CN1091399C - Process for modifying Y-zeolite - Google Patents
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- CN1091399C CN1091399C CN99107940A CN99107940A CN1091399C CN 1091399 C CN1091399 C CN 1091399C CN 99107940 A CN99107940 A CN 99107940A CN 99107940 A CN99107940 A CN 99107940A CN 1091399 C CN1091399 C CN 1091399C
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Abstract
The present invention relates to a method for modifying Y type zeolite. The method comprises the following steps: mixing Y type zeolite whose sodium content is smaller than 1 wt% with oxides or oxyacid salts of at least one acid-forming metal element and oxides or salts of at least one alkali-forming or amphoteric metal element except for alkali metals in a weight ratio of 100: (1 to 30): (0.1 to 15); contacting the mixture with steam at 400 DEG C to 800 DEG C and weight space velocity of 0.05 to 3.5/hour in a steam-contained atmosphere. Compared with the prior art, the modified method has the advantages of simple steps and easy control, and the obtained modified zeolite is especially suitable for carriers and/or active components of catalysts in the isomerization reaction of n-alkane.
Description
The invention relates to a kind of method of modifying of y-type zeolite.
The catalyst that with the zeolite is active component has been widely used in the various hydrocarbon conversion reactions.For different hydrocarbon conversion reactions, the composition of employed zeolite, structure and character are also different in the catalyst.In order to adapt to the needs of various hydrocarbon conversion reactions, people have carried out various study on the modification to zeolite, are purpose with activity, selectivity and the stability of improving zeolite mainly.The report of existing so far many successful methods, for example common H that uses
+Substitute the Na in the NaY zeolite
+, can form hydrogen Y zeolite with more Bronsted acids center; NaY zeolite and different metal ion (comprising alkaline-earth metal, transition metal, rare earth metal etc.) exchange forms the metal y-type zeolite, can improve the stability of zeolite; NaY zeolite and metal salt solution and ammonia salting liquid exchange, and form the metallic hydrogen y-type zeolite, good stability not only, and the catalytic pyrolysis activity also increases.USP3293172, USP3402996, USP3449070 disclose the method for high-temperature vapor processing y-type zeolite, can make structure cell shrink the structure super stabilizing.
Because y-type zeolite mainly is the active constituent as catalytic cracking catalyst,, people should have high crystallization reservation, high hydrothermal stability and generation gasoline selective so often only emphasizing the zeolite after the modification.In recent years, produce middle distillate oil or lube base wet goods heavy fraction of oil Application of Catalyst with richness, people have further research again to the modification of wherein zeolite component.
USP4874729 discloses a kind of method of modifying of y-type zeolite, and modifying process comprises to be handled the zeolite of mol ratio between 0.13 to 1.0 of basic anhydride and aluminium oxide and two steps of high-temperature roasting with the saline solution of one or more polyvalent metals.The atomic number of suitable metal is between 12-83, preferably magnesium, aluminium, gallium, iron, copper, nickel, manganese, cobalt, zinc.Zeolite after the modification is suitable for preparing hydrotreatment or hydrocracking catalyst.
USP4874730 and EP288112 disclose a kind of method of modifying of y-type zeolite, and modifying process comprises that the mol ratio with alkali metal oxide and aluminium oxide is not more than 0.13 y-type zeolite and handles and roasting with a kind of metal salt solution.The multivalent metal cation radius that is suitable for is between 0.6-1.0A, according to CRC Handbook ofChemistry and Physics, Cleveland, Ohio, 56th ed.1975-1976, the data that F-209 and F-210 page or leaf provide, the multivalent metal cation that satisfies this requirement comprises: Ag
2+, Bi
3+, Bi
5+, Ca
2+, Cd
2+, Ce
4+, Co
2+, Co
3+, Cr
2+, Cr
3+, Cu
2+, Fe
2+, Fe
3+, Ga
3+, In
3+, Ir
4+, Mg
2+, Mn
2+, Mn
3+, Mn
4+, Mo
4+, Ni
2+, Pb
4+, Pd
2+, Pd
4+, Pt
2+, Pt
4+, Re
4+, Rh
3+, Ru
4+, Sn
2+, Sn
4+, Ta
5+, Ti
2+, Ti
3+, Ti
4+, V
3+, V
4+, W
6+And Zn
2+The Zeolite modifying processing procedure comprises: prepare certain density saline solution, solution and zeolite mix by the agent of 10 milliliters/gram, carry out ion-exchange at 95 ℃, after filtration, washing, dry, following 600～700 ℃ of roastings of steam existence obtain the purpose product.It is the hydrogenation conversion catalyst of purpose product that zeolite after modification is suitable for preparing with the intermediate oil.
