CN101862671B - Introducing method of active components formed and processed by beta molecular sieve based catalyst - Google Patents
Introducing method of active components formed and processed by beta molecular sieve based catalyst Download PDFInfo
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- CN101862671B CN101862671B CN 200910082448 CN200910082448A CN101862671B CN 101862671 B CN101862671 B CN 101862671B CN 200910082448 CN200910082448 CN 200910082448 CN 200910082448 A CN200910082448 A CN 200910082448A CN 101862671 B CN101862671 B CN 101862671B
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Abstract
The invention relates to an introducing method of active components formed and processed by a beta molecular sieve based catalyst, which comprises the steps of: 1, putting raw powder of a hydrogen type beta-H molecular sieve and a binding agent into a mixer and mixing for 20-40min, wherein the weight ratio of the raw powder and the binding agent is 15-17kg:2.2-5.0kg; and 2, adding 19-21L of nitric acid water solution containing the active components in a mixture of the step 1, adding 0.10-1.7kg of active components in the nitric acid water solution, wherein the weight ratio of the raw powder and the active components is 15-17kg:0.10-1.2kg, kneading for 30-50min in a kneading machine, processing and forming, drying, roasting to obtain the beta molecular sieve based catalyst containing the active components. The prepared catalyst is added in a first step kneading process of a forming processing procedure after the active components are mixed with the raw powder of the hydrogen type beta-H molecular sieve and the binding agent and the like, which can omit the processes of washing, water-removing, drying and roasting in a hydrogen after-forming/ionic reaction and saves more energy so as to have low cost.
Description
Technical field
The present invention relates to a kind of introducing method of active components formed and processed by beta molecular sieve based catalyst.
Background technology
Beta-molecular sieve can divide sodium type and Hydrogen, and sodium type beta-molecular sieve does not have acidity, and Hydrogen has acidity, has possessed a certain amount of surface acidity center, and some chemical reaction is had the acid catalyst effect.For guaranteeing that catalyst can satisfy chemical reaction conversion rate and optionally requirement, needing that as a rule beta-molecular sieve is carried out acidity regulates, to change wherein all total acid acid amounts and the proportioning of heterogeneity acid (strong acid, weak acid), this way is called molecular sieve modified, and molecular sieve catalysts active component introducing method commonly used has following several:
1, the former powder/ion-exchange of sodium type
With the metallic salt material aqueous solution the former powder of sodium type beta-molecular sieve is carried out cation exchange, with metal cation sodium ion is exchanged away, more after filtration, the processing procedure such as roasting can obtain the former powder in certain acid catalyst activated centre.This former powder often needs to carry out processing and forming and makes it become certain grain shape in industrial use difficulty, so that use.Add formed substances such as to add sticky agent man-hour and guarantee that it has enough intensity.
2, after the moulding of sodium type/ion-exchange
After first the former powder of sodium type beta-molecular sieve and sticky agent etc. being mixed, carry out the processing and forming operation, has the shaped article of certain granules after roasting has some strength, carry out cation exchange with the sodium type beta-molecular sieve of the metallic salt material aqueous solution after to moulding again, with metal cation sodium ion is exchanged away, more after filtration, the processing procedure such as roasting can obtain the preformed catalyst in certain acid catalyst activated centre.
3, the former powder of Hydrogen/ionization method
With the metallic salt material aqueous solution and the former powder effect of Hydrogen beta-molecular sieve, its mode of action is former powder to be put into the excessive metallic salt material aqueous solution flood, behind the dipping more after filtration, the processing procedures such as roasting can obtain that (the former powder that obtains is to burn once through the 450-550 degree with the former powder of the original Hydrogen beta-molecular sieve different modification of former powder Acidity here, the former powder after the modification), use again the former powder of modification and adhesive, forming agent, aqueous solution of nitric acid is mediated, moulding, oven dry, the processing and forming operation of roasting is used after making it become certain grain shape.
