 formwork Methods 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000011259 mixed solution Substances 0.000 abstract description 3
- 229910052593 corundum Inorganic materials 0.000 abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 abstract 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 abstract 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 abstract 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000005642 Oleic acid Substances 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 abstract 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 abstract 1
- 239000011734 sodium Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- 239000003921 oil Substances 0.000 description 5
- 206010013786 Dry skin Diseases 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000000320 mechanical mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000002101 lytic effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention provides combined zeolite and a preparation method thereof. The combined zeolite is composed of two kinds of zeolite, namely modified Y zeolite with a cell parameter of 2.435 to 2.452 nm and beta zeolite with an organic template agent removed through calcination. Both kinds of zeolite are mixed, and then treated by a mixed solution containing H<+> and NH4 <+>. Finally, the zeolite is dried. The obtained combined zeolite can be used as an acid component of a catalyst for distillate oleic acid catalytic conversion, and is especially suitable for hydrocracking catalysts. When matched with amorphous SiO2-Al2O3 or Al2O3 as a carrier to carry a hydrocracking catalyst composed of metal in a VI-B family and (or) a VIII family, the combined zeolite has the characteristics of high activity and good flexibility.
Description
Technical field
The present invention relates to a kind of zeolite and preparation method thereof, especially relate to a kind of zeolite by β zeolite and Y combination of zeolites and preparation method thereof.
Background technology
At present, the acidic components that the acid catalyzed reaction catalyst is used are normally with Al
2O
3, SiO
2-Al
2O
3, SiO
2-MgO, acid-treated clays, various zeolites are main.Oil refining catalyst particularly, for example catalytic cracking, hydrocracking are especially with the main provider of modified zeolite as acidity.All contain modified zeolite in the catalyst of many processes such as hydrotreatment in recent years,, hydrofinishing and hydro-upgrading.And in certain catalyst, use the kind of zeolite also to develop to two or more combination of zeolites by a kind of zeolite gradually.
United States Patent (USP) 5,279,726 have announced a kind of hydrocracking catalyst of being made up of jointly Y zeolite and β zeolite, described Y zeolite is after carrying out ammonium exchange and steam treatment, also need carry out the ammonium exchange again, cell parameter is limited in the narrower scope that (2.452～2.459nm), difficult control is SiO to the requirement of β zeolite
2/ Al
2O
3Be 20～30, grain size is 0.1～0.7 micron, specific area 700～750m
2/ g, as seen this patent is narrower to the scope restriction of the various indexs of described zeolite, difficult control.In addition, two kinds of zeolites that use in the described catalyst are after modification is handled respectively, to carry out mechanical mixture again, and preparation process is complicated.
United States Patent (USP) 5,350,501 also relate to the applied in any combination of β zeolite and Y zeolite, the modifying process of its Y zeolite is more complicated, comprise ammonium exchange, steam treatment, ammonium exchange for the second time and steam treatment once again, the modified Y zeolite cell parameter that makes belongs to super-hydrophobic Y zeolite (UHPY) type between 2.425～2.435nm, also require its water adsorption amount less than 10 heavy %.Requirement to the β zeolite is identical with above-mentioned U.S. Pat 5,279,726, and Y and β zeolite also are after modification is handled respectively, to carry out mechanical mixture again, exist the preparation process complicated problems equally.
United States Patent (USP) 5,536,687 what provide also is the combination technique of β zeolite and modified Y zeolite, and its preparation principle and above-mentioned United States Patent (USP) 5,350,501 are similar, and the Y zeolite is through twice exchange, twice steam treatment, cell parameter is low, and hydrophobicity is strong, and operating process is long.
Summary of the invention
The purpose of this invention is to provide a kind of combined zeolite and preparation method thereof, preparation process is simple, processing ease, and the combined zeolite good reproducibility that makes is particularly suitable for the acidic components as the acid catalyzed reaction catalyst.
Combined zeolite of the present invention comprises: the percentage by weight with combined zeolite is a benchmark, modified Y zeolite 10%～95%, β zeolite 5%～90%; The silica alumina ratio of combined zeolite is 10～45, and specific surface is 600～900m
2/ g, pore volume 0.30～0.50cm
3/ g, infrared acidity 0.40～1.1mmol/g.