But above-mentioned patent is in the cation that provides, and high valent cationic is hydrolysis easily in the aqueous solution, even picture Fe
3+This trivalent metal cation also must be only stable in the aqueous medium of high acidity.And W
6+On the high price metal, then can only be in aqueous medium with the oxyacid root, poly-polyacid root form exists.Obviously, some high valent cationic is unsuitable for providing the modification that method is carried out zeolite according to patent, and the processing procedure more complicated.
Zeolites, 1993, Vol 13,269～274b has reported at high temperature NaY zeolite and V
2O
5, MoO
3, WO
3Solid reacting method, point out V in 680～750K temperature range
2O
5, MoO
3Transportable and embed in the duct or supercage of zeolite, when embedded quantity is lower than R
V2O5=0.05 and R
MoO3(silicon+aluminium) atomicity in=0.07[R=metallic atom number/NaY structure cell] time, V
2O
5Or MoO
3Existence to not influence of zeolite crystal structure.When temperature surpasses 750K and along with the increase of oxide concentration, V
2O
5Or MoO
3To cause the amorphization of zeolite.Because WO
3The fusing point height, water insoluble, make it pass through this solid function and be difficult to embed in the zeolite cavity.
Zeolites, 1990, Vol 10,772 has reported the method for introducing vanadium by solid ionic exchange in y-type zeolite, is in containing the thermal air current of steam, makes VO in the mixture of vanadic anhydride and HY zeolite
3+Cation and H
+Solid phase ion-exchange takes place, so that vanadium can enter in the supercage and β cage of zeolite.
The objective of the invention is on the basis of above-mentioned prior art, a kind of method of modifying of y-type zeolite is provided, make it have isomerization performance, and the operation of preparation process is simple relatively, easily control.
Method provided by the invention comprises and becomes the oxide or the oxysalt of sour metallic element to mix by 100: 1～30: 0.1～15 weight ratio with at least a oxide that becomes alkali or tellurium or salt except that alkali metal less than the y-type zeolite of 1 heavy % with at least a sodium content (in sodium oxide molybdena weight), is 0.05～3.5 hour with mixture and steam weight space velocity under 400～800 ℃
-1Containing water vapor atmosphere contact 0.5～8 hour.
According to method provided by the invention, described y-type zeolite can be NaY, NH
4Y-type zeolite after Y, HY, REY, REHY or super stabilizing are handled, described sodium content can be that NaY type zeolite is obtained through ion-exchange (as ammonium ion exchange) less than the y-type zeolite of 1 heavy %.
Described metallic element is classified according to Figure 20-2 of the 402nd page of " inorganic chemistry " volume two (People's Education Publishing House, in March, 1978 front page): become sour metallic element to comprise V, Cr, Mo, Tc, Ru, Rh, Pd, W, Os, Ir, Pt, Au.Become alkali or tellurium to comprise: Mg, Ca, Sc, Sr, Y, Ba, La, Ti, Zr, Nb, Hf, Ta, Al, Zn, Ga, Ge, In, Sn, Mn, Fe, Co, Ni, Cu, Ag, Cd, Hg, Tl, Sb, Pb, Bi, Po.
The preferred V of one-tenth acid metallic element described in the present invention, Cr, Mo, W, the preferred Mg of base element, Ti, Zr, Nb, Al, Fe, Co, Ni, Zn, Sb.
The oxide of the one-tenth acid metallic element described in the present invention is an acid anhydrides that this element becomes, oxysalt is meant the inorganic salts that the oxyacid root by these elements is become, but preferably cation burn off or cation after high-temperature roasting is the inorganic salts that remain to be introduced base element, tellurium.
