CN1350887A - Modified Y zeolite containing both notable metal and non-notable metal and its preparing process - Google Patents
Modified Y zeolite containing both notable metal and non-notable metal and its preparing process Download PDFInfo
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- CN1350887A CN1350887A CN 00123138 CN00123138A CN1350887A CN 1350887 A CN1350887 A CN 1350887A CN 00123138 CN00123138 CN 00123138 CN 00123138 A CN00123138 A CN 00123138A CN 1350887 A CN1350887 A CN 1350887A
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Abstract
A modified Y zeolite containing both noble metal and non-noble metal is prepared from NaY zeolite through ion exchange of noble metal and non-noble metal, hydrothermal treating, and ammonium salt exchange. The content of noble metal is 0.05-2 wt.%. The content of non-noble metal is 0.5-15 wt.%. Its advantages include uniform dispersion of nobe metal, and excellent hydrogenation and sulfur-resistant performance.
Description
The present invention relates to a kind of modified Y zeolite and preparation method thereof, contain precious metal and non-noble metal modified Y zeolite and preparation method thereof especially simultaneously.
Y zeolite be a kind of be structural unit with octahedra top rake cage (β cage), a kind of Si of containing, the Al that forms by diamond crystal arrangement mode at three-dimensional space, the zeolite crystal structure of Na, O.The β cage forms octahedra zeolite cages (supercage) by six-ring with Si (Al)-O-Si (Al) key joint.Connect mutually along three crystalline axis direction by twelve-ring between the octahedra zeolite cages, form structure cell.
Because form crystal, Y zeolite has high heat and hydrothermal stability, and has preferable Na ion-exchange capacity and stronger dealuminzation ability.The ion that higher ion-exchange capacity can make exchange get on has high dispersity.Stronger dealuminzation ability can make Y zeolite be easy to carry out the dealuminzation modification.Y zeolite after the dealuminzation modification can form B acid and L acid, and can be in a big way modulation strength of acid and acids type neatly.Above characteristic makes Y zeolite be suitable for the acid carrier as cracking reactions such as catalytic cracking, hydrocracking.The important component of catalyzer and carrier in the technological process such as simultaneously, the Y zeolite polymolecularity makes that it becomes that hydrocracking, aromatic hydrocarbons are saturated, open loop, hydrodenitrification, hydrogenating desulfurization, alkene are saturated.When adopting ion-exchange or pickling process to be supported on precious metal on the Y zeolite (or on the respective carrier time), prepared catalyzer will have higher hydrogenation activity, use comparatively general in saturated in two-stage method hydrocracking, aromatic hydrocarbons usually, the hydrofining technologies such as (desulfurization, denitrogenations).
United States Patent (USP) 4882307,4683052,4683274 have introduced a kind of precious metal Y zeolite preparation technology that contains.These patents all adopt pickling process in the introducing mode of precious metal, compare with general preparation method, adopt different calcination atmospheres (nitrogen, oxygen, air) in the patent, are intended to the dispersion of remarkably influenced precious metal on the Y zeolite surface.They think in different atmosphere can form Pd (Pt) H and Pd (Pt) O causes precious metals pd, Pt in the surface arrangement difference.
United States Patent (USP) 4897178 disclosed technologies of preparing are to prepare catalyzer on LZ-210 molecular sieve basis, can adopt heat and hydrothermal treatment consists, ammonium ion exchange, and carry out active ingredient and support.Active metal component can carry out one or many to be introduced, but points out in the patent that common precious metal and base metal can not coexist as in the same catalyst system.And there is not precious metal and the base metal same system implementation example that coexists in this patent.
Do not consider on a kind of molecular sieve, to support simultaneously precious metal and non-noble metal situation in the above technology.
United States Patent (USP) 4225418,4175033 discloses a kind of Ni, Mo, Pt and has been supported on simultaneously and contains catalyzer and preparation method on the Y zeolite carrier.This catalyzer preparation earlier contains the Y zeolite carrier, floods Ni, Mo, Pt more respectively.The catalyzer of this patent preparation is because of containing precious metal and base metal simultaneously, catalyzer has certain anti-sulphur and higher hydrogenation activity, can be used for various hydrogenation techniques such as hydrocracking, rocket engine fuel open loop, aromatic hydrogenation, hydrofining, hydrogenating desulfurization, hydrodenitrification.Preparation of catalysts adopts prepares carrier earlier, and metal is introduced in the back.The introducing mode of metal adopts pickling process, and there is the not good enough problem of degree of uniformity in Metal Distribution.
