CN103127950B - Preparation method of Cu-ZSM catalyst - Google Patents
Preparation method of Cu-ZSM catalyst Download PDFInfo
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- CN103127950B CN103127950B CN201310056989.3A CN201310056989A CN103127950B CN 103127950 B CN103127950 B CN 103127950B CN 201310056989 A CN201310056989 A CN 201310056989A CN 103127950 B CN103127950 B CN 103127950B
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Abstract
The invention relates to a Cu-ZSM catalyst, and a preparation method and an application thereof. The Cu loading amount of the catalyst is 23-28% of the mass of the Cu-ZSM catalyst. The method comprises the steps that: ZSM molecular sieve is mixed and stirred with a solution comprising alkali metal ions, such that M-ZSM zeolite molecular sieve is obtained; the prepared M-ZSM molecular sieve is mixed and grinded with copper acetate; the mixture is heated in a microwave heating device and is subjected to a reaction, such that a Cu-ZSM catalyst loading Cu(AC)2 is obtained. The copper catalyst has high NO conversion rate in the application of NO removing.
Description
Technical field
The present invention relates to Cu-ZSM Catalysts and its preparation method, be specifically related to a kind of Cu-ZSM catalyst of high-copper load capacity, and use Microwave Solid legal system for the method for described catalyst.Background technology
Along with the increase of industrial expansion and vehicles number, to the nitrogen oxide (NO discharging in atmosphere
x) amount is more and more, and environment and people's life is caused to serious harm.Therefore, how to take efficient denitrification, eliminate NO
xpollute and become the research topic of paying much attention in environmental protection.Can direct catalytic decomposition NO from discovery Copper Ion Exchange type zeolite molecular sieves such as Iwamoto
xafter, Cu-ZSM-5 has good catalytic activity and stability, be considered to the NO cartalytic decomposition effect catalyst of at present tool application prospect, and its catalytic activity is relevant with the content of copper ion.Because the ion exchange capacity of molecular sieve is limited, it is quite difficult that employing ion-exchange is prepared the copper zeolite of high-load, need to repeatedly exchange and roasting, and the cycle is long and efficiency is low, repeatedly after exchange and roasting, easily makes the crystal structure of molecular sieve be destroyed.According to people's researchs such as Xie Youchang, after being dry mixed, the carrier of many salts or oxide and high-ratio surface carries out heat treated, can spontaneously be individual layer or sub-Monolayer Dispersion, therefore utilize solid phase dispersion method can prepare the molecular sieve catalyst of high-activity component load capacity, as the people such as Jia Mingjun have prepared the CuCl/ZSM-5 catalyst that copper content is 8%.But catalyst prepared by the method need to carry out long high-temperature calcination, metal component is difficult to be controlled effectively in the distribution of molecular sieve surfaces externally and internally, can cause the loss of active component simultaneously.In addition, active component major part exists with non-exchange state form, has affected the activity of catalyst.
The disclosed method of prior art can not obtain the high-activity component load capacity molecular sieve catalyst of (as more than 20%), and the method complex process of the catalyst of disclosed so-called high capacity amount in prior art, consume energy high, and can not control active component in the dispersion of carrier surfaces externally and internally.Therefore, its catalytic conversion efficiency for nitrogen oxide is lower, can not in the nitrogen oxide field in removing waste gas, carry out good commercial Application.
Summary of the invention
In order to address the above problem, the invention provides a kind of Cu-ZSM catalyst of high Cu load capacity, the load capacity of described Cu can reach more than 23%, a kind of method that the present invention also provides microwave-assisted solid-state reaction to prepare described Cu-ZSM catalyst, and described catalysis is removing the application of nitrogen oxides of exhaust gas.
The invention provides a kind of Cu-ZSM catalyst, the load capacity of the Cu of described catalyst is the 23-28% of described Cu-ZSM catalyst quality; Described Cu-ZSM catalyst is preferably Cu-ZSM-11 catalyst.
The present invention also provides a kind of method of the Cu-ZSM of preparation catalyst, and it comprises the following steps:
I) ZSM molecular sieve and the solution that contains alkali metal ion are carried out to mix and blend, obtain M-ZSM zeolite molecular sieve; Described M is selected from a kind of in alkali metal; Described ZSM molecular sieve is preferably ZSM-11 molecular sieve;
Ii) by step I) the M-ZSM molecular sieve and the Schweinfurt green mixed grinding that make, and be placed in microwave heating equipment and heat and react, obtain the Cu-ZSM catalyst of loaded Cu ion, described Schweinfurt green is preferably with the Schweinfurt green of the crystallization water.
Described M is sodium and/or potassium, is preferably sodium.
