CN100531909C - ZSM-5/SAPO-11 composite zeolite and catalytically cracked gasoline hydrogenation quality-improved catalyzer and the method for preparing the same - Google Patents
ZSM-5/SAPO-11 composite zeolite and catalytically cracked gasoline hydrogenation quality-improved catalyzer and the method for preparing the same Download PDFInfo
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Abstract
The present invention is one kind of catalyst with ZSM-5/SAPO-11 composite zeolite for hydrogenating and modifying catalytically cracked gasoline and its preparation process. The composite zeolite is prepared through compounding solution A with aluminum sulfate, sulfuric acid and water; compounding solution B with water glass, tetraethyl ammonium hydroxide and water; mixing solution A and solution B to form homogeneous colloid; crystallizing the colloid mixture at 150-180 deg.c for 24-72 hr; adding phosphoric acid, pseudoboehite, silica sol and SAPO-11 synthesizing template agent; and final crystallizing at 170-200 deg.c for 24-48 hr to obtain sodium type composite zeolite. The catalyst with the composite zeolite as carrier has excellent hydrogenating and desulfurizing performance, high stability, high gasoline yield, high isomerization activity and certain aromatization activity, and may be applied in producing high quality clean gasoline product.
Description
Technical field
The present invention relates to ZSM-5/SAPO-11 composite zeolite and catalytic gasoline hydrogenation modifying catalyst and preparation method thereof, especially for the ZSM-5/SAPO-11 composite zeolite of catalytic cracking (FCC) gasoline hydrogenation modifying and catalytic gasoline hydrogenation modifying catalyst and preparation method thereof.
Background technology
At present, high olefin(e) centent and sulfur content become the key issue that puzzlement world clean gasoline is produced in the catalytically cracked gasoline.Under the less situation of antiknock component reformation gasoline and gasoline alkylate, for satisfying the clean gasoline standard-required of increasingly stringent, the hydro-upgrading of FCC gasoline just becomes one of key technology that clean fuel for vehicle produces.
United States Patent (USP) 5,770,047 has introduced the desulfurization based on hydroisomerizing, the olefine lowering catalyst of Intevep company exploitation.Carrier is MFI type zeolite (as ZSM-5 or ZSM-12) and Al
2O
3, the Si of zeolite (mol)/Al (mol)=10～200, specific area is 250～1200m
2/ g, active component of load can be the Ga or the B of IIIA family, the Cr of VIB on it; Al
2O
3(specific area 50～2900m
2/ g) active component of last load can be the Ni or the Co of VIII family, the P of the Cr of group vib, Mo and VA family.65～170 ℃ of boiling ranges, sulfur content 600 μ g.g
-1The FCC light distillate after above-mentioned catalyst treatment, sulfur content can be reduced to 74 μ g.g
-1, gasoline research method octane number (RON) is 95.2, be significantly improved than 92.6 of charging, and the product vapour pressure also is improved.When handling the heavy distillat of FCC gasoline, adopt two-stage method, first section is adopted conventional hydrodesulfurization (HDS) catalyst desulfurizing, and second section is adopted above-mentioned catalyst to recover octane number, can be with the 3820 μ g.gs of sulfur content by charging
-1Reduce to 28 μ g.g
-1, the RON of product gasoline reduces with comparing slightly of charging, but is more or less the same C
5 +Liquid yield is 94wt%.They think that this mainly is owing to zeolite, Al
2O
3Last load different metal has respectively been given full play to advantage separately, and the Ga species are moved to Al by zeolite
2O
3On, further strengthen both cooperative effects, thereby reached the purpose that under high desulfurization rate, keeps octane number.