Introduced PdW/Y in the United States Patent (USP) 5868921, PdCr/Y (dealuminzation Y) catalyzer.This method for preparing catalyst floods for adopting the corresponding nitrate of W, Cr earlier, and the back utilizes H with pickling process
2PdCl
4Carry out the introducing of precious metals pd.This catalyzer can be used for Tuo Fang and heteroatoms removes.The introducing mode of metal is not improved in the technology of preparing that this patent is announced, exists Metal Distribution to have the not good enough problem of degree of uniformity equally.
The object of the invention provides a kind of precious metal and non-noble metal modified Y zeolite and preparation method thereof of containing simultaneously, improves the hydrogenation performance and the sulfur resistance of modified Y zeolite.
Modified Y zeolite of the present invention is characterized as: the weight percent with modified Y zeolite is a benchmark, contains the precious metal of the heavy % in 0.05 heavy %～2.0 on the Y zeolite, the base metal of the heavy % in 0.5 heavy %～15.0, the silica alumina ratio (SiO of Y zeolite
2/ Al
2O
3) be 5.0～50, unit cell parameters is 2.430～2.455nm, surface-area is 500～850m
2/ g, pore volume 0.30～0.50ml/g.
Described precious metal is generally and is selected among Ru, Rh, Pd, Os, Ir, the Pt one or more, be preferably among Pd, the Pt one or both, described base metal generally is the transition metal in the periodic table of elements, better be group vib and/or VIII family base metal in the periodic table of elements, preferably be selected from one or more of Mo, W in the group vib and Fe, Co in the group VIII, Ni.
The content of described precious metal on Y zeolite is 0.05～1.5 heavy % preferably, and the content of described base metal on Y zeolite is 0.5～10.0wt% preferably.
Silica alumina ratio (the SiO of described modified Y zeolite
2/ Al
2O
3) being preferably 6.0～30.0, unit cell parameters is preferably 2.432～2.450nm, and surface-area is preferably 550～800m
2/ g, pore volume is preferably 0.35～0.45ml/g.
Precious metal of the present invention and base metal are that the method by ion-exchange is incorporated on the Y zeolite.
The preparation method of modified Y zeolite of the present invention comprises: be that raw material carries out base metal ion-exchange with NaY, obtain containing base metal ionic molecular sieve behind the washing and drying, resultant molecular sieve is carried out exchanging precious metal ion again after the hydrothermal treatment consists, wash then, dry and steps such as hydrothermal treatment consists, ammonium ion exchange, pickling for the second time, prepare a kind of modified Y zeolite that contains precious metal and transition metal ion simultaneously of the present invention.
Can change precious metal and the introducing of base metal ion order and number of times among the above-mentioned preparation technology as required.As exchanging the modification Ni-Pd-Y of Ni (Fe, Co) back exchange Pd earlier, exchange the modification Pd-Ni-Y of Ni etc. earlier behind the exchange Pd.Preferably introduce base metal earlier, introduce precious metal again.
Degree of crystallinity 〉=95% of wherein said raw material NaY zeolite, unit cell parameters 2.465～2.470nm, SiO
2/ Al
2O
3Be 4.8～5.5.
During the above-mentioned modified Y zeolite of concrete preparation, can carry out with reference to following steps:
A, base metal ion-exchange: with NaY is raw material, use base metal, generally be transition metal, better be group vib and/or VIII the group base metal, be more preferably one or more of water soluble salt of the Mo, the W that are selected from the group vib and Fe, Co in the group VIII base metal, Ni, preferably the nitrate of Fe, Co, Ni, carbonate, vitriol, phosphoric acid salt, halogenide and ammonium molybdate or ammonium tungstate carry out ion-exchange.The exchange temperature is 50～99 ℃, and the time is 0.5～10 hour, and regulates pH value to 2～8 with acid or ammoniacal liquor.Used acid can be hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid or acetic acid etc.The exchange number of times is 1～5 time, and last exchange back is with distilled water wash 1～3 time, then 100～150 ℃ of dryings 1～48 hour.Base metal content in the exchange is generally 0.5%～15.0 heavy %, is preferably 0.5%～10.0 heavy %.