The cell parameter of above-mentioned modified Y zeolite should better be between 2.440～2.445nm between 2.435～2.452nm, SiO
2/ Al
2O
3Than should be 5.0～11.0, better be 5.0～8.0, Na
2The O weight content better is less than 2.3% less than 2.7%, and relative crystallinity better is greater than 85%, more preferably greater than 90%.Described β zeolite SiO
2/ Al
2O
3Than should better being 15～60 between 10～100, restricted index be less than 2, and preferably between 0.6～1.8, grain size is preferably between 0.1～0.7 micron, and specific area is preferably 650～750m
2/ g.。
The content of described modified Y zeolite in combined zeolite preferably 30%～90%, the content of described β zeolite preferably 10%～70%, the silica alumina ratio of described combined zeolite preferably 15～40, specific surface is 650～850m preferably
2/ g, pore volume is 0.38～0.48cm preferably
3/ g, infrared acidity is 0.50～0.90mmol/g preferably, the ratio of wherein infrared B acid and the acidity value of infrared L acid preferably 2～5: 1.
The preparation method of combined zeolite of the present invention is: after described modified Y zeolite and described β zeolite are mixed in proportion, with containing H
+And NH
4 +Cationic solution is handled, and treatment conditions are: zeolite is 1: 2～10 with the ratio of solution weight, be preferably 1: 3～and 8, treatment temperature is 25 ℃～100 ℃, is preferably 60 ℃～90 ℃, the processing time is 1～3 hour; The cell parameter of described modified Y zeolite should be between 2.435～2.452nm, SiO
2/ Al
2O
3Than should be 5.0～11.0, Na
2The O weight content is less than 2.7%.Described β zeolite SiO
2/ Al
2O
3Ratio should be between 10～100, and restricted index is less than 2.
The above-mentioned H that contains
+And NH
4 +H in the cationic solution
+Concentration is generally 0.05～0.35mol/L, is preferably 0.08～0.30mol/L, NH
4 +Concentration is generally 0.5～3.0mol/L, is preferably 1.0～2.0mol/L.
Above-mentioned modified Y zeolite is preferably: cell parameter is between 2.440～2.445nm, SiO
2/ Al
2O
3Than 5.0～8.0, relative crystallinity is greater than 85%, more preferably greater than 90%, and Na
2The O weight content is less than 2.3%.
Above-mentioned Y zeolite x optical diffraction figure preferably can meet United States Patent (USP) 3,130, and 007 or 3,929,672 results that provided.
Described β zeolite SiO
2/ Al
2O
3Better be 15～60, preferably between 0.6～1.8, grain size is preferably between 0.1～0.7 micron restricted index, and specific area is preferably 650～750m
2/ g.
Described modified Y zeolite can prepare as follows:
With containing NH
4 +Solution carries out NH to NaY zeolite raw material
4 +Exchange makes Na in the zeolite
2The O weight content is reduced to below 2.7%, then it is carried out steam treatment, and treatment conditions are: temperature is 400～700 ℃, and water vapor pressure is 0.01～0.3Mpa, and the time is 0.5～6 hour.
The SiO of used NaY zeolite raw material
2/ Al
2O
3Than being generally 4.8～5.2, more preferably greater than 5.0～5.2, relative crystallinity should be more preferably greater than 95% greater than 93%, and preferably greater than 97%, cell parameter should be between 2.464～2.470.
The x optical diffraction figure of described NaY zeolite preferably meets United States Patent (USP) 3,130, and 007 and 3,929,672 results that provided.
Described steam treatment can be with reference to United States Patent (USP) 3,929,672 or 3,923,640 or Deutsche Bundespatent 1,567,536 methods that provided carry out, the water vapour that promptly utilizes the self-contained water of exchange back zeolite at high temperature to produce is handled.Treatment conditions are preferably: 520～680 ℃ of temperature, and water vapor pressure 0.05～0.25Mpa, the time is 1～3 hour.
The used β zeolite of the present invention can prepare as follows:
Get β zeolite powder burning-off organic formwork agent and get final product, concrete grammar can for:
The β zeolite powder is placed mesh-belt kiln or electric furnace, feed air through being preheated to 500 ℃, under 600～650 ℃ of conditions, roasting 18～32 hours, burning-off organic formwork agent.