In the method for preparing Cu-ZSM catalyst of the present invention, also comprise:
At step I i) in by M-ZSM zeolite molecular sieve and Cu (AC)
2during mixed grinding, add therein organic solvent, for wet mix surface, increase intergranular contact and diffusion.
Described organic solvent preferred alcohol, the ethanol that more preferably volume fraction is 99%.
Step I i in the present invention) milling time of described grinding is 20-120min.
Due in microwave-assisted solid-state reaction, reactant Cu (AC)
2h
2o and ZSM molecular sieve are to add with solid state, contact each other not as in solution fully, therefore reaction the former two, to fully grind, and add a small amount of organic solvent to come wet mix surface, increase intergranular contact and diffusion, promote the carrying out of reaction.Therefore, in order to improve initial action speed, before reaction, add 99% ethanol, grind 30min.Meanwhile, Cu (AC)
2.H
2the crystallization water containing in O can be in reaction effective microwave energy absorbing, thereby reaction is carried out more fast.
Step I i in the present invention) operating frequency of described microwave Muffle furnace is 950-2450MHz.
Step I i in the present invention) described reaction is to carry out at 160-260 ℃ in temperature, and the reaction time is 15-30min.
Described step I i) in, the mol ratio of Schweinfurt green and M-ZSM molecular sieve is 1:1～9.
Step I i in the present invention) addition of described organic solvent is the 5-25% of the gross mass of M-ZSM molecular sieve and Schweinfurt green.
The present invention also provides a kind of application of described Cu-ZSM catalyst in removing nitrogen oxides of exhaust gas that utilize.
The microwave technology of utilization of the present invention is to utilize microwave as a kind of unionized electromagnetic energy, it has Fast Heating and the special features such as galvanomagnetic-effect, the principle of spontaneous dispersion on bigger serface carrier based on metallic salt or metal oxide, active component and molecular sieve are carried out by microwave, it being heated to cause solid ionic exchange reaction after mechanical mixture, control active component in the distribution on molecular sieve surface, with the catalyst of preparation high capacity amount, the method can make up traditional heating solid phase dispersion method shortcoming.
The beneficial effect of the inventive method is:
1, adopting Microwave Solid legal system is a kind of efficient, easy method for Cu-ZSM catalyst, required time be only under traditional heating condition ion-exchange required time 1/39, just can obtain equal or higher Cu ion load amount, can promote active component to disperse and solid ionic exchange reaction on molecular sieve surface simultaneously.
2, at high temperature (400-600 ℃) roasting of traditional heating method at least 8h just to make high capacity amount be 8.1wt%Cu-ZSM-5 catalyst.The present invention, than conventional method, can prepare higher Cu ion load amount Cu-ZSM catalyst, and Cu species and molecular sieve on exchanged exist multiple cooperate and bond function, and in the dispersion of molecular sieve outer surface more than the catalyst that has ion-exchange to prepare.
3, the Activity and stabill aspect of the standby catalyst decomposing N O of Microwave Solid legal system all substantially exceeds traditional heating method and ion-exchange, and under oxygen free condition, initial NO conversion ratio is up to 92.4%, and after reaction 25h, conversion ratio still maintains more than 75%.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in detail, but scope of the present invention is not limited to following examples.
The device using in an embodiment of the present invention and instrument and sign condition are as follows:
1) X-ray diffraction of catalyst (XRD) is characterized on the D/MAX-1200 type X-ray diffractometer that Rigaku company produces and carries out, Cu K alpha ray, and pipe is pressed 40kV, pipe stream 30mA, 2 °/min of sweep speed, sweep limits is that 2 θ are 5～50 °.
2) infrared spectrum (IR) is characterized on the Nicolet308 type FT-IR infrared spectrometer that U.S. Thermo company produces and carries out, KBr compressing tablet, resolution ratio 4crn
-1, get 4000～400crn-1 infrared spectrum.
3) specific area and pore size distribution sign (BET) are carried out on the NOVA4000e type physical adsorption appearance of U.S. Kang Ta company, by nitrogen adsorption volumetric determination specific area and pore structure, and BET method measuring and calculating for specific area, BJH method mensuration for pore-size distribution.
4) SEM (SEM) is characterized in the Vega TS2136MX type SEM of Czech Tescan company and completes, and catalyst sample surface adopts ion sputtering to carry out metal spraying processing, under different amplification, observes and takes pictures.
5) the 5100PC type Atomic Absorption Spectrometer that in catalyst, Cu content is produced by U.S. Perkin-Elmer company is measured.
6) reaction unit of the present invention is the micro-anti-experimental provision of MRT-6123 type that Beijing Xin Hangdun petrochemical industry Science and Technology Ltd. produces.Device is comprised of carrier gas system, reaction system, temperature control system and sampler.Reactor inside diameter is 10mm, the stainless steel tube of long 500mm, and Catalyst packing is in flat-temperature zone, reaction tube middle part.