B, hydrothermal treatment consists: above-mentioned dried zeolite is carried out hydrothermal treatment consists, at 450～800 ℃, preferably 500～700 ℃, steam partial pressure 0.02～0.15MPa.Hydrothermal treatment consists 0.5～10 hour, preferably 0.5～4 hour.
C, precious metal ion exchange: with the Y zeolite after the above-mentioned exchange is raw material, with VIII family precious metal, can be Ru, Rh, Pd, Os, Ir, Pt, the water soluble salt of best Pd, Pt, and the water soluble salt of Pd, Pt can be H
2PdCl
4, Pd (NO
3)
2, Pd (NH
3)
4Cl
2, Pd (NH
3)
4(NO
3)
2, H
2PtCl
4, Pt (NH
3)
4Cl
2, Pt (NH
3)
4(NO
3)
2, Pt (NO
3)
2Or the mixture of Pd, the corresponding salt of Pt.The exchange temperature is 50～99 ℃, and the time is 0.5～10 hour, regulates ion exchange liquid pH value to 2 or 8 with acid or ammoniacal liquor, and used acid can be hydrochloric acid, nitric acid etc., exchanges 1～2 time.Last exchange back is with distilled water wash 1～3 time, then 100～150 ℃ of dryings 1～48 hour.Bullion content in the final exchange should be 0.05%～2.0% of modified Y zeolite gross weight, and preferably 0.05%～1.5%.
D, hydrothermal treatment consists for the second time.Zeolite after the top precious metal exchange is carried out the hydrothermal treatment consists second time by the b step.
E, ammonium ion exchange, pickling: with ammonium concentration is 0.5～5N, the ammonia salts solution of 1～4N preferably, preferably ammonium nitrate, volatile salt, ammonium chloride solution for exchange liquid with corresponding acid for adjusting pH value less than 2, stirred 0.5～5 hour down at 50～99 ℃, exchange number of times 1～5 time, last exchange back is with distilled water wash 1～3 time, then 100～150 ℃ of dryings 1～48 hour.Obtain the purpose product at last---contain precious metal and non-noble metal Y zeolite simultaneously.
Compared with prior art, modified Y zeolite characteristics of the present invention are to contain one or more precious metals and one or more base metals simultaneously.Because the base metal dispersity height that gets on of ion-exchange, and precious metal played further isolation, dissemination, make the precious metal dispersity further improve.Simultaneously, because contained base metal itself is a kind of metal with hydrogenation activity, and base metal hydrogenation activity under the situation of sulfur-bearing is higher, therefore, with the modified Y zeolite of the technical program preparation, not only can improve the dispersity of precious metal, also can obviously improve the anti-sulphur of precious metal.Hydrogenation performance and excellent in sour resistance are a kind of good hydrocracking and aromatic hydrogenation, hydrofining, rocket engine fuel open loop, aromatic hydrogenation, hydrogenating desulfurization and hydrodenitrogenation catalyst carrier main ingredient.
The present invention is further described below by embodiment.
Embodiment 1
Present embodiment has been introduced the preparation of solution, gets a certain amount of nickelous nitrate, Xiao Suangu is dissolved in water, and being mixed with concentration respectively is that 10g/100ml contains NiO, CoO solution, and get a certain amount of ammonium molybdate and be dissolved in water,
Being mixed with concentration is that 10g/100ml contains MoO
3Solution is got a certain amount of Pd (NH
3)
4Cl
2With Pt (NH
3)
4Cl
2Be dissolved in water, be mixed with concentration respectively for containing Pd or Pt 1.0g/100ml solution, the above-mentioned precious metal aqueous solution that contains also can add the aqueous solution that other Pd, Pt were prepared or adopted in the acid dissolving by metal Pd or Pt.