4, after the Hydrogen moulding/the ionization method
To have first after the former powder of Hydrogen beta-molecular sieve of certain acid centre and sticky agent etc. mix, carry out the processing and forming operation, has the shaped article of certain granules after roasting has some strength, with methods such as dipping, fumigations active constituent is incorporated on the molecular sieve catalyst again, wash again, dewater, oven dry and roasting, obtain the modified catalyst different from the former powder acid centre of Hydrogen beta-molecular sieve.
5, synthetic introducing method
Active constituent (being generally metallic element) when the Zeolite synthesis, is introduced in the framework of molecular sieve (or surface), makes it have the function that generates the active sites structure.Process the former powder that can obtain certain acid catalyst activated centre through respective process again.After the processing and forming, can use in engineering.
Summary of the invention
The object of the present invention is to provide a kind of introducing method of active components formed and processed by beta molecular sieve based catalyst.
For achieving the above object, the invention provides following technical scheme:
A kind of introducing method of active components formed and processed by beta molecular sieve based catalyst, the method may further comprise the steps:
(1) the former powder of Hydrogen β-H molecular sieve is dropped in the mixer with binder mixed 20-40 minute, wherein, the weight ratio of former powder and binder is: the 15-17 kilogram: the 2.2-5.0 kilogram;
(2) in the mixture of step (1), add the aqueous solution of nitric acid that contains active component, adding the aqueous solution of nitric acid amount that contains active component is 19 liters-21 liters, the active component that wherein in this aqueous solution of nitric acid, adds 0.10 kilogram-1.2 kilograms, the weight ratio of described former powder and active component is: the 15-17 kilogram: the 0.10-1.2 kilogram; Then in kneader, mediated machine-shaping post-drying, the rear beta-molecular sieve catalyst that under 540 ℃ of-560 ℃ of temperature conditions, can obtain containing active component in roasting 5-6 hour of oven dry 30-50 minute.
The silica molar ratio of the former powder of employed Hydrogen β-H molecular sieve is 24-26 in the described step (1).
Employed active component is generally metallic salt in the described step (2), but is preferably nitrate.Nitrate such as AgNO
3, Cu
2+(NO
3)
23H
2O, Al
3+(NO
3)
39H
2O etc.When use contains aluminium type binder, select active component should avoid using aluminium salt, as, use to contain aluminium type binder, and active component selection nitrate is Al
3+(NO
3)
39H
2During O, following problem will occur: in step (1), the weight ratio of former powder and binder is: the 15-17 kilogram: the 2.2-5.0 kilogram, wherein, contain a large amount of aluminium in the binder of 2.2-5.0 kilogram, and add again 0.10 kilogram of-1.2 kilograms of Al
3+(NO
3)
39H
2During O, " the active component aluminium " that it adds can not play a big part.So contain in the aluminium type binder situation in use, the aluminium active component is generally the metallic salt of non-aluminum metal, is preferably the nitrate of non-aluminum metal, that is to say the nitrate beyond the preferred aluminum nitrate.And using non-containing in aluminium binder (such as the silica-type) situation, available aluminium salt is that active component is added.
Employed salpeter solution is the aqueous solution of nitric acid of 6-10wt% in the described step (2).
Described bake out temperature is 100-120 ℃, and the time of oven dry is 6-7 hour.
In described step (1), in the former powder and binder mixing of Hydrogen β-H molecular sieve, also add the sesbania powder, the weight ratio of described former powder and sesbania powder is: the 15-17 kilogram: the 0.14-0.16 kilogram.
The present invention is in molecular sieve catalyst machine-shaping process, needing to add diluted nitric acid aqueous solution mediates, utilize this forming process link, a certain amount of active constituent material (being generally metallic salt) is dissolved in the diluted nitric acid aqueous solution, be added in the compound together and mediate, then carry out each step operation of machine-shaping.The disposable corresponding site that enters into the corresponding duct of molecular sieve of active constituent, in the calcination activation process, corresponding group on metal ion and the framework of molecular sieve reacts, realize the foundation of active sites and the change of active sites character, thereby make active sites number change (relevant with the valence state of metal ion), finish the task of disposable adjusting active sites quantity and active sites character, reduced the processing procedure of a supported active component.