United States Patent (USP) 6,042,719 have introduced the selectivity HDS catalyst of Mobil company exploitation.This catalyst is at Co-Mo/Al
2O
3The basis on increased ZSM-5 as carrier, wherein contain Co2.7wt%, Mo9.6wt%, can under low temperature, low-speed, operate, to avoid alkene and H
2S is again in conjunction with generating mercaptan.Under the identical operations condition, the full cut FCC gasoline of sulfur-bearing 0.28wt% is after this catalyst treatment, and the product sulfur content can be reduced to 100 μ g.g
-1, 3.6 units of road method loss of octane number; After the FCC light fraction of sulfur-bearing 0.049wt% (cut point is 90 ℃) the gasoline wherethrough reason, the product sulfur content also can be reduced to 100 μ g.g
-1, and road method loss of octane number 2.5 units only; For sulfur content is the FCC heavy distillat of 1.42wt%, and the product sulfur content is less than 40 μ g.g
-1, road method octane number increases by 0.7 unit.Three's C
5 +Liquid is received higher, is respectively 102 v%, 96.8 v% and 101 v%.As seen, Co-MoZSM-5/Al
2O
3Catalyst have that adaptability to raw material is wide, desulfuration selectivity is high and liquid yield than advantages such as height.
The patent EP 0537372 of Uop Inc. has reported and has adopted two-step method to carry out the process of FCC gasoline hydrogenation modifying.The first step of this process utilizes clay to remove high unsaturates (for example alkadienes) in the FCC gasoline, thereby forms stable FCC gasoline; Second step adopted the SAPO-11 zeolite as the gasoline isomerization catalyst, carried out isomerization reaction.Compare with feedstock oil, isomerization product in the products obtained therefrom significantly increases, isoparaffin brings up to 3.97 with n-alkane than by 1.09 of feedstock oil, the yield of gasoline of product is 100wt%, and the anti-knock index of the product mean value of motor octane number (research octane number (RON) with) equates with feedstock oil.But the desulfurization performance of SAPO-11 zeolite based catalysts is relatively poor.
External gasoline blend component is generally: FCC gasoline～33%, reformation gasoline～33%, (alkylation+isomerization+etherificate) gasoline～33%, and China's gasoline blend component about 80% is a FCC gasoline, and its sulphur, olefin(e) centent are all higher.Form the significant difference of structure just because of domestic and international gasoline, cause the FCC gasoline hydrogenation isomerization modification technology of external widespread usage not to be suitable for the upgrading of domestic gasoline, make that under the situation that olefin(e) centent significantly reduces, the product loss of octane number is bigger.
In view of the lower characteristics of arene content in China FCC gasoline, CN1350051A has introduced a kind of low-quality FCC gasoline upgrading and has produced aromatized catalyst of clean gasoline and preparation method thereof.Thick FCC gasoline carries out aromatization modification containing on the little crystal grain HZSM-5 of rare-earth oxide and transition metal oxide, obtains the clean gasoline of low alkene, low-sulfur and low benzene.Because the little crystal grain HZSM-5 outer surface of zeolite acid strength and the sour density that are adopted are all higher, make that non-shape selectivity reaction is serious on this aromatized catalyst, coking deactivation is very fast, and catalytic stability is not ideal enough.In addition, simple aromatization technology can need frequent regeneration because of producing a large amount of carbon deposits on the catalyst on the one hand, and this technology is that the aromatic hydrocarbons of certain content restriction is arranged in the gasoline is main purpose to produce on the other hand, therefore also is difficult to directly apply to the upgrading of FCC gasoline.
Above-mentioned FCC gasoline upgrading process is difficult to really realize that the basic reason of gasoline cleaningization is, the catalyst system that it adopted is difficult to provide hydrodesulfurization, isomerization and the aromatization activity of balance all based on the zeolite of simple function (hydrodesulfurization or isomerization or aromatisation function); Because of the economy requirement of emphasizing that too a kind of function causes it to satisfy desulfurization simultaneously, falls alkene, keeps octane number requirement and process, this is the difficult point place of FCC gasoline upgrading just.
Summary of the invention
The objective of the invention is to develop a kind of novel catalyst carrier, make its hydrodesulfurization, hydroisomerizing/aromatisation performance with balance, and based on a kind of catalyst of this preparing carriers, in order to solve catalytic stability difference and the not good problem of combination property that existing modifying catalytically cracked gasoline catalyst exists.