Comparative example 1
The above-mentioned aqueous solution adding distil water that 100ml is contained Pd is diluted to 1000ml, adds 250g NaY zeolite (Wenzhou catalyst plant, degree of crystallinity 102%, a
02.466nm, SiO
2/ Al
2O
35.1, Na
2The heavy % of O 2.4, butt 80 heavy %), be heated to 60 ℃, stir exchange 2 hours down at 60 ℃, regulate pH=3 with nitric acid and filter washing 3 times then, the filter cake after the 3rd washing was in 110 ℃ of dryings 8 hours.Dried filter cake adding distil water 40ml, put into 550 ℃ in hydrothermal treatment consists stove and carried out hydrothermal treatment consists 4 hours, steam partial pressure is 0.05MPa, Y zeolite after the hydrothermal treatment consists is put into 1000ml 1N ammonium nitrate/aqueous nitric acid (pH=2) carry out the ammonium exchange, be 2 hours swap time, 70 ℃ of exchange temperature, repeated exchanged 2 times.Filter washing 3 times then, the filter cake after the 3rd washing was in 110 ℃ of dryings 8 hours.Obtain modification Y-1, its character sees Table 1.
Comparative example 2
The above-mentioned aqueous solution adding distil water that 100ml is contained Pt is diluted to 1000ml, add 250g NaY zeolite (Wenzhou catalyst plant, with embodiment 2), be heated to 60 ℃, stir exchange 2 hours down at 60 ℃, regulate pH=3 with nitric acid, filter washing 3 times then, the filter cake after the 3rd washing was in 110 ℃ of dryings 8 hours.Dried filter cake adding distil water 40ml, put into 550 ℃ in hydrothermal treatment consists stove and carried out hydrothermal treatment consists 4 hours, steam partial pressure is 0.05MPa, Y zeolite after the hydrothermal treatment consists is put into 1000ml 1N ammonium nitrate/aqueous nitric acid (pH=2) carry out the ammonium exchange, be 2 hours swap time, 60 ℃ of exchange temperature, repeated exchanged 2 times.Filter washing 3 times then, the filter cake after the 3rd washing obtains modified Y zeolite Y-2 in 110 ℃ of dryings 8 hours, and its character sees Table 1.
Embodiment 2
The above-mentioned aqueous solution adding distil water that 150ml is contained NiO is diluted to 1000ml, adds 250g NaY zeolite (Wenzhou catalyst plant, degree of crystallinity 98%, unit cell parameters 2.466nm, SiO
2/ Al
2O
3Be 5.1, Na
2The heavy % of O 10, butt 80 heavy %), be heated to 70 ℃, stir exchange 2 hours down at 70 ℃, filter washing 3 times then, the filter cake after the 3rd washing was in 110 ℃ of dryings 8 hours.Dried filter cake adding distil water 40ml puts into 600 ℃ in hydrothermal treatment consists stove and carried out hydrothermal treatment consists 4 hours, and steam partial pressure is 0.10MPa
The above-mentioned aqueous solution adding distil water that 100ml is contained Pd is diluted to 1000ml, and sample after the above-mentioned hydrothermal treatment consists of adding 200g is heated to 60 ℃, stir exchange 2 hours down at 60 ℃, regulate pH=3 with nitric acid, filter washing 3 times then, the filter cake after the 3rd washing was in 110 ℃ of dryings 8 hours.Dried filter cake adding distil water 40ml, put into 550 ℃ in hydrothermal treatment consists stove and carried out hydrothermal treatment consists 6 hours, steam partial pressure is 0.05MPa, Y zeolite after the hydrothermal treatment consists is put into 1000ml 1N ammonium nitrate/aqueous nitric acid (pH=2) carry out the ammonium exchange, be 2 hours swap time, 70 ℃ of exchange temperature, filter washing 3 times then, filter cake after the 3rd washing obtains modified Y zeolite Y-3 in 110 ℃ of dryings 8 hours, and its character sees Table 1.