The molecular sieve catalytic mechanism of action is very complicated, relates to several factors.With regard to molecular sieve catalyst itself, the molecular sieve acid site is the focus of paying close attention to.Because it is a lot of to affect the factor of molecular sieve acid site formation, and each factor affecting degree is not identical again, so acid site formation research on mechanism is very complicated.However, the theory of relatively generally acknowledging has been arranged also, as producing Bronsted acid (B acid) mechanism, producing aprotic acid (L acid) mechanism etc.
About the Bronsted acid center (B acid) of beta-molecular sieve and the formation at aprotic acid center
(1) formation at Bronsted acid (B acid) center
The preparation of β-H molecular sieve is to have this principle of ion-exchange performance according to molecular sieve to carry out.Generally with ammonium salt sodium type beta-molecular sieve is carried out heat exchange, make it NH through heat treatment again
3, NH
4 +In H
+Substituted in the molecular sieve and Al
-The Na that keeps balance
+, reach charge balance, make it become demetalization cation or part demetalization cationic molecule sieve, and have acidity:
The hydrogen of β-H in the formula (H) and skeleton function present three kinds of states of continuous reversible: the first state is complete Ionized hydrogen ion (H
+, so-called Bronsted acid); State is hydrogen ion (H in second
+) the transition situation H...O that combines with oxygen, present and intensify attitude; The third state is hydrogen ion (H
+) form surface hydroxyl (OH) with the effect of skeleton oxygen.This moment, β-H was owing to there has been complete Ionized hydrogen ion (H
+), had acidity (B acid) center.And the hydrogen of these three kinds of states can transform under certain condition mutually, such as rising temperature, raising silica alumina ratio or exchange polyvalent cation etc. whole reversible process is moved to the first state direction, thereby make acid the raising.
(2) formation at aprotic acid (L acid) center
If above-mentioned β-H molecular sieve＞450 ℃ of roastings, dehydration reversible reaction progressively can be occured, its reason is the H in β-H molecular sieve
+, can form surface hydroxyl-OH with the effect of skeleton oxygen under certain condition, when high-temperature heat treatment, among β-H with Al
-The H that keeps balance
+Will with framework of molecular sieve in hydroxyl-OH generate H
2O and being removed.At this moment, lose H
+Three-fold coordination Al
-Be considered to aprotic acid (L acid) center.At this moment, β-H molecular sieve has had again aprotic acid (L acid) center.
Formation about polyvalent cation exchange beta-molecular sieve acid centre
Multistage cation exchange refers generally to can the sodium ion in the sodium type beta-molecular sieve be exchanged with the multistage cation of sodium ion exchange with certain.For the polyvalent cation beta-molecular sieve after the exchange, containing an amount of moisture content in the molecular sieve is the necessary condition that produces acid centre, and the formation of its Bronsted acid is the result that dissociation occurs with being subjected to cationic polarization moisture:
M
+++H
2O＝M(OH
2)
++
(MOH
2)
++＝(MOH)
++H
+
M represents metallic element in the formula.Following formula shows M
++Water there is polarization, can in molecular sieve, produces a Bronsted acid (H
+), this Bronsted acid can play acid catalysis.In addition, the generation of aprotic acid (L acid) then is Bronsted acid (H
+) further with skeleton in oxygen form hydroxyl and (OH), then remove the result of hydroxyl, with identical described in (one) :-OH and H
+Generate water and be removed.Like this, M
++Molecular sieve after the exchange has just had the acid centre of Bronsted acid (B acid) and two kinds of character of aprotic acid (L acid).
For the Hydrogen beta-molecular sieve, if multistage cation can be with proton H
+Exchange is got off, and so, the formation mechanism of its acid centre should be identical with above-mentioned mechanism.
Analysis is the multivalence of raw material introducing or the situation of univalent cation with Hydrogen β-H molecular sieve on the basis of the formation mechanism of generation Bronsted acid (B is sour) mechanism, generation aprotic acid (L acid) mechanism and polyvalent cation exchange beta-molecular sieve acid centre.