To achieve these goals, the invention provides a kind of ZSM-5/SAPO-11 composite zeolite, described composite zeolite prepares by the following method: with aluminum sulfate, sulfuric acid and water wiring solution-forming A, with waterglass, tetraethyl ammonium hydroxide and water wiring solution-forming B; Then, under intensively stirred situation, solution A is slowly added in the solution B, until forming even colloid; Again with colloid admixture 150～180 ℃ of following crystallization 24～72 hours, in crystallization product, add the used template agent of phosphoric acid, boehmite, Ludox and synthetic SAPO-11 then, after 24～48 hours, obtain a kind of sodium type composite zeolite that SAPO-11 is arranged in ZSM-5 surface outgrowth 170～200 ℃ of following crystallization again; The weight percentage of ZSM-5 zeolite is 20～40% in the described sodium type composite zeolite, and the silica alumina ratio value is 50～70; The weight percentage of SAPO-11 zeolite is 60～80%, and the silica alumina ratio value is 0.2～0.8.
To achieve these goals, it is compound that the SAPO-11 that the present invention will have the ZSM-5 of good hydrodesulfurization, aromatization activity and have an excellent hydroisomerization activity stability carries out original position, and a kind of ZSM-5/SAPO-11 composite zeolite is provided.This composite zeolite prepares by the following method:
(1) at first, with aluminum sulfate, sulfuric acid and water wiring solution-forming A, with waterglass, tetraethyl ammonium hydroxide and water wiring solution-forming B; Then, under intensively stirred situation, solution A is slowly added in the solution B, until forming even colloid; Again with colloid admixture in 150～180 ℃ of following crystallization 24～72 hours, reduce to normal temperature, obtain crystallization product sodium type ZSM-5;
(2) in above-mentioned ZSM-5 crystallization product, add the used template agent of phosphoric acid, boehmite, Ludox and synthetic SAPO-11 successively without any post processing (filtration, washing, drying and roasting etc.), and constantly stir, until obtaining uniform reaction mixture gel; This gel 100 ℃ of ageings 4 hours, after 24～48 hours, can be got ZSM-5/SAPO-11 sodium type composite zeolite in 170～200 ℃ of following crystallization again; The weight percentage of ZSM-5 zeolite is 20～40% in the described sodium type composite zeolite, and the silica alumina ratio value is 50～70; The weight percentage of SAPO-11 zeolite is 60～80%, and the silica alumina ratio value is 0.2～0.8.
Wherein used template agent is a di-n-propylamine in the step (2).
The interfacial effect of ZSM-5 and SAPO-11 has strengthened the two synergy aspect acidity and pore structure in the ZSM-5/SAPO-11 composite zeolite of the present invention.
The present invention also provides more than one to state the catalytic gasoline hydrogenation modifying catalyst that the ZSM-5/SAPO-11 composite zeolite is a carrier, and its preparation method is as follows:
(1) above-mentioned ZSM-5/SAPO-11 composite zeolite is carried out ammonium exchange and organic acid is handled to reduce sodium content, ZSM-5/SAPO-11 Hydrogen composite zeolite is made in drying and roasting again, and described organic acid is treated to oxalic acid solution 90-95 ℃ of processing 4 hours down;
(2) described ZSM-5/SAPO-11 Hydrogen composite zeolite is mixed by weight 1～4:1 with binding agent, in the mixture that forms, add sesbania powder and HNO
3The aqueous solution, the final concentration that makes the sesbania powder by weight are 1～3% and HNO
3Final concentration be 2～5%, pinch through mixing again, after extrusion modling, drying and the roasting, to make catalyst carrier;
(3) carried metal active component on described catalyst carrier, finished product is made in drying and roasting again.
Wherein the binding agent of step (2) employing is a boehmite; The described carried metal active component of step (3) is to adopt equi-volume impregnating load nickel oxide and molybdenum oxide on described catalyst carrier.This loading process comprises:
A) described catalyst carrier be impregnated in the ammonium molybdate solution, then drying and calcination process;
B) catalyst carrier after the step a) processing be impregnated in the nickel nitrate solution, then drying and calcination process.