Embodiment 3
The above-mentioned aqueous solution adding distil water that 30ml is contained Pd is diluted to 1000ml, adds the above-mentioned NaY molecular sieve of 250g, is heated to 60 ℃, stirs exchange 2 hours down at 60 ℃, filters washing 3 times then, and the filter cake after the 3rd washing was in 110 ℃ of dryings 8 hours.Dried filter cake adding distil water 40ml puts into 550 ℃ in hydrothermal treatment consists stove and carried out hydrothermal treatment consists 4 hours, and steam partial pressure is 0.05MPa
The above-mentioned aqueous solution adding distil water that 60ml is contained NiO is diluted to 1000ml, sample after the above-mentioned hydrothermal treatment consists of adding 200g, be heated to 70 ℃, stir exchange 2 hours down at 70 ℃, repeated exchanged 1 time, regulate pH=2 or 8 with acid and ammoniacal liquor respectively, filter washing 3 times then, the filter cake after the 3rd washing was in 110 ℃ of dryings 8 hours.Dried filter cake adding distil water 40ml puts into 550 ℃ in hydrothermal treatment consists stove and carried out hydrothermal treatment consists 4 hours, and steam partial pressure is 0.05MPa.Y zeolite after the hydrothermal treatment consists is put into 1000ml 1N ammonium nitrate/aqueous nitric acid (pH=2) carry out the ammonium exchange, be 2 hours swap time, 70 ℃ of exchange temperature, filter washing 3 times then, washing back filter cake obtains modified Y zeolite Y-4 in 110 ℃ of dryings 8 hours for the third time, and its character sees Table 1.
Embodiment 4
The above-mentioned aqueous solution adding distil water that 150ml is contained NiO is diluted to 1000ml, adds 250g NaY zeolite (Wenzhou catalyst plant, degree of crystallinity 98%, unit cell parameters 2.466nm, SiO
2/ Al
2O
35.1, Na
2The heavy % of O10, butt 80 heavy %), be heated to 70 ℃, stir exchange 2 hours down at 70 ℃, repeated exchanged 1 time is regulated pH=2 or 8 with acid and ammoniacal liquor respectively, filters washing 3 times then, and the filter cake after the 3rd washing was in 110 ℃ of dryings 8 hours.Dried filter cake adding distil water 40ml puts into 600 ℃ in hydrothermal treatment consists stove and carried out hydrothermal treatment consists 4 hours, and steam partial pressure is 0.05MPa.
The above-mentioned aqueous solution adding distil water that 100ml is contained Pt is diluted to 1000ml, and sample after the above-mentioned hydrothermal treatment consists of adding 200g is heated to 60 ℃, stir exchange 2 hours down at 60 ℃, regulate pH=3 with nitric acid, filter washing 3 times then, the filter cake after the 3rd washing was in 110 ℃ of dryings 8 hours.Dried filter cake adding distil water 40ml, put into 600 ℃ in hydrothermal treatment consists stove and carried out hydrothermal treatment consists 6 hours, steam partial pressure is 0.05MPa, Y zeolite after the hydrothermal treatment consists is put into 1000ml 1N ammonium nitrate/aqueous nitric acid (pH=2) carry out the ammonium exchange, be 2 hours swap time, 70 ℃ of exchange temperature, filter washing 3 times then, filter cake after the 3rd washing obtains modified Y zeolite Y-5 in 110 ℃ of dryings 8 hours, and its character sees Table 1.
Embodiment 5
The above-mentioned aqueous solution adding distil water that 60ml is contained NiO is diluted to 1000ml, sample after the above-mentioned hydrothermal treatment consists of adding 200g, be heated to 70 ℃, stir exchange 2 hours down at 70 ℃, repeated exchanged 1 time, regulate pH=2 or 8 with acid and ammoniacal liquor respectively, filter washing 3 times then, the filter cake after the 3rd washing was in 110 ℃ of dryings 8 hours.Dried filter cake adding distil water 40ml puts into 550 ℃ in hydrothermal treatment consists stove and carried out hydrothermal treatment consists 4 hours, and steam partial pressure is 0.05MPa.Y zeolite after the hydrothermal treatment consists is put into 1000ml 1N ammonium nitrate/aqueous nitric acid (pH=2) carry out ammonium exchange, be 2 hours swap time, and 70 ℃ of exchange temperature are filtered washing 3 times then, and the filter cake after the 3rd washing was in 110 ℃ of dryings 8 hours.