7) the 42C type NOx analyzer that in tail gas, NO concentration is produced by U.S. Thermo Environmental Instruments company detects online.
With X
nOthe conversion ratio that represents NO,
C in formula
in(NO) be NO concentration (mol/L) in unstripped gas before reaction, C
out(NO) be exit NO concentration (mol/L) after reaction.Catalytic activity with the conversion ratio evaluate catalysts of NO.
In following examples, Cu (AC)
2for Schweinfurt green, Cu (AC)
2.H
2o is the Schweinfurt green with the crystallization water.
The preparation of embodiment 1 catalyst
The method of Cu-ZSM-11 catalyst comprises the following steps:
I) ZSM-11 molecular sieve and excessive NaOH solution are carried out to mix and blend, then through washing, suction filtration, oven dry, obtain Na-ZSM-11 zeolite molecular sieve;
Ii) by step I) the Na-ZSM-11 molecular sieve and the Cu (AC) that make
2mix and add 99% ethanol, fully grind 30min, be then placed in microwave heating equipment, control operating frequency is 2450MHz, in temperature, is to heat 15-30min at 160-260 ℃, washing, filter, dry at 100 ℃, the catalyst making is with MCu-ZSM-11 catalyst.
Embodiment 2: the impact of rate of charge on catalyst loadings
Preparation process, as embodiment 1, adds according to different Cu (AC) in table 1
2.H
2the Cu of the mol ratio of O:ZSM-11 (AC)
2.H
2o and ZSM-11 prepare described catalyst, investigate different material impact on the catalyst cupport preparing than mol ratio, and experimental result is in Table 1.
The impact of table 1 rate of charge on catalyst loadings
| Cu(AC) 2.H 2O:mZSM-11 | 1：9 | 1：7 | 1：5 | 1：3 | 1：1 |
| The load of Cu (wt%) | 2.31 | 3.66 | 5.65 | 8.96 | 23.11 |
As shown in Table 1, under microwave action, be dispersed in molecular sieve surface Cu (AC) 2 can with Na-ZSM-11 molecular sieve in Na
+solid ionic exchange reaction occurs, and its solid ionic exchange capacity increases along with the increase of Cu (AC) 2 input amounts.And when the load capacity of Cu (AC) 2 in Na-ZSM-11 molecular sieve is increased to 23.11wt%, Cu (AC)
2still can disperse completely on molecular sieve surface.
The embodiment impact of 3 microwave action time on catalyst loadings
Preparation method, with embodiment 1, controls respectively Cu (AC)
2.H
2the mol ratio of O:ZSM-11 is 1:5 and 1:3,200 ℃ of microwave heating temperature, are prepared according to microwave heating time different in table 2 and 3, the impact of the time of investigation microwave action on catalyst loadings, experimental result is in Table 2 and table 3, and that table 2 represents is Cu (AC)
2.H
2the impact of microwave action time on catalyst loadings when the mol ratio of O:ZSM-11 is 1:3, that table 3 represents is Cu (AC)
2.H
2when the mol ratio of O:ZSM-11 is 1:5, the microwave action time affects Cu (AC) to catalyst loadings
2.H
2the impact of microwave action time on catalyst loadings when the mol ratio of O:ZSM-11 is 1:3.
The impact of table 2 microwave action time on catalyst loadings
| Time/min | 10 | 15 | 20 | 25 | 30 |
| The load of Cu (wt%) | 2.65 | 5.11 | 6.32 | 6.26 | 5.65 |
The impact of table 3 microwave action time on catalyst loadings
| Time/min | 10 | 15 | 20 | 25 | 30 |
| The load of Cu (wt%) | 3.55 | 6.71 | 8.96 | 8.76 | 8.65 |
From table 2 and table 3, at the temperature of microwave action, the time of microwave action is a very important factor that affects catalyst loadings.The microwave irradiation effect time is short, and solid phase reaction is incomplete, and the load capacity of Cu is low, but the microwave action time is 15-30min, is best, especially at 20min, makes load capacity maximum, when the time, surpasses after 25min, and the load capacity of Cu declines on the contrary.Therefore, rationally control the microwave action time, under identical condition, can improve catalyst loadings and save the energy.