One preferred version of this loading process is:
Ammonium molybdate is dissolved in the deionized water, be made into the salting liquid that oxide concentration is 0.1～0.5mol/L, (0.7～1.5ml/g), incipient impregnation is 8～12 hours under the room temperature, and drying, roasting obtain containing the catalyst intermediate of molybdenum oxide then by the water absorption rate of catalyst carrier; Is in the nickel nitrate solution of 0.1～0.4mol/L with this catalyst intermediate incipient impregnation in oxide concentration, and to make with the composite zeolite be the catalyst of carrier for drying, roasting again.
When the organic acid of step (1) employing is oxalic acid, preferably be added with competitive adsorbate ammonium nitrate in the described nickel nitrate solution, so that metal active constituent rationally distributes.
Described catalyst preferably contains 1% nickel oxide and 3% molybdenum oxide by weight.
Adopt the invention catalyst to carry out modifying catalytically cracked gasoline, the product olefin(e) centent (v/v) that obtains :≤25%; Arene content (v/v) :≤35%; Benzene content (v/v) :≤1%; Desulfurization degree (%): 〉=80%; Liquid yield (wt%): 〉=98; Anti-knock index loss :≤1 unit, product quality be improved significantly.
Description of drawings
Fig. 1 is the sem photograph of ZSM-5/SAPO-11 composite zeolite of the present invention.
Fig. 2 is the sem photograph of the ZSM-5/SAPO-11 composite zeolite of Comparative Examples 1.
Fig. 3 is the sem photograph of the ZSM-5/SAPO-11 mechanical impurity of Comparative Examples 2.
The specific embodiment
Below by embodiment method provided by the invention is given further instruction, but not thereby limiting the invention.
In the composite zeolite, the relative amount of ZSM-5 and SAPO-11 is determined according to the XRD spectra internal standard method of CN 1565967A.
Embodiment 1
Present embodiment synthesizes sodium type ZSM-5/SAPO-11 composite zeolite I.
By chemical composition (mol ratio) 9.7Na
2O:1Al
2O
3: 55SiO
2: 10TEAOH (tetraethyl ammonium hydroxide): 3500H
2The initial gel of O preparation ZSM-5, and with in its 500ml reactor of packing into, crystallization is 48 hours under 175 ℃ of conditions, obtains the ZSM-5 crystallization product.In this crystallization product, by chemical composition (mol ratio) 1DPA (di-n-propylamine): 1Al
2O
3: 1P
2O
5: 0.4SiO
2: 50H
2O quantitatively adds phosphorus source, aluminium source, silicon source and organic amine successively, and with reaction mixture gel in 185 ℃ of following crystallization 24 hours, the sodium type composite zeolite I that obtains consists of: the sial ratio of sodium type ZSM-5 is 50, weight percentage is 30%; The sial ratio of sodium type SAPO-11 is 0.3, and weight percentage is 70%.Its stereoscan photograph is seen Fig. 1.
Embodiment 2
Present embodiment synthesizes sodium type ZSM-5/SAPO-11 composite zeolite II.
By chemical composition (mol ratio) 8.5Na
2O:Al
2O
3: 68SiO
2: 15TEAOH (tetraethyl ammonium hydroxide): 3000H
2The initial gel of O preparation ZSM-5, and with in its 500ml reactor of packing in 175 ℃ of following crystallization 48 hours, obtains the ZSM-5 crystallization product.In this crystallization product, by chemical composition (mol ratio) DPA (di-n-propylamine): Al
2O
3: P
2O
5: 0.8SiO
2: 50H
2O quantitatively adds phosphorus source, aluminium source, silicon source and organic amine successively, and with reaction mixture gel in 190 ℃ of following crystallization 24 hours, obtain sodium type ZSM-5/SAPO-11 composite zeolite II, wherein: ZSM-5 sial ratio is 62, weight percentage is 20%; The sial ratio of SAPO-11 is 0.6, and weight percentage is 80%.
Embodiment 3
Present embodiment synthesizes sodium type ZSM-5/SAPO-11 composite zeolite III.