The above-mentioned aqueous solution adding distil water that 100ml is contained Pd is diluted to 1000ml, and sample after the above-mentioned hydrothermal treatment consists of adding 200g is heated to 60 ℃, stir exchange 2 hours down at 60 ℃, regulate pH=3 with nitric acid, filter washing 3 times then, the filter cake after the 3rd washing was in 110 ℃ of dryings 8 hours.Dried filter cake adding distil water 40ml, put into 550 ℃ in hydrothermal treatment consists stove and carried out hydrothermal treatment consists 4 hours, steam partial pressure is 0.05MPa, Y zeolite after the hydrothermal treatment consists is put into 1000ml 1N ammonium nitrate/aqueous nitric acid (pH=2) carry out the ammonium exchange, be 2 hours swap time, 70 ℃ of exchange temperature, filter washing 3 times then, filter cake after the 3rd washing obtains modified Y zeolite Y-6 in 110 ℃ of dryings 8 hours, and its character sees Table 1.
The physico-chemical property of table 1 modified Y zeolite 1～6
| Sample number into spectrum | ????1 | ????2 | ????3 | ????4 | ????5 | ????6 |
| The modified Y zeolite kind | ???PdY | ???PtY | ?Ni-Pd-Y | ?Pd-Ni-Y | ?Ni-Pt-Y | ?Co-Pd-Y |
| ??????NiO％ | ???- | ???- | ??6.94 | ??5.84 | ??6.73 | ??4.22 |
| ??????Pd％ | ???0.48 | ???- | ??0.47 | ??0.44 | ??- | ??0.47 |
| ??????Pt％ | ???- | ???0.49 | ??- | ??- | ??0.47 | ??- |
| Specific surface, m 2/g | ???701 | ???698 | ??598 | ??642 | ??708 | ??671 |
| Pore volume, ml/g | ???0.384 | ???0.375 | ??0.355 | ??0.390 | ??0.367 | ??0.374 |
| ??SiO 2/Al 2O 3，wt％ | ???10.23 | ???9.22 | ??12.92 | ??11.23 | ??11.39 | ??10.82 |
| ????a 0，nm | ???2.444 | ???2.440 | ??2.434 | ??2.436 | ??2.432 | ??2.435 |
Embodiment 6
For further modified Y zeolite activity of the present invention being described further, on the 10ml micro-reactor, test, loaded catalyst 10ml adopts analytical pure toluene and thiophene as model compound, volume space velocity 4.0h
-1, reaction pressure 4.0MPa, hydrogen-oil ratio 800: 1,200 ℃ of temperature of reaction, toluene is analytical pure in the raw material.Thiophene content 3000ppmw.Gas chromatograph, hydrogen flame detects, the on-line analysis toluene conversion.Sample time t
0=0.5 hour, t
1=6 hours, t
2=48.
In each test, the toluene hydrogenation activity is represented with toluene conversion X%.
X％＝∑P/∑T×100
∑ P represents in the product that toluene transforms behind the hydrogenation products methylcyclohexane and hydrogenation the positive structure of C1～C7 that further cracking generates and the molar content sum of isomerized products.On behalf of the said products molar content sum, ∑ T add the molar content that remains unconverted toluene, promptly total molar content.
Each modified molecular screen toluene hydrogenation activity (toluene conversion X%) of table 2
| Sample | PdY | ?Ni-Pd-Y | ?Pd-Ni-Y | ?Ni-Pt-Y | ?Co-Pd-Y |
| T=0.5 hour | 100 | ?100 | ?100 | ?100 | ?100 |
| T=6 hour | 87 | ?97 | ?92 | ?98 | ?93 |
| T=48 hour | 56 | ?94 | ?93 | ?97 | ?91 |
Table 2 is several toluene hydrogenation performances of modified Y zeolite under 3000ppmw thiophene condition that contain precious metal.Though all show excellent initial activity by the visible several modified Y zeolites of table 2.Be contained in 48 hours marquis in the modified Y zeolite raw material of base metal and precious metal and still can keep height more than 90% to transform and comparatively stable (comparing with t=6 hour) but contain simultaneously, hydrogenation performance and sulfur resistance will obviously be better than not containing non-noble metal modified Y zeolite.Possibility is dispersity height afterwards because base metal ion-exchange is got on, and precious metal is played further isolation, dissemination, makes the precious metal dispersity further improve.Thereby make and of the present inventionly contain precious metal simultaneously and non-noble metal modified Y zeolite has higher anti-sulphur and has better hydrogenation performance.It can be used as the catalyst carrier for hydrgenating main ingredient, is applied in the various hydrogenation reactions such as hydrocracking and aromatic hydrogenation, hydrofining, rocket engine fuel open loop, aromatic hydrogenation, hydrogenating desulfurization and hydrodenitrification.