The synthetic of described β zeolite powder can silochrom be the silicon source, with the sodium metaaluminate is the aluminium source, with the tetraethyl ammonium hydroxide is the template agent, regulate the basicity of slurries with NaOH, 150～170 ℃ of crystallization 48～72 hours, be cooled to less than 70 ℃, carry out Separation of Solid and Liquid, be washed to pH less than 7.5, obtained the β zeolite powder in 4～8 hours 100～140 ℃ of dryings.
The H that contains of the present invention
+Solution generally is HNO
3, HCl, H
2SO
4Deng; The described NH that contains
4 +Solution generally be NH
4Cl, (NH
4)
2SO
4, NH
4NO
3Deng.
Combined zeolite provided by the present invention can be used for the acidic components of acid catalyzed reaction catalyst.With it is that the basis is equipped with matrix (as Al
2O
3, SiO
2-Al
2O
3Deng) and the made catalyst of group vib and VIII family hydrogenation metal be applicable to hydrocarbon conversion process, be specially adapted to heavy hydrocarbon and change into liquefied gas, naphtha, jet fuel, the hydrocracking process of diesel oil distillate.This catalyst both can be used for second section hydrocracking catalyst of one-stage serial flow process, after promptly the higher heavy distillates of impurity such as sulfur-bearing, nitrogen, oxygen are introduced into Hydrobon catalyst and remove sulphur, nitrogen oxygen, contacted with hydrocracking catalyst again.Also can be the promptly refining section of two sections operations effluent through separate remove anhydrate, ammonia, hydrogen sulfide or part light fraction, contact with hydrocracking catalyst again.
When combined zeolite of the present invention is used for the acidic components of hydrocracking catalyst, catalyst comprises: the percentage by weight with catalyst is a benchmark, combined zeolite of the present invention accounts for 10%-30%, binder constitutes 10%-15%, amorphous silicon aluminium accounts for 25%-60%, hydrogenation active metals ingredients constitute 20%-30%.
What described adhesive was commonly used is aluminium oxide, and the hydrogenation active metals component is commonly used is among W, Mo, Ni, the Co one or more, and that the most frequently used is W and Ni.
Compared with prior art, the present invention has following beneficial effect:
Method β zeolite provided by the invention is except that the burning amine of necessity, before processing, do not need again through any processing, the Y zeolite only needs two to three exchanges, a steam treatment, carry out solution-treated again after two kinds of zeolites after will handling then mix, so preparation process is simple, processing ease, flow process is short, thereby good reproducibility.Zeolite of the present invention is equipped with other matrix (Al
2O
3, SiO
2-Al
2O
3) cooperate the hydrocracking catalyst of making strong to feedstock oil adaptability with periodic table of elements VIB and/or VIII family hydrogenation component again, the lytic activity height, product selectivity is good and have a stronger flexibility.
The specific embodiment
Example 1:
Get SiO
2/ Al
2O
3Be 5.1, relative crystallinity is 98%, and cell parameter is 2.468nm, Na
2The O weight content is 10.3% NaY Zeolites Zeolites 100 grams, is crushed to less than 20 orders, contains 80 gram NH with 800ml
4NO
3Solution stirred 1 hour down at 90～95 ℃, be cooled to 45 ℃, the elimination mother liquor, repeat 4 times, add 2 liters of washing leaching cakes of deionized water then, filter cake is placed in the hydrothermal treatment consists stove at last, under 620 ℃ of conditions, control system pressure was handled 3 hours at 0.08MPa.The products obtained therefrom cell parameter is 2.444nm, SiO
2/ Al
2O
3Than being: 5.7, Na
2The O weight content is: 2.5%, and relative crystallinity is: 82%.
Example 2: get SiO
2/ Al
2O
3Be 5.1, relative crystallinity is 98%, and cell parameter is 2.468nm, Na
2The O weight content is that 10.3% NaY zeolite, 100 grams are crushed to less than 20 orders, with the NH of 1.5N
4Cl solution exchanges 2 hours for 0.5 liter under 85～95 ℃, be cooled to less than 45 ℃ the elimination mother liquor, repeat 3 times, add 2 liters of deionized water washing leaching cakes then, at last filter cake is placed the hydrothermal treatment consists stove, the control steam partial pressure is warming up to 677 ℃ less than 0.15MPa to electricity, keeps 1 hour.The cell parameter of products obtained therefrom is 2.442～2.445nm, SiO
2/ Al
2O
3Than being 5.8, Na
2The O weight content is: 2.2%, and relative crystallinity is: 83%.