By chemical composition (mol ratio) 10.6Na
2O:Al
2O
3: 79SiO
2: 20TEAOH (tetraethyl ammonium hydroxide): 3600H
2The initial gel of O preparation ZSM-5, and with in its 500ml reactor of packing in 175 ℃ of following crystallization 48 hours, obtains the ZSM-5 crystallization product.In this crystallization product, by chemical composition (mol ratio) DPA (di-n-propylamine): Al
2O
3: P
2O
5: 1.0SiO
2: 50H
2O quantitatively adds phosphorus source, aluminium source, silicon source and organic amine successively, and with reaction mixture gel in 190 ℃ of following crystallization 24 hours, obtain sodium type ZSM-5/SAPO-11 composite zeolite III, wherein: ZSM-5 sial ratio is 70, weight percentage is 40%; The sial ratio of SAPO-11 is 0.8, and weight percentage is 60%.
Comparative Examples 1
This Comparative Examples is synthesized sodium type ZSM-5/SAPO-11 composite zeolite.
With the commercially available sial ratio of 20 grams is that 50 ZSM-5 adds chemical composition (mol ratio) and is DPA (di-n-propylamine): Al
2O
3: P
2O
5: 0.4SiO
2: 50H
2In the initial gel of O, and with this gel in 185 ℃ of following crystallization 24 hours, obtain sodium type ZSM-5/SAPO-11 composite zeolite Comparative Examples, wherein: ZSM-5 sial ratio is 50, content is 30wt%; The sial ratio of SAPO-11 is 0.3, and content is 70wt%.Its stereoscan photograph is seen Fig. 2.
Comparative Examples 2
The ZSM-5/SAPO-11 mechanical mixture zeolite of preparation of this Comparative Examples and composite zeolite I same composition.
With the commercially available sial ratio of 30 grams be 50 ZSM-5 and 70 gram sial ratios are that 0.3 SAPO-11 (press USP 4,440,871 synthesize) porphyrize evenly mixes, and makes ZSM-5/SAPO-11 mechanical mixture zeolite.Its stereoscan photograph is seen Fig. 3.
Comparison diagram 1～3 as can be known, two kinds of zeolites are just independent in the mechanical mixture zeolite exists, the small part particle sticks together, and does not produce the coating (Fig. 3) of outer surface; And after commercially available treated ZSM-5 being dropped in the synthetic environment of SAPO-11, identical (Fig. 2) of the pattern of the composite zeolite Comparative Examples of being synthesized and mechanical impurity, this explanation post processing (filtration, washing, drying and roasting etc.) can change the alkaline environment on ZSM-5 crystallization product surface and the quantity of alkali metal cation, and has therefore suppressed SAPO-11 in its surperficial outgrowth.
Different with said two devices, present the phenomenon (Fig. 1) in the tangible ZSM-5 one end implantation SAPO-11 zeolite on the stereoscan photograph of sodium type composite zeolite I, this point can be confirmed by the data in the table 1.
The SEM energy spectrum analysis of table 1 sample
Embodiment 4
This examples preparation is the catalyst A of carrier with composite zeolite I.
Get 40 gram sodium type composite zeolite I, 90～95 ℃ down with 400 milliliters of 1mol/L ammonium nitrate solution exchange 4 hours, filtration, washing, drying, twice of repetitive operation; Handled 4 hours down at 90～95 ℃ with the oxalic acid solution of 400 milliliters of 1mol/L again, filter, wash filtrate is to neutral, 120 ℃ of dryings 3 hours, Hydrogen composite zeolite I is made in 540 ℃ of roastings 5 hours.
Take by weighing 20 gram Hydrogen composite zeolite I, 9 gram Al
2O
3With 0.9 gram sesbania powder, its ground and mixed is even, add the 3ml mass concentration and be 65% salpeter solution, fully mix and pinch back extruded moulding in banded extruder, after 120 ℃ of dryings, 520 ℃ of roastings, make catalyst carrier.