Claims (18)
1, a kind of precious metal and non-noble metal modified Y zeolite of containing simultaneously, weight percent with modified Y zeolite is a benchmark, contain 0.05%～2.0% precious metal on the Y zeolite, 0.5%～15.0% base metal, the silica alumina ratio of Y zeolite is 5.0～50, unit cell parameters is 2.430～2.455nm, and surface-area is 500～850m
2/ g, pore volume are 0.30～0.50ml/g.
2, according to the described modified Y zeolite of claim 1, it is characterized in that described precious metal is to be selected among Ru, Rh, Pd, Os, Ir, the Pt one or more, described base metal is one or more in group vib and/or the VIII family base metal in the periodic table of elements.
3, according to the described modified Y zeolite of claim 1, it is characterized in that described precious metal is to be selected among Pd, the Pt one or both, described base metal is to be selected from Mo, W in the group vib and Fe, Co in the group VIII, among the Ni one or more.
4, according to the described modified Y zeolite of claim 1, it is characterized in that the weight content of described precious metal on Y zeolite is 0.05%～1.5%, the institute's weight content of base metal on Y zeolite is 0.5%～10.0%.
5, according to the described modified Y zeolite of claim 1, the silica alumina ratio that it is characterized in that described Y zeolite is 6.0～30.0, and unit cell parameters is 2.432～2.450nm, and surface-area is 550～800m
2/ g, pore volume are 0.35～0.45ml/g.
6,, it is characterized in that described precious metal and base metal are that method by ion-exchange is incorporated on the Y zeolite according to the described modified Y zeolite of claim 1.
7, the preparation method of the described modified Y zeolite of a kind of claim 1 comprises:
With the NaY zeolite is that raw material carries out base metal ion-exchange, washing, dry, hydrothermal treatment consists for the first time, precious metal ion exchange, described precious metal and the base metal ionic modified Y zeolite of containing simultaneously prepared in washing, dry, hydrothermal treatment consists and ammonium ion exchange, pickling for the second time.
8, according to the preparation method of the described modified Y zeolite of claim 7, the exchange sequence that it is characterized in that described precious metal and base metal and NaY zeolite is to exchange base metal earlier, exchanges precious metal again.
9, according to the preparation method of the described modified Y zeolite of claim 7, the exchange sequence that it is characterized in that described precious metal and base metal and NaY zeolite is to exchange precious metal earlier, exchanges base metal again.
10,, it is characterized in that described NaY zeolite crystallinity 〉=95%, unit cell parameters 2.465～2.470nm, SiO according to the preparation method of the described modified Y zeolite of claim 7
2/ Al
2O
3Be 4.8～5.5.
11, according to the preparation method of the described modified Y zeolite of claim 7, the actual conditions that it is characterized in that described base metal ion-exchange is: the exchange temperature is 50～99 ℃, time is 0.5～10 hour, and regulate ion exchange liquid pH value to 2～8 with acid or ammoniacal liquor, the exchange number of times is 1～5 time, last exchange back is with distilled water wash 1～3 time, and 100～150 ℃ of dryings 1～48 hour, the base metal content in the exchange should be 0.5%～10% of described modified Y zeolite gross weight then.
12,, comprise non-noble metal water soluble salt in the metallic solution when it is characterized in that described base metal ion-exchange according to the preparation method of the described modified Y zeolite of claim 7.
13,, comprise one or more of water soluble salt of the Mo, the W that are selected from group vib and Fe, Co in the group VIII base metal, Ni in the metallic solution when it is characterized in that described base metal ion-exchange according to the preparation method of the described modified Y zeolite of claim 7.