Example 3:
The SiO that will under alkali condition, synthesize
2/ Al
2O
3β zeolite powder 100 grams than for 25-32 in the muffle furnace of packing into, feed the air through preheating, and temperature is 653 ℃ in the control stove, keeps 24 hours.Product property is: relative crystallinity is 82%, Na
2The O weight content is: 3.2%, and SiO
2/ Al
2O
3Than being 28.7, restricted index 1.8.
Example 4:
β zeolite 100 grams identical with example 3 are crushed to less than 100 orders, and in the Fluo-Solids roaster of packing into, temperature is 680 ℃ in the control stove, and aerating oxygen, oxygen flow are 3L/ hour, keep 8 hours.Product property is: relative crystallinity is 80%, Na
2The O weight content is: 3.2%, and SiO
2/ Al
2O
3Than being 28.7, restricted index 1.9.
Example 5:
Example 1 gained modified Y zeolite is mixed by the proportioning of table 1 with the β zeolite of example 4, get the mixed zeolite 100 gram HNO that contain 0.14M
3NH with 0.8M
4NO
3Mixed solution 0.8L handled under 80～90 ℃ 2 hours, filtered, and repeated 2～3 times, added 2 liters of washings of deionized water, and filter cake promptly obtains product in 8 hours dryings of 110～120 ℃ of dryings.The proportioning and the product property of combined zeolite are listed in the table below.
Table 1
| Combination | 1 | 2 | 3 | 4 |
| β/Y (weight) | 1/9 | 1/4 | 1/1 | 4/1 |
| SiO 2/Al 2O 3 | 11.3 | 17.8 | 33.4 | 42.1 |
| C I，mmol/g | 1.077 | 0.989 | 0.956 | 0.637 |
| C B，mmol/g | 0.638 | 0.662 | 0.416 | 0.358 |
| C L，mmol/g | 0.394 | 0.327 | 0.540 | 0.315 |
| Specific surface m 2/g | 837 | 813 | 783 | 664 |
| Pore volume ml/g | 0.485 | 0.483 | 0.411 | 0.397 |
Annotate: C in the table
iRepresent infrared acidity, C
BRepresent infrared B acid, C
LRepresent infrared L acid, following table together.
Example 6:
Example 2 is mixed by the proportioning of table 2 with the β zeolite of example 3, get the mixed zeolite 100 gram H that contain 0.14M
+NH with 0.8M
4 +Mixed solution 0.8L handled under 80～90 ℃ 2 hours, filtered, and repeated 3 times, added 2 liters of washings of deionized water, and filter cake promptly obtains product 110～120 ℃ of dryings 8 hours.The proportioning and the product property of combined zeolite are listed in the table below.
Table 2
| Combined zeolite | 1 | 2 | 3 | 4 |
| β/Y | 1/9 | 1/4 | 1/1 | 4/1 |
| SiO 2/Al 2O 3 | 12.9 | 18.1 | 33.7 | 41.8 |
| C i，mmol/g | 1.003 | 0.956 | 0.917 | 0.587 |
| C B，mmol/g | 0.617 | 0.643 | 0.472 | 0.317 |
| C L，mmol/g | 0.386 | 0.313 | 0.445 | 0.27 |
| Specific surface m 2/g | 814 | 798 | 765 | 647 |
| Pore volume ml/g | 0.489 | 0.478 | 0.401 | 0.376 |
Example 7:
Four kinds of combined zeolites with example 5 are acidic components respectively, and combined zeolite is joined SiO
2-Al
2O
3Do in the matrix of carrier, again with Al
2O
3Make adhesive mixing extruded moulding, support W-Ni hydrogenation metal component, make corresponding hydrocracking catalyst.Catalyst is formed transitivity and is listed in the table below, and the numbering of catalyst is with the combined zeolite numbering that is adopted in the table.