Said catalyst carrier 20 grams be impregnated in 16ml contain 0.6 gram MoO
3Ammonium molybdate solution in, 3 hours, 480 ℃ roastings of 8 hours, 120 ℃ dryings of ageing at room temperature 4 hours; Then, product of roasting be impregnated in nickel nitrate and the 2.2 gram NH that 16ml contains 0.2 gram NiO
4NO
3Solution in, after 120 ℃ of dryings, 480 ℃ of roastings, make catalyst A.
In the present embodiment, can be by adjusting the content that the concentration of ammonium molybdate and nickel nitrate in the solution change nickel oxide and molybdenum oxide in the catalyst, for example for the catalyst of the molybdenum oxide that obtains to contain by weight 1% nickel oxide and 3%.
Embodiment 5
The present embodiment preparation is the catalyst B of carrier with the mechanical mixture zeolite of Comparative Examples 2.The preparation method is identical with embodiment 4, and different is no ammonium exchange and organic acid processing procedure.
Embodiment 6
Present embodiment preparation is that 50 HZSM-5 zeolite is the catalyst C of carrier with sial ratio.The preparation method is identical with example 4, and different is no ammonium exchange and organic acid processing procedure.
Embodiment 7
Present embodiment preparation is that 0.3 SAPO-11 zeolite is the catalyst D of carrier with sial ratio.The preparation method is identical with embodiment 3, and different is no ammonium exchange and organic acid processing procedure.
Embodiment 8
Present embodiment explanation ZSM-5/SAPO-11 composite zeolite is catalyst based in the application that improves aspect the FCC quality of gasoline.
Catalyst A～D is respectively charged in the small stationary bed bioreactor, and charge weight is 10ml, airtight qualified after, at first carry out presulfiding of catalyst.Sulfurized oil is a direct steaming gasoline, and vulcanizing agent is CS
2, its concentration is 3.0wt%; Sulfide stress is 2.8MPa, vulcanizes 1 hour down at 150 ℃, vulcanizes respectively under 230 ℃, 290 ℃, 320 ℃ and 340 ℃ 6 hours; The sulfurized oil volume space velocity is 2.0h
-1After sulfuration finishes, switch to feedstock oil displacement 2 hours, then reaction pressure is reduced to 2.0MPa, reaction temperature rises to 380 ℃, stablize 10 hours after, sampling analysis.Reaction result after 24 hours sees Table 2.
The last FCC gasoline upgrading of table 2 catalyst A～D result
As can be seen from Table 2, catalyst A～D all has excellent desulfurization initial activity, but alkene falls, there were significant differences to keep the ability of octane number.HZSM-5 zeolite based catalysts (catalyst C) has very high coke content, lower liquid yield and minimum anti-knock index, and these illustrate that all this catalyst is not suitable for the upgrading of FCC gasoline; And SAPO-11 zeolite based catalysts (catalyst D) is though have the active and very high liquid yield of excellent hydroisomerization, and its aromatization activity is lower, the octane number of product lower (with 3.9 units of feedstock oil anti-knock index loss).Compare with single S APO-11 zeolite based catalysts, the hydroisomerization performance of ZSM-5/SAPO-11 mechanical impurity catalyst based (catalyst B) descends, but its aromatisation performance makes moderate progress, the product anti-knock index increases by 1.1 units, yet still lose 2.8 units with comparing of feedstock oil, and the coke content of this catalyst is bigger, shows its less stable.Compare with former three, composite zeolite catalyst based (catalyst A) has remarkable advantages, not only has higher hydroisomerization activity, also has more excellent aromatization activity, and the anti-knock index of product and feedstock oil is suitable, coke content on the catalyst is less, this be since in the composite zeolite interfacial effect of ZSM-5 and SAPO-11 strengthened the two synergy aspect acidity and pore structure.