The oxide of one-tenth alkali described in the present invention or tellurium is meant these element stable oxide, the hydrate of oxide, described salt is meant the water-soluble inorganic salt of these elements, organic salt, but preferably inorganic salts, organic salt or the anion of anion burn off after high-temperature roasting contain the acid ion that remains to be introduced into sour metallic element.
The mixed process of the zeolite described in the present invention and two kinds of dissimilar oxides or salt can be carried out synchronously, also can finish step by step; Can do in the mechanical lapping condition and mix, also can wet mixing in the presence of the water arranged.Mixed material can directly carry out high-temperature water vapor and handle except that employing pulp process needs after filtration.
Zeolite described in the present invention and at least a oxide that becomes sour metallic element or oxysalt with at least a except that alkali metal the oxide that becomes alkali metal or amphotere or the weight ratio preferred 100: 2～20: 0.5～10 of salt.
Preferred 450～750 ℃ of hydrothermal treatment consists temperature described in the present invention.Described moisture vapor atmosphere is one or more the mixture in water vapour or water vapour and air, oxygen, the inert gas, the preferred water steam.Preferred 0.1～2.5 hour of the weight space velocity of steam
-1Mixed material and preferred 2～6 hours of time of contact of containing water vapor atmosphere.
According to method provided by the invention, process of zeolite modification is simple than prior art, easily control.Zeolite structure cell after modification is handled shrinks, structure is super steady, and lattice constant can be retracted to from the 24.56A of NaY and be lower than 24.43A.Become sour metallic element with the form of oxide or oxysalt under the high temperature moisture vapor atmosphere with the zeolite effect after, though impel the zeolite dealuminzation, but the acid amount of zeolite does not reduce, from the acid result of pyridine adsorption, FT-IR working sample, and its total acid content＞20A/ gram-centimeter
2Become the cationic existence of alkali metal that acid centre intensity is reduced, the reduction lytic activity.Two kinds of elements have been realized adjustment and control to zeolitic acid intensity and lytic activity to the acting in conjunction of zeolite, make between the zeolite and aluminium oxide of lytic activity before modification of the zeolite after the modification, and isomerization performance improve greatly.
Can be widely used as with the zeolite after the method modification provided by the invention and to emphasize isomerization, particularly the carrier of normal alkane isomerization catalyst for reaction and/or active component.Though the conversion ratio of the n-alkane of the catalyst of the preparation of the zeolite after this method modification is lower than the catalyst of the zeolite preparation that provides according to prior art, the catalyst that the zeolite that the isomerization reaction selectivity obviously is better than providing according to prior art prepares.For example be reaction raw materials with the normal heptane, 350 ℃ of reaction temperatures, hydrogen pressure 2.5MPa, volume space velocity 1 hour
-1Reaction condition under, during with the hydrotreating catalyst of the zeolite that contains 10.5 heavy % the inventive method preparations, the isomerization selectivity of normal heptane is brought up to 83.9～92.2 heavy %, and uses the catalyst of unmodified HY zeolite preparation, and the isomerization selectivity of its normal heptane has only 11.5 heavy %.
The following examples will the present invention is further illustrated.
Embodiment 1～6 is for to carry out modification according to method provided by the invention to y-type zeolite.
Embodiment 7～12 illustrates the catalytic performance of the hydrotreating catalyst of the zeolite that contains the inventive method modification.
Embodiment 1
With 800 gram NaY type zeolite (SiO
2/ Al
2O
3=4.8, degree of crystallinity is decided to be 100%, Chang Ling refinery product) to place 4000 ml concns be in ammonium chloride (Beijing Chemical Plant's product the is analyzed pure) aqueous solution of 1.0M, exchange 1 hour down at 90 ℃, filter, with the deionized water cyclic washing to not having chlorion, 120 ℃ of oven dry, 550 ℃ of roastings 4 hours, repeat said process twice, obtain the HY type zeolite of the heavy % of sodium content (in sodium oxide molybdena)＜0.35 (flame atomic absorption spectrometry mensuration), its physico-chemical property is listed in the table 1.Wherein lattice constant, relative crystallinity adopt x-ray diffraction method to measure, and the acid amount adopts the fourier infrared spectroscopic assay.