Table 3
| Catalyst | 1 | 2 | 3 | 4 |
| Combined zeolite, % | 22.8 | 19 | 21 | 20.1 |
| SiO 2-Al 2O 3，％ | 32.6 | 35.5 | 34.2 | 35.1 |
| Adhesive, % | 14.7 | 16 | 15 | 14.9 |
| WO 3，m％ | 24.5 | 22.7 | 23.4 | 24.8 |
| NiO，m％ | 5.37 | 6.82 | 6.53 | 4.99 |
| Specific surface, m 2/g | 317 | 319 | 298 | 287 |
| Pore volume, ml/g | 0.341 | 0.320 | 0.323 | 0.311 |
Example 8:
Four kinds of combined zeolites with example 6 are acidic components respectively, and the preparation method with example 7 makes corresponding hydrocracking catalyst.Catalyst is formed transitivity and is listed in the table below, and the numbering of catalyst is with the numbering of the combined zeolite that is adopted.
Table 4
| Catalyst | 5 | 6 | 7 | 8 |
| Combined zeolite, % | 23.1 | 18 | 17.5 | 18 |
| SiO 2-Al 2O 3，％ | 32.2 | 35.4 | 38.1 | 37.1 |
| Adhesive, % | 15 | 17 | 17.4 | 16.2 |
| WO 3, heavy % | 23.9 | 23.7 | 24.0 | 24.8 |
| NiO, heavy % | 5.79 | 5.87 | 5.84 | 5.84 |
| Specific surface, m 2/g | 309 | 317 | 301 | 273 |
| Pore volume, ml/g | 0.347 | 0.308 | 0.315 | 0.292 |
Embodiment 9
Subtracting three-way distillate with Iran is the hydrocracking catalyst 6 that the raw material evaluation is made with combined zeolite, and Iran subtracts three-way distillate character and is listed in the table below:
Table 5
The evaluation result of catalyst on small-sized hydrocracking unit is listed in the table below:
| Density, g/cm 3 | 0.9151 |
| Boiling range, ℃ | 254～545 |
| Sulphur, m% | 1.67 |
| Nitrogen, m% | 0.1944 |
Table 6
| Cracking catalyst | Composite zeolite catalyst | The reference agent |
| Feedstock oil | Iran subtracts three-way | Iran subtracts three-way |
| Reaction pressure (always), MPa | 15.7 | 15.7 |
| Volume space velocity, h -1 | 1.21 | 1.21 |
| Hydrogen to oil volume ratio | 1150 | 1150 |
| Reaction temperature, ℃ | 378～383 | 390 |
| The refined oil nitrogen content, μ g/g | ～30 | ～30 |
| ＞350 ℃ of conversion ratios, m% | 75 | 75 |
Claims (28)
1, a kind of combined zeolite is a benchmark with the percentage by weight, comprising: modified Y zeolite 10%～95%, β zeolite 5%～90%; The silica alumina ratio of combined zeolite is 10～45, and specific surface is 600～900m
2/ g, pore volume 0.30～0.50cm
3/ g, infrared acidity 0.40～1.1mmol/g.
2, combined zeolite in accordance with claim, the cell parameter that it is characterized in that described modified Y zeolite between 2.435～2.452nm, SiO
2/ Al
2O
3Than being 5.0～11.0, Na
2The O weight content is less than 2.7%,
3, described combined zeolite in accordance with claim is characterized in that described β zeolite SiO
2/ Al
2O
3Than between 10～100, restricted index is less than 2.
4,, it is characterized in that described modified Y zeolite weight content is 30%～90% according to the described combined zeolite of claim 1.
5, according to the described combined zeolite of claim 1, the weight content that it is characterized in that described β zeolite is 10%～70%.
6, according to the described combined zeolite of claim 1, the silica alumina ratio that it is characterized in that described combined zeolite is 15～40.
7, according to the described combined zeolite of claim 1, the specific surface that it is characterized in that described combined zeolite is 650～850m
2/ g, pore volume are 0.38～0.48cm
3/ g.
8, according to the described combined zeolite of claim 1, it is characterized in that the infrared acidity of described combined zeolite is 0.50～0.90mmol/g, wherein infrared B acid is 2～5 with the ratio of the acidity value of infrared L acid: 1.