14, according to the preparation method of the described modified Y zeolite of claim 7, it is characterized in that the actual conditions of described hydrothermal treatment consists is: 450～800 ℃ of hydrothermal treatment consists temperature, steam partial pressure 0.02～0.15Mpa, 0.5～10 hour hydrothermal treatment consists time.
15, according to the preparation method of the described modified Y zeolite of claim 7, the actual conditions that it is characterized in that described precious metal ion exchange is: the exchange temperature is 50～99 ℃, time is 0.5～10 hour, regulate ion exchange liquid pH value to 2～8 with acid or ammoniacal liquor, the exchange number of times is 1～5 time, last exchange back is with distilled water wash 1～3 time, and 100～150 ℃ of dryings 1～48 hour, the bullion content in the exchange should be 0.05%～2.0% of described modified Y zeolite gross weight then.
16,, it is characterized in that comprising in the metallic solution of described precious metal ion exchange process in the water soluble salt that is selected from precious metal one or more according to the preparation method of the described modified Y zeolite of claim 7.
17,, it is characterized in that comprising in the metallic solution of described precious metal ion exchange process in the water soluble salt that is selected from Pd, Pt one or both according to the preparation method of the described modified Y zeolite of claim 7.
18, according to the preparation method of the described modified Y zeolite of claim 7, the detailed process that it is characterized in that described ammonium ion exchange, pickling is: with ammonium concentration is that the ammonium salt solution of 0.5～5N is an exchange liquid, regulate ion exchange liquid pH value less than 3 with acid, under 50～99 ℃ condition, stir process 0.5～5 hour, exchange 2～5 times, last exchange back distilled water wash 1～3 time, 100～150 ℃ of dryings 1～48 hour, obtain described precious metal and the non-noble metal modified Y zeolite of containing simultaneously then.
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|---|---|---|---|
| CN 00123138 CN1111089C (en) | 2000-10-26 | 2000-10-26 | Modified Y zeolite containing both notable metal and non-notable metal and its preparing process |
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| CN 00123138 CN1111089C (en) | 2000-10-26 | 2000-10-26 | Modified Y zeolite containing both notable metal and non-notable metal and its preparing process |
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| Publication Number | Publication Date |
|---|---|
| CN1350887A true CN1350887A (en) | 2002-05-29 |
| CN1111089C CN1111089C (en) | 2003-06-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00123138 Expired - Lifetime CN1111089C (en) | 2000-10-26 | 2000-10-26 | Modified Y zeolite containing both notable metal and non-notable metal and its preparing process |
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| Country | Link |
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| CN (1) | CN1111089C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100345632C (en) * | 2004-10-29 | 2007-10-31 | 中国石油化工股份有限公司 | Alumina carrier containing compound zeolite and preparation method thereof |
| FR3012125A1 (en) | 2013-10-22 | 2015-04-24 | China Petroleum & Chemical | |
| CN104556126A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of metallic oxide modified Y-shaped molecular sieve |
| US9855552B2 (en) | 2013-10-22 | 2018-01-02 | China Petroleum & Chemical Corporation | Metal modified y zeolite, its preparation and use |
| US9943836B2 (en) | 2013-10-22 | 2018-04-17 | China Petroleum & Chemical Corporation | Metal modified Y zeolite, its preparation and use |
-
2000
- 2000-10-26 CN CN 00123138 patent/CN1111089C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100345632C (en) * | 2004-10-29 | 2007-10-31 | 中国石油化工股份有限公司 | Alumina carrier containing compound zeolite and preparation method thereof |
| FR3012125A1 (en) | 2013-10-22 | 2015-04-24 | China Petroleum & Chemical | |
| CN104556126A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of metallic oxide modified Y-shaped molecular sieve |
| CN104556126B (en) * | 2013-10-22 | 2016-08-24 | 中国石油化工股份有限公司 | A kind of preparation method of metal oxide modified Y type molecular sieve |
| US9855552B2 (en) | 2013-10-22 | 2018-01-02 | China Petroleum & Chemical Corporation | Metal modified y zeolite, its preparation and use |
| US9943836B2 (en) | 2013-10-22 | 2018-04-17 | China Petroleum & Chemical Corporation | Metal modified Y zeolite, its preparation and use |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1111089C (en) | 2003-06-11 |
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