Take by weighing aluminum nitrate [Al (NO
3)
3.9H
2O, chemical pure, Beijing Chemical Plant's product] 6.0 grams, ammonium metatungstate [(NH
4)
2W
4O
13.18H
2O, chemical pure, Sichuan Zigong Hard Alloy Foundry product] 7.0 the gram be dissolved in 50 ml deionized water, this solution and above-mentioned HY type zeolite 100 grams are mixed, mixed material is placed tube furnace, feed deionized water by 100 Grams Per Hours, be warming up to 700 ℃, constant temperature 4 hours obtains after the cooling containing after the modification and adds aluminium and tungsten (in oxide weight) and be respectively 0.7% and 4.6% Y zeolite A, and its physico-chemical property is listed in the table 1.
Embodiment 2
Take by weighing aluminum nitrate [Al (NO
3)
3.9H
2O, chemical pure, Beijing Chemical Plant's product] 6.0 grams, ammonium metatungstate [(NH
4)
2W
4O
13.18H
2O, chemical pure, Sichuan Zigong Hard Alloy Foundry product] 20.6 the gram be dissolved in 50 ml deionized water, HY zeolite 100 grams of preparation among this solution and the embodiment 1 are mixed, mixed material is placed tube furnace, feed deionized water by 10 Grams Per Hours, be warming up to 650 ℃, constant temperature 4 hours obtains after the cooling containing after the modification and adds aluminium and tungsten (in oxide weight) and be respectively 0.6% and 12.5% Y zeolite B, and its physico-chemical property is listed in the table 1.
Embodiment 3
Take by weighing zinc oxide (ZnO, chemical pure, auxiliary reagent factory, Shenyang City product) 4.0 grams, vanadic anhydride (V
2O
5Chemical pure, Chengdu, Sichuan chemical reagent work product) HY zeolite 100 grams, 30 ml deionized water of preparation mix among 3.0 grams and the embodiment 1, mixed material is placed tube furnace, feed deionized water by 5 Grams Per Hours, be warming up to 650 ℃, constant temperature 4 hours, obtain containing after the modification zinc and vanadium (in oxide weight) after the cooling and be respectively 3.7% and 2.8% Y zeolite C, its physico-chemical property is listed in the table 1.
Embodiment 4
Take by weighing cobalt oxide (CoO, chemical pure, Shanghai reagent two factory's products) 2.0 grams, vanadic anhydride (V
2O
5Chemical pure, Chengdu, Sichuan chemical reagent work product) HY zeolite 100 grams, 30 ml deionized water of preparation mix among 5.0 grams and the embodiment 1, mixed material is placed tube furnace, feed deionized water by 250 Grams Per Hours, be warming up to 650 ℃, constant temperature 4 hours, obtain containing after the modification cobalt and vanadium (in oxide weight) after the cooling and be respectively 1.8% and 4.6% Y zeolite D, its physico-chemical property is listed in the table 1.
Embodiment 5
Weighing magnesium nitrate [Mg (NO
3)
2.6H
2O, chemical pure, Beijing Chemical Plant's product] 6.4 grams, ammonium dichromate [(NH
4)
2Cr
2O
7, technical grade, Tianjin is with biochemical plant's product] 4.0 grams, ammonium metatungstate [(NH
4)
2W
4O
13.18H
2O, chemical pure, Sichuan Zigong Hard Alloy Foundry product] 10.6 the gram be dissolved in 50 ml deionized water, HY zeolite 100 grams of preparation among this solution and the embodiment 1 are mixed, mixed material is placed tube furnace, feed deionized water by 300 Grams Per Hours, be warming up to 450 ℃, constant temperature 6 hours obtains containing after the modification magnesium, chromium and tungsten (in oxide weight) and is respectively 0.8%, 2.8% and 6.7% Y zeolite E after the cooling, its physico-chemical property is listed in the table 1.