9, according to the described combined zeolite of claim 1, it is characterized in that described modified Y zeolite is: cell parameter is 2.440～2.445nm, SiO
2/ Al
2O
3Than being 5.0～8.0, relative crystallinity is greater than 85%, Na
2The O weight content is less than 2.3%.
10,, it is characterized in that described β zeolite SiO according to the described combined zeolite of claim 1
2/ Al
2O
3Be 15～60, restricted index is between 0.6～1.8, and grain size is between 0.1～0.7 micron, and specific area is 650～750m
2/ g.
11, the preparation method of the described combined zeolite of a kind of claim 1 comprises: after described modified Y zeolite and described β zeolite are mixed in proportion, with containing H
+And NH
4 +Cationic solution is handled, and treatment conditions are: zeolite is 1: 2～10 with the ratio of solution weight, and treatment temperature is 25 ℃～100 ℃, and the processing time is 0.5～5 hour; The cell parameter of described modified Y zeolite should be between 2.435～2.452nm, SiO
2/ Al
2O
3Than should be 5.0～11.0, Na
2The O weight content is less than 2.7%, described β zeolite SiO
2/ Al
2O
3Ratio should be between 10～100, and restricted index is less than 2; The above-mentioned H that contains
+And NH
4 +H in the cationic solution
+Concentration is 0.05～0.35mol/L, NH
4 +Concentration is 0.5～3.0mol/L.
12,, it is characterized in that described usefulness contains H according to the preparation method of the described combined zeolite of claim 11
+And NH
4 +The condition that cationic solution is handled is: zeolite is 1: 3～8 with the ratio of solution weight, and treatment temperature is 60 ℃～90 ℃, and the processing time is 1～3 hour.
13, according to the preparation method of the described combined zeolite of claim 11, it is characterized in that described modified Y zeolite is: cell parameter is 2.440～2.445nm, SiO
2/ Al
2O
3Than being 5.0～8.0, relative crystallinity is greater than 85%, Na
2The O weight content is less than 2.3%.
14,, it is characterized in that described β zeolite SiO according to the preparation method of the described combined zeolite of claim 11
2/ Al
2O
3Be 15～60, restricted index is between 0.6～1.8, and grain size is between 0.1～0.7 micron, and specific area is 650～750m
2/ g.
15,, it is characterized in that described modified Y zeolite prepares as follows according to the preparation method of the described combined zeolite of claim 11:
With containing NH
4 +Solution carries out NH to NaY zeolite raw material
4 +Exchange makes Na in the zeolite
2The O weight content is reduced to below 2.7%, then it is carried out steam treatment, and treatment conditions are: temperature is 400～700 ℃, and water vapor pressure is 0.01～0.3Mpa, and the time is 0.5～6 hour.
16,, it is characterized in that described β zeolite is by obtaining behind the organic formwork agent in the burning-off β zeolite powder according to the preparation method of the described combined zeolite of claim 11.
17,, it is characterized in that the SiO of described NaY zeolite raw material according to the preparation method of the described combined zeolite of claim 15
2/ Al
2O
3Than being 4.8～5.2, relative crystallinity is greater than 93%, and cell parameter should be between 2.464～2.470.
18, according to the preparation method of the described combined zeolite of claim 15, it is characterized in that described steam treatment is meant that the water vapour that utilizes the self-contained water of exchange back zeolite at high temperature to produce handles, treatment conditions are: 520～680 ℃ of temperature, water vapor pressure 0.05～0.25Mpa, the time is 1～3 hour.
19, a kind of hydrocracking catalyst that contains combined zeolite, comprise: the percentage by weight with catalyst is a benchmark, combined zeolite accounts for 10%-30%, binder constitutes 10%-15%, and amorphous silicon aluminium accounts for 25%-60%, hydrogenation active metals ingredients constitute 20%-30%, described combined zeolite is a benchmark with the percentage by weight, comprising: modified Y zeolite 10%～95%, β zeolite 5%～90%, the silica alumina ratio of combined zeolite is 10～45, and specific surface is 600～900m
2/ g, pore volume 0.30～0.50cm
3/ g, infrared acidity 0.40～1.1mmol/g.