(1), about introducing polyvalent cation
The present invention is to be raw material with Hydrogen β-H molecular sieve, and the polyvalent cation of introducing just has two kinds of situations, one: have exchange to replace H in the molecular sieve
+Ability; Its two: exchange replaces H in the molecular sieve
+Ability.The first situation is discussed first, and namely polyvalent cation has exchange to replace H in the molecular sieve
+The situation of ability.Forming mechanism based on above-mentioned molecular sieve acid site, is raw material with β-H molecular sieve, and certain metal ion is added in batch mixing is mediated with aqueous solution form, and polyvalent cation is mediated and later moulding, an oven dry and roasting link at batch mixing, all will occur and H
+Exchange replace.Finish polyvalent cation that exchange replaces and be combined formation M (OH with water
2)
++, afterwards with regard to as discussed above the same, through M
++Molecular sieve after the exchange has just had the acid centre of Bronsted acid (B acid) and two kinds of character of aprotic acid (L acid).Certainly, this method still exists polyvalent cation and H
+The problem of the exchange degree of ion, not exchanged polyvalent cation just is dispersed on the skeleton surface, their existence also exerts an influence to acid amount and Acidity, belongs to the polyvalent cation active constituent loading, and this all plays a role to the acid amount of molecular sieve and the change of Acidity.
The second situation, namely polyvalent cation does not exchange and replaces H in the molecular sieve
+The situation of ability.For polyvalent cation in such cases, can belong to polyvalent cation fully and load to processing procedure on the molecular sieve, this processing procedure also can play regulating action to acid amount and the Acidity of molecular sieve.
(2), about introducing univalent cation
The present invention is to be raw material with Hydrogen β-H molecular sieve, and the univalent cation of introducing just has two kinds of situations, one: have exchange to replace H in the molecular sieve
+Ability; Its two: exchange replaces H in the molecular sieve
+Ability.The first situation is discussed first, and namely univalent cation has exchange to replace H in the molecular sieve
+The situation of ability.Forming mechanism based on above-mentioned molecular sieve acid site, is raw material with Hydrogen β-H molecular sieve, and certain metal ion is added in batch mixing is mediated with aqueous solution form, and univalent cation is mediated and later moulding, an oven dry and roasting link at batch mixing, all will occur and H
+Exchange replace, then form the process that B acid and L acid etc. change acid amount and Acidity.This method still exists univalent cation and H
+The problem of the exchange degree of ion, not exchanged univalent cation just is dispersed on the skeleton surface, their existence also exerts an influence to acid amount and Acidity, belongs to the univalent cation active constituent loading, and this has certain impact to the acid amount of molecular sieve and the change of Acidity.
The second situation, namely univalent cation does not exchange and replaces H in the molecular sieve
+The situation of ability.For univalent cation in such cases, can belong to univalent cation fully and load to processing procedure on the molecular sieve, this processing procedure also can play regulating action to acid amount and the Acidity of molecular sieve.
The present invention utilizes in molecular sieve catalyst machine-shaping process, needs to add diluted nitric acid aqueous solution and mediates, and utilizes this forming process link, and (the nitrate active component that the present invention uses is nitrate, such as, AgNO with a certain amount of active constituent material
3, Cu
2+(NO
3)
23H
2O, Al
3+(NO
3)
39H
2O etc.) be dissolved in the diluted nitric acid aqueous solution, be added in the compound together and mediate, then carry out each step operation of machine-shaping.The disposable corresponding site that enters into the corresponding duct of molecular sieve of active constituent, in the calcination activation process, metal ion will with framework of molecular sieve on corresponding group react, realize the foundation of active sites and the change of active sites character, thereby make active sites number change (relevant with the valence state of metal ion), finish the task of disposable adjusting active sites quantity and active sites character, reduced the processing procedure of a supported active component.