Embodiment 6
Take by weighing iron oxide (Fe
2O
3, chemical pure, chemical plant, Hangu, Tianjin product) and 5.0 gram and vanadic anhydride (V
2O
5, chemical pure, Chengdu, Sichuan chemical reagent work product) and the HY zeolite 100 of preparation restrains and mixes among 4.5 grams and the embodiment 1, takes by weighing ammonium molybdate [(NH
4)
4Mo
7O
24.4H
2O, chemical pure, Changsha reagent chemical plant product] 6.1 the gram be dissolved in 40 ml deionized water, the mixture and the ammonium molybdate solution of iron oxide and HY zeolite are mixed, mixed material is placed tube furnace, feed deionized water by 150 Grams Per Hours, be warming up to 500 ℃, constant temperature 8 hours obtains iron content after the modification, vanadium and molybdenum (in oxide weight) and is respectively 4.3%, 3.9% and 4.2% Y zeolite F after the cooling, its physico-chemical property is listed in the table 1.Table 1
| Example number | 1 | 2 | 3 | 4 | 5 | 6 | Comparative Examples 1 |
| The zeolite product numbering | A | B | C | D | E | F | |
| Lattice constant, dust | 24.35 | 24.32 | 24.39 | 24.37 | 24.42 | 24.43 | 24.56 |
| The acid amount, the A/ gram-centimeter 2 | 30.1 | 34.3 | 20.4 | 24.8 | 22.7 | 25.2 | 24.2 |
Embodiment 7～12
With the modified Y zeolite A～F of example 1～6 preparation by the weight ratio of 15: 85 (butt) respectively and boehmite (Shandong Aluminum Plant's production) mix, add an amount of extrusion aid and water, on banded extruder, extrude 2 millimeters bar shaped, 120 ℃ of oven dry, 600 ℃ of roastings 4 hours, six kinds of catalyst carriers that contained modified zeolite A～F respectively take by weighing each 100 gram of these six kinds of catalyst carriers, more respectively with containing WO
3638.5 the ammonium metatungstate [(NH of grams per liter and NiO 63.85 grams per liters
4)
2W
4O
13.18H
2O, chemical pure, Sichuan Zigong Hard Alloy Foundry product] and nickel nitrate [Ni (NO
3)
3.6H
2O, chemical pure, Beijing Chemical Plant's product] 65 milliliters of dippings of solution, 120 ℃ of oven dry, 500 ℃ of roastings 4 hours obtain containing the catalyst I～VI of modified zeolite, contain NiO 2.7 heavy %, WO in the catalyst
327.0 heavy % (calculated value).
Catalyst I～VI is broken into 40～60 purpose particles respectively, and mix with equigranular quartz sand by 1: 1 volume ratio respectively, the 2 milliliters of reactors of packing into, with the normal heptane is that model compound is estimated respectively the catalytic performance of catalyst I～VI, under 300 ℃ of nitrogen atmosphere, catalyst was carried out presulfurization 2 hours earlier before estimating with the normal heptane that contains 3 heavy % carbon disulfide, appreciation condition is 350 ℃ of reaction temperatures, Hydrogen Vapor Pressure 2.5MPa, volume space velocity 1 hour
-1, hydrogen flowing quantity 400 ml/min product gas chromatographic analysis, normal heptane conversion ratio and isomerization selectivity are listed in the table 2, here, isomery selectivity=isomerized products yield/conversion ratio * 100%.
Comparative Examples 1
The explanation of this Comparative Examples the invention provides the zeolite catalyst of method preparation and compares with the catalyst for preparing with the HY zeolite among the embodiment 1, has high isomerization selectivity.
Prepare catalyst V II with the HY zeolite among the embodiment 1 according to the method for example 7～12, contain NiO 2.7 heavy %, WO in the catalyst
327.0 heavy % (calculated value).