On the basis of above-mentioned work, further investigated the catalyst based stability of ZSM-5/SAPO-11 composite zeolite, the results are shown in Table 3.As seen from table, behind the catalyst based operation of the composite zeolite 350h, isoparaffin has on average increased 11.43v%, shows good hydroisomerization stability; Aromatic hydrocarbons has on average increased 4.09v%, demonstrates certain aromatisation stability; Alkene has on average reduced 21.49v%, shows well to fall the alkene ability; Liquid yield mean value is 99.4wt%; Desulfurization degree is 80%, and the loss of octane number of product is very little.This shows that the ZSM-5/SAPO-11 composite zeolite is catalyst based has good desulfurization performance, the excellent alkene ability of falling and very high liquid and receives, and is a kind of high performance FCC gasoline hydrogenation modifying catalyst.
The stability test result that table 3 ZSM-5/SAPO-11 composite zeolite is catalyst based
*Desulfurization degree-80%, liquid yield-99.4wt%
Claims (8)
1, a kind of ZSM-5/SAPO-11 composite zeolite is characterized in that described composite zeolite prepares by the following method:
With aluminum sulfate, sulfuric acid and water wiring solution-forming A, with waterglass, tetraethyl ammonium hydroxide and water wiring solution-forming B; Then, under intensively stirred situation, solution A is slowly added in the solution B, until forming even colloid; Again with colloid admixture 150～180 ℃ of following crystallization 24～72 hours, in crystallization product, add the used template agent of phosphoric acid, boehmite, Ludox and synthetic SAPO-11 then, after 24～48 hours, obtain a kind of sodium type composite zeolite that SAPO-11 is arranged in ZSM-5 surface outgrowth 170～200 ℃ of following crystallization again; The weight percentage of ZSM-5 zeolite is 20～40% in the described sodium type composite zeolite, and the silica alumina ratio value is 50～70; The weight percentage of SAPO-11 zeolite is 60～80%, and the silica alumina ratio value is 0.2～0.8.
2, ZSM-5/SAPO-11 composite zeolite according to claim 1 is characterized in that described template agent is a di-n-propylamine.
3, a kind of preparation method of catalytic gasoline hydrogenation modifying catalyst is characterized in that may further comprise the steps:
(1) claim 1 or 2 described ZSM-5/SAPO-11 composite zeolites are carried out the ammonium exchange and organic acid is handled with the reduction sodium content, ZSM-5/SAPO-11 Hydrogen composite zeolite is made in drying and roasting again, and described organic acid is treated to oxalic acid solution and handled 4 hours down at 90-95 ℃;
(2) described ZSM-5/SAPO-11 Hydrogen composite zeolite is mixed by weight 1～4:1 with binding agent, in the mixture that forms, add sesbania powder and HNO
3The aqueous solution, the final concentration that makes the sesbania powder by weight are 1～3% and HNO
3Final concentration be 2～5%, pinch through mixing again, after extrusion modling, drying and the roasting, to make catalyst carrier;
(3) carried metal active component on described catalyst carrier, finished product is made in drying and roasting again.
4, preparation method according to claim 3 is characterized in that the described carried metal active component of step (3) is to adopt equi-volume impregnating load nickel oxide and molybdenum oxide on described catalyst carrier.
5, preparation method according to claim 4 is characterized in that described loading process comprises:
A) described catalyst carrier be impregnated in the ammonium molybdate solution, then drying and calcination process;
B) catalyst carrier after the step a) processing be impregnated in the nickel nitrate solution, then drying and calcination process.
6, preparation method according to claim 3 is characterized in that the binding agent that step (2) adopts is a boehmite.
7, a kind of catalytic gasoline hydrogenation modifying catalyst that obtains according to each preparation method of claim 3～6.
8, catalytic gasoline hydrogenation modifying catalyst according to claim 7 is characterized in that containing by weight in the described catalyst 1% nickel oxide and 3% molybdenum oxide.
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| CN104107721B (en) * | 2013-04-16 | 2018-06-08 | 中国石油化工股份有限公司 | ZSM-11/SAPO-11 binary structure zeolites catalyst, preparation method and applications |
| CN104108727B (en) * | 2013-04-16 | 2016-02-10 | 中国石油化工股份有限公司 | ZSM-11/SAPO-11 binary structure zeolite and synthetic method thereof |
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| CN101081370A (en) | 2007-12-05 |
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