The invention has the advantages that: introducing method of active components formed and processed by beta molecular sieve based catalyst of the present invention can be called for short and be called: " the Hydrogen molding process is introduced method ".Method of the present invention institute controlling catalyst main points be with active component (being generally metallic element) after the former powder of Hydrogen beta-molecular sieve and sticky agent etc. mix, carry out adding in the first step-kneading process of processing and forming operation, after can saving the Hydrogen moulding described in the background technology/washing in the ionization method (the 4th kind of method), dewater, oven dry and roasting process, more economically with energy-conservation.
Description of drawings
Fig. 1 is the ammonia desorption figure of 1#, 2# and 3# sample in the embodiment of the invention;
Fig. 2 is the ammonia desorption figure of 1# and 4# sample in the embodiment of the invention.
The specific embodiment
The used salpeter solution of following embodiment and comparative example is the aqueous solution of nitric acid of wt%.
The comparative example 1
The raw material proportioning
The former powder of Hydrogen β-H molecular sieve (silica alumina ratio is 25): 16 kilograms
Binder (SB powder: boehmite): 4 kilograms
Sesbania powder: 0.15 kilogram
Active component addition: nothing
8%HNO
3The aqueous solution: 20 liters
The machine-shaping process
Press the above-mentioned raw materials proportioning, with 16 kilograms of Hydrogen β-H molecular sieve, 0.15 kilogram in 4 kilograms of binders and sesbania powder are put in the mixer 30 minutes kinds of dry powder blend; Pour into afterwards in the kneader, add again 20 liters of 8% concentration aqueous solution of nitric acid, carry out wet feed and mediate mixing, knead and mixed 40 minutes; Carry out afterwards the extruded moulding manufacturing procedure.100-120 ℃ of baking is after 6 hours in baking oven for wet strip catalyst, and cooling is put into roasting in kilns afterwards near room temperature naturally.550 ℃ of roasting maximum temperatures, the maximum temperature duration is 5 hours.Finished product is designated as 1#.
The raw material proportioning
The former powder of Hydrogen β-H molecular sieve (silica alumina ratio is 25): 16 kilograms
Binder (SB powder: boehmite): 4 kilograms
Sesbania powder: 0.15 kilogram
Active component silver ion (Ag
+) addition: add AgNO
3, 0.34 kilogram
8%HNO
3The aqueous solution: 20 liters
The machine-shaping process
Press the above-mentioned raw materials proportioning, with 16 kilograms of Hydrogen β-H molecular sieve, 0.15 kilogram in 4 kilograms of binders and sesbania powder are put in the mixer 30 minutes kinds of dry powder blend; Pour into afterwards in the kneader, add again and contain AgNO
30.34 20 liters of 8% concentration aqueous solution of nitric acid of kilogram carry out wet feed and mediate mixing, knead and mix 40 minutes; Carry out afterwards the extruded moulding manufacturing procedure.100-120 ℃ of baking is after 6 hours in baking oven for wet strip catalyst, and cooling is put into roasting in kilns afterwards near room temperature naturally.550 ℃ of roasting maximum temperatures, the maximum temperature duration is 5 hours.Finished product is designated as 2#.
The raw material proportioning
The former powder of Hydrogen β-H molecular sieve (silica alumina ratio is 25): 16 kilograms
Binder (SB powder: boehmite): 4 kilograms
Sesbania powder: 0.15 kilogram
Active component silver ion (Cu
2+) addition: add Cu
2+(NO
3)
23H
2O, 0.48 kilogram
8%HNO
3The aqueous solution: 20 liters
The machine-shaping process
Press the above-mentioned raw materials proportioning, with 16 kilograms of Hydrogen β-H molecular sieve, 0.15 kilogram in 4 kilograms of binders and sesbania powder are put in the mixer 30 minutes kinds of dry powder blend; Pour into afterwards in the kneader, add again and contain Cu
2+(NO
3)
23H
2O, 20 liters of 0.48 kilogram 8% concentration aqueous solution of nitric acid carry out wet feed and mediate mixing, knead and mix 40 minutes; Carry out afterwards the extruded moulding manufacturing procedure.100-120 ℃ of baking is after 6 hours in baking oven for wet strip catalyst, and cooling is put into roasting in kilns afterwards near room temperature naturally.550 ℃ of roasting maximum temperatures, the maximum temperature duration is 5 hours.Finished product is designated as 3#.