With example 7～12 the same terms under catalyst V II is estimated, normal heptane conversion ratio and isomerization selectivity are listed in the table 2.Table 2
| Example number | 7 | 8 | 9 | 10 | 11 | 12 | Comparative Examples 1 |
| The catalyst numbering | I | II | III | IV | V | VI | VII |
| Conversion ratio, % | 44.8 | 43.3 | 38.5 | 47.6 | 35.2 | 45.1 | 60.2 |
| The isomerization selectivity, % | 89.1 | 91.1 | 90.3 | 85.2 | 92.2 | 83.9 | 11.5 |
Claims (10)
1. the method for modifying of a y-type zeolite, it is characterized in that becoming the oxide or the oxysalt of sour metallic element to mix by 100: 1～30: 0.1～15 weight ratio less than the y-type zeolite of 1 heavy % with at least a sodium content, and be 0.05～3.5 hour at 400 ℃～800 ℃ with the water vapour weight space velocity mixture with at least a oxide that becomes alkali or tellurium or salt except that alkali metal
-1Moisture vapor atmosphere contact 0.5～8 hour.
2. in accordance with the method for claim 1, wherein said y-type zeolite is NaY, NH
4Y, HY, REY, REHY or the y-type zeolite behind super stabilizing.
3. in accordance with the method for claim 2, wherein said y-type zeolite is NH
4Y or HY zeolite.
4. in accordance with the method for claim 1, the sour metallic element of wherein said one-tenth is V, Cr, Mo, W.
5. in accordance with the method for claim 1, wherein said one-tenth alkali or tellurium are Mg, Ti, Zr, Nb, Al, Fe, Co, Ni, Zn, Sb.
6. in accordance with the method for claim 1, y-type zeolite and the oxide that becomes sour metallic element or oxysalt with at least a except that alkali metal the oxide that becomes alkali or tellurium or the weight ratio of salt be 100: 2～20: 0.5～10.
7. in accordance with the method for claim 1, wherein said moisture vapor atmosphere is one or more the mixture in water vapour or water vapour and air, oxygen, the inert gas.
8. in accordance with the method for claim 7, wherein said moisture vapor atmosphere is steam.
9. according to the described method of arbitrary claim in the claim 1,7 or 8, the weight space velocity of water vapour is 0.1～2.5 hour in the wherein said water vapour atmosphere
-1
10. in accordance with the method for claim 1, wherein said mixture and moisture vapor atmosphere contact 2～6 hours under 450～750 ℃ of temperature.
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|---|---|---|---|
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|---|---|---|---|
| CN99107940A CN1091399C (en) | 1999-06-04 | 1999-06-04 | Process for modifying Y-zeolite |
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| CN1091399C true CN1091399C (en) | 2002-09-25 |
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Cited By (1)
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|---|---|---|---|---|
| CN102874838A (en) * | 2012-08-05 | 2013-01-16 | 青岛惠城石化科技有限公司 | Method for regulating composition of Y-type molecular sieve |
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| 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 |
| CN105435835B (en) * | 2014-08-29 | 2019-01-08 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and its preparation and application |
| CN105435837B (en) * | 2014-08-29 | 2019-01-08 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and its preparation and application |
| CN110668462B (en) * | 2019-11-15 | 2021-06-01 | 林卿 | Rapid synthesis of nano Fe3O4Method for @ NaY magnetic composite material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US487429A (en) * | 1892-12-06 | Clothes-drier | ||
| EP0288112A2 (en) * | 1987-04-14 | 1988-10-26 | Shell Internationale Researchmaatschappij B.V. | Process for the preparation of modified zeolites |
| CN1122111A (en) * | 1994-02-09 | 1996-05-08 | 巴西石油公司 | Process for preparing a modified Y-zeolite |
-
1999
- 1999-06-04 CN CN99107940A patent/CN1091399C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US487429A (en) * | 1892-12-06 | Clothes-drier | ||
| EP0288112A2 (en) * | 1987-04-14 | 1988-10-26 | Shell Internationale Researchmaatschappij B.V. | Process for the preparation of modified zeolites |
| CN1122111A (en) * | 1994-02-09 | 1996-05-08 | 巴西石油公司 | Process for preparing a modified Y-zeolite |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102874838A (en) * | 2012-08-05 | 2013-01-16 | 青岛惠城石化科技有限公司 | Method for regulating composition of Y-type molecular sieve |
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