Embodiment 4 impacts of microwave action temperature on catalyst loadings
Preparation process, with embodiment 1, is controlled Cu (AC)
2.H
2the mol ratio of O:ZSM-11 is 1:5, during the time t=20min of heating using microwave, investigates the impact of different microwave heating temperature on catalyst loadings, and experimental result is in Table 3:
The impact of table 4 microwave action temperature on catalyst loadings
| Temperature/℃ | 160 | 200 | 220 | 240 | 260 |
| The load of Cu (wt%) | 4.40 | 5.65 | 6.09 | 6.54 | 6.31 |
As shown in Table 4, when temperature is during lower than 240 ℃, raising along with microwave action temperature, the load capacity of Cu also increases thereupon, this is mainly because improve the temperature of microwave action, also be just equivalent to increase under identical condition the power of microwave action, the raising of power can be strengthened the penetration capacity of microwave, thereby has accelerated the carrying out of solid phase reaction.When microwave action temperature is 240 ℃, the load capacity of Cu is up to 6.54wt%.After temperature surpasses 240 ℃, the load capacity of Cu starts to decline, and this is mainly because surpassing Cu (AC)
2at the temperature of boiling point, caused its distillation, the loss of Cu increases.
The Performance Ratio of Cu-ZSM-11 catalyst prepared by the application of embodiment 5 catalyst and distinct methods
At reaction velocity (GHSV), be 3000h
-1, NO concentration (volume fraction) is 5 * 10
-3, reaction temperature is, under 550 ℃, the condition of anaerobic, to have investigated respectively shown in the upper NO cartalytic decomposition effect results of property table 5 of the Cu-ZSM-11 catalyst (the load capacity 5.65wt% of Cu) that uses distinct methods to prepare.From table 5, standby Cu-ZSM-11 catalyst its active fall of prolongation along with the reaction time in the reaction of decomposing N O of Microwave Solid legal system is less, substantially at reaction 10h rear catalyst, reach certain stable state, after reaction 25h, the conversion ratio of its NO still maintains more than 75%.Under same condition, Cu-ZSM-11 catalyst prepared by ion-exchange before reaction in 15h the conversion ratio of NO by 78%, drop to 57.3%, reaction reaches stable state after 15h, the conversion ratio of NO maintains 57% left and right substantially.And Cu-ZSM-11 catalyst prepared by general heating method is 89% at the conversion ratio of initial reaction stage NO, after reaction 15h, reach stable state, NO conversion ratio maintains 50% left and right substantially.Above experimental data shows, compares with catalyst prepared by ion-exchange, general heating method, and the standby catalyst of Microwave Solid legal system has better catalytic activity and stability.
Cu-ZSM-11 catalyst decomposing N O conversion ratio prepared by table 5 distinct methods
| Reaction time | Microwave Solid method | Ion-exchange | Traditional heating method |
| 1 hour | 90% | 78% | 89% |
| 5 hours | 88% | 73% | 80% |
| 10 hours | 79% | 60% | 60% |
| 15 hours | 78% | 57.3% | 53% |
| 20 hours | 76% | 57.3% | 51% |
| 25 hours | 75.7% | 57.5% | 50% |
| 30 hours | 75.7% | 57.5% | 50% |
Claims (4)
1. a method of preparing Cu-ZSM catalyst, the load capacity of the Cu of described catalyst is the 23-28% of described Cu-ZSM catalyst quality; Comprise the following steps:
I) ZSM-11 molecular sieve and the solution that contains alkali metal ion are carried out to mix and blend, obtain M-ZSM-11 molecular sieve; Described M is selected from a kind of in alkali metal;
Ii) by step I) the M-ZSM-11 molecular sieve and the Schweinfurt green mixed grinding that make, and be placed in microwave heating equipment and heat and react, obtain the Cu-ZSM-11 catalyst of loaded Cu ion;
Wherein, at step I i) in during by M-ZSM-11 molecular sieve and Schweinfurt green mixed grinding, add therein organic solvent, for wet mix surface, increase intergranular contact and diffusion; Described organic solvent is 99% ethanol;
Step I i) milling time of described grinding is 20-120min;
Step I i) operating frequency of described microwave heating equipment is 950-2450MHz;
Step I i) described reaction is to carry out at 160-260 ℃ in temperature, and the reaction time is 15-30min.
2. method according to claim 1, is characterized in that, described M is sodium and/or potassium.
3. method according to claim 1 and 2, is characterized in that, the mol ratio of described Schweinfurt green and M-ZSM molecular sieve is 1:1～9.
4. method according to claim 1 and 2, is characterized in that, step I i) addition of described organic solvent is the 5-25% of the gross mass of M-ZSM-11 molecular sieve and Schweinfurt green.
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| CN110548537A (en) * | 2019-06-25 | 2019-12-10 | 无锡威孚环保催化剂有限公司 | Preparation method of molecular sieve catalyst for removing nitrogen oxides |
| CN110252386A (en) * | 2019-07-03 | 2019-09-20 | 福州大学 | A kind of monatomic Ru base ammonia synthetic catalyst and preparation method thereof |
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