20, according to the described hydrocracking catalyst that contains combined zeolite of claim 19, the cell parameter that it is characterized in that described modified Y zeolite between 2.440～2.452nm, SiO
2/ Al
2O
3Than being 5.0～11.0, Na
2The O weight content is less than 2.7%,
21,, it is characterized in that described β zeolite SiO according to the described hydrocracking catalyst that contains combined zeolite of claim 19
2/ Al
2O
3Than between 10～100, restricted index is less than 2.
22,, it is characterized in that described modified Y zeolite weight content is 30%～90% according to the described hydrocracking catalyst that contains combined zeolite of claim 19.
23, according to the described hydrocracking catalyst that contains combined zeolite of claim 19, the weight content that it is characterized in that described β zeolite is 10%～70%.
24, according to the described hydrocracking catalyst that contains combined zeolite of claim 19, the silica alumina ratio that it is characterized in that described combined zeolite is 15～40.
25, according to the described hydrocracking catalyst that contains combined zeolite of claim 19, the specific surface that it is characterized in that described combined zeolite is 650～850m
2/ g, pore volume are 0.38～0.48cm
3/ g.
26, according to the described hydrocracking catalyst that contains combined zeolite of claim 19, it is characterized in that the infrared acidity of described combined zeolite is 0.50～0.90mmol/g, wherein infrared B acid is 2～5 with the ratio of the acidity value of infrared L acid: 1.
27, according to the described hydrocracking catalyst that contains combined zeolite of claim 19, it is characterized in that described modified Y zeolite is: cell parameter is 2.440～2.445nm, SiO
2/ Al
2O
3Than being 5.0～8.0, relative crystallinity is greater than 85%, Na
2The O weight content is less than 2.3%.
28,, it is characterized in that described β zeolite SiO according to the described combined zeolite of claim 19
2/ Al
2O
3Be 15～40, restricted index is between 0.6～1.8, and grain size is between 0.1～0.7 micron, and specific area is 650～750m
2/ g.
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|---|---|---|---|
| CN 00123139 CN1112245C (en) | 2000-10-26 | 2000-10-26 | Composite zeolite and its preparing process |
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|---|---|
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| CN1112245C true CN1112245C (en) | 2003-06-25 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9469817B2 (en) | 2014-02-20 | 2016-10-18 | China Petroleum & Chemical Corporation | Hydrocracking catalyst and use of the same |
| US9623403B2 (en) | 2014-08-25 | 2017-04-18 | China Petroleum & Chemical Corporation | Naphtha reforming catalyst and preparation method thereof |
| US12172903B2 (en) | 2018-10-26 | 2024-12-24 | China Petroleum & Chemical Corporation | Phosphorus-containing high-silica molecular sieve, its preparation and application thereof |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7098161B2 (en) * | 2000-10-20 | 2006-08-29 | Abb Lummus Global Inc. | Method of treating zeolite |
| CN104667968B (en) * | 2013-11-26 | 2017-04-12 | 中国石油化工股份有限公司 | A hydrocracking catalyst carrier and a preparing method thereof |
| CN105618119B (en) * | 2014-11-03 | 2017-12-19 | 中国石油化工股份有限公司 | A kind of method for preparing hydrocracking catalyst |
| CN108264927A (en) * | 2016-12-30 | 2018-07-10 | 中国石油天然气股份有限公司 | Hydrogenation catalyst carrier and preparation method thereof |
| US11524281B2 (en) | 2017-10-31 | 2022-12-13 | China Petroleum & Chemical Corporation | Phosphorus-containing molecular sieve, its preparation and application thereof |
-
2000
- 2000-10-26 CN CN 00123139 patent/CN1112245C/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9469817B2 (en) | 2014-02-20 | 2016-10-18 | China Petroleum & Chemical Corporation | Hydrocracking catalyst and use of the same |
| US9623403B2 (en) | 2014-08-25 | 2017-04-18 | China Petroleum & Chemical Corporation | Naphtha reforming catalyst and preparation method thereof |
| US12172903B2 (en) | 2018-10-26 | 2024-12-24 | China Petroleum & Chemical Corporation | Phosphorus-containing high-silica molecular sieve, its preparation and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1350886A (en) | 2002-05-29 |
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