The comparative example 4
The raw material proportioning
The former powder of Hydrogen β-H molecular sieve (silica alumina ratio is 25): 16 kilograms
Binder (SB powder: boehmite): 4 kilograms
Sesbania powder: 0.15 kilogram
Active component silver ion (Al
3+) addition: add Al
3+(NO
3)
39H
2O, 0.75 kilogram
8%HNO
3The aqueous solution: 20 liters
The machine-shaping process
Press the above-mentioned raw materials proportioning, with 16 kilograms of Hydrogen β-H molecular sieve, 0.15 kilogram in 4 kilograms of binders and sesbania powder are put in the mixer 30 minutes kinds of dry powder blend; Pour into afterwards in the kneader, add again and contain Al
3+(NO
3)
39H
2O, 20 liters of 0.75 kilogram 8% concentration aqueous solution of nitric acid carry out wet feed and mediate mixing, knead and mix 40 minutes; Carry out afterwards the extruded moulding manufacturing procedure.100-120 ℃ of baking is after 6 hours in baking oven for wet strip catalyst, and cooling is put into roasting in kilns afterwards near room temperature naturally.550 ℃ of roasting maximum temperatures, the maximum temperature duration is 5 hours.Finished product is designated as 4#.
Carry out catalyst sample acid scale for 1#, 2#, 3# and 4# finished product and levy analysis.Acid amount and Acidity are topmost performances in the catalyst performance, although hydrogen type molecular sieve has certain catalytic activity, a lot of situations are to add one or more metals with modulation Acidity and acid amount, because the active metal substance that adds is not enough to detect in XRD detects, use alkaline matter (molecular size requires to enter the material of molecular sieve pore passage and stable chemical nature, generally adopts ammonia or pyridine etc.) to detect Acidity and the acid amount of catalyst in the experiment.Acidity and acid amount generally are with temperature programmed desorption of ammonia (NH
3-TPD) experiment and infrared the detection, infrared detection still can not be quantitative.The present invention adopts temperature programmed desorption of ammonia (NH
3-TPD) experiment detects.With regard to temperature programmed desorption of ammonia, Acidity is to determine with the peak position of ammonia desorption curve, and the acid amount is to determine with the peak area size of ammonia desorption curve.
(1) the catalyst acid amount detects
The measuring instrument: full-automatic chemical adsorption instrument (Automated Catalyst Characterization System),
Model: Autochem 2920,
Manufacturer: U.S. MICROMERITICS company product,
Ammonia: wt 〉=99.95%, Beijing oxygen installation are adopted in experiment.
Experiment condition and operation:
Take by weighing about 0.1g sample and put into sample cell, sweep under the condition in the He air-blowing and rise to 200 ℃ with 10 ℃/min, stop 1h, be down to 40 ℃; Changing gas is 10%NH again
3-He gaseous mixture is with the throughput absorption 1h of 10ml/min; And then use instead and be that He gas purges 1h with the throughput of 20ml/min; Begin counting after the baseline stability, rise to 700 ℃ with 10 ℃/min, stop record, finish experiment.
(2) sample detection result
Utilize shaping of catalyst processing introducing method of active components provided by the invention, prepared the Ag that introduces the active component unit price
+, divalence Cu
2+Al with trivalent
3+Three samples are investigated the feasibility of method for preparing catalyst of the present invention.
The total acid of each sample 1#, 2# and 3#, strong acid and weak acid amount are listed in the table 1, and wherein sample 1# is not for adding the benchmark sample of active component.For more convenient, with the NH of 1#, 2# and 3# sample
3Desorption figure is stacked together and is shown in Fig. 1, the NH of 1# and 4# sample
3Desorption figure is stacked together and is shown in Fig. 2.
From table 1 total acid, strong acid and weak acid amount, sample 1#, 2# and 3# have some difference, and this difference illustrates that this active component introducing method is effective; Also can obviously find out from the data of strong acid amount/weak acid amount, it can to heterogeneity acid ratio effectively regulate.The ammonia desorption figure of sample 1#, 2# and 3# obviously finds out this difference among Fig. 1.
Table 1 data show that also the difference of 1# and 4# sample is very little, trace it to its cause mainly be since in batching, added 20% contain the aluminium binder because the existence of a large amount of aluminium adds a small amount of " active component aluminium " again, can not play a big part.This also prepares the purpose that the 4# sample compares just simultaneously.The ammonia desorption figure of sample 1# and 4# shows that difference is little among Fig. 2.Therefore, when use contains aluminium type binder, select active component should avoid using aluminium salt; If active component is used aluminium salt, such as Al
3+(NO
3)
39H
2O, the non-aluminium type binder that contains is used in the binder suggestion so, as using the silica-type binder.
Table 1 sample total acid content, strong acid and weak acid quantitative determination result
| Sample | Total acid content (mml/g) | Weak acid amount (mml/g) | Strong acid amount (mml/g) | Strong acid amount/ |
| 1# | 1.656 | 0.902 | 0.754 | 0.836 |
| 2# | 1.594 | 0.956 | 0.638 | 0.667 |
| 3# | 1.707 | 0.712 | 0.995 | 1.397 |
| 4# | 1.652 | 0.902 | 0.750 | 0.831 |
Claims (5)
1. introducing method of active components formed and processed by beta molecular sieve based catalyst is characterized in that the method may further comprise the steps:
(1) the former powder of Hydrogen β-H molecular sieve is dropped in the mixer with binder mixed 20-40 minute, wherein, the weight ratio of former powder and binder is: the 15-17 kilogram: the 2.2-5.0 kilogram;
(2) in the mixture of step (1), add the aqueous solution of nitric acid that contains the nitrate active component, the aqueous solution of nitric acid amount that this that adds contains the nitrate active component is 19 liters-21 liters, the wherein said aqueous solution of nitric acid that contains the nitrate active component is to add 0.10 kilogram-1.2 kilograms nitrate active component in aqueous solution of nitric acid, and the weight ratio of described former powder and nitrate active component is: the 15-17 kilogram: the 0.10-1.2 kilogram; Then in kneader, mediated machine-shaping post-drying, the rear beta-molecular sieve catalyst that under 540 ℃ of-560 ℃ of temperature conditions, can obtain containing active component in roasting 5-6 hour of oven dry 30-50 minute.
2. introducing method of active components formed and processed by beta molecular sieve based catalyst according to claim 1, it is characterized in that: the silica molar ratio of the former powder of employed Hydrogen β-H molecular sieve is 24-26 in the described step (1).
3. introducing method of active components formed and processed by beta molecular sieve based catalyst according to claim 1 and 2, it is characterized in that: employed aqueous solution of nitric acid is the aqueous solution of nitric acid of 6-10wt% in the described step (2).
4. a kind of introducing method of active components formed and processed by beta molecular sieve based catalyst according to claim 1 and 2, it is characterized in that: described bake out temperature is 100-120 ℃, the time of oven dry is 6-7 hour.
5. introducing method of active components formed and processed by beta molecular sieve based catalyst according to claim 1 and 2, it is characterized in that: in described step (1), in the former powder and binder mixing of Hydrogen β-H molecular sieve, also add the sesbania powder, the weight ratio of described former powder and sesbania powder is: the 15-17 kilogram: the 0.14-0.16 kilogram.
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| CN1074392A (en) * | 1992-01-13 | 1993-07-21 | 中国科学院大连化学物理研究所 | The zeolite catalyst of preparing ethyl benzene from alkylated styrene |
| CN1289641A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Solid acid catalyst containing heteropoly acid and its preparing process |
| CN1517149A (en) * | 2003-01-15 | 2004-08-04 | 中国科学院大连化学物理研究所 | Catalyst containing beta-zeolite and its preparation method and application |
| JP2006212466A (en) * | 2005-02-01 | 2006-08-17 | Idemitsu Kosan Co Ltd | Co removal catalyst and its production method |
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