CN102962094A - Method for improving acidity of MCM-22 molecular sieve based catalyst - Google Patents

Method for improving acidity of MCM-22 molecular sieve based catalyst Download PDF

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CN102962094A
CN102962094A CN2012104544284A CN201210454428A CN102962094A CN 102962094 A CN102962094 A CN 102962094A CN 2012104544284 A CN2012104544284 A CN 2012104544284A CN 201210454428 A CN201210454428 A CN 201210454428A CN 102962094 A CN102962094 A CN 102962094A
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molecular sieve
mcm
solution
mol
degrees centigrade
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徐龙伢
辛文杰
刘克峰
魏会娟
谢素娟
刘盛林
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention provides a method for improving acidity of an MCM-22 molecular sieve based catalyst. The method comprises the following specific steps of: processing a roasted Na-type MCM-22 molecular sieve for 5-180 hours at a temperature of 50 to 250 DEG C by 0.01-1.0 mol/L Al(NO3)3 solution; and washing and drying the obtained products and exchanging the obtained products with ammonium nitrate solution; and filtering the obtained products, washing the obtained products by deionized water, drying the obtained products, and then roasting the obtained products to obtain the H-type catalyst. According to the method, in the process of preparing the catalyst by modifying the MCM-22 molecular sieve by the Al(NO3)3 solution, the acid density and the acid strength of the molecular sieve can be effectively improved; and compared with those of the unprocessed MCM-22 molecular sieve based catalyst, the activity and the stability for catalyzing transformation of propylene and butane of the catalyst provided by the invention are obviously improved in the process of catalyzing alkylation reaction of benzene and liquefied gas.

Description

A kind of method that improves MCM-22 molecular sieve catalyst acidity
Technical field
The invention belongs to the molecular sieve catalyst field, be specifically related to a kind of method of the MCM-22 of raising molecular sieve catalyst acidity.
Background technology
MCM-22 molecular sieve (US 4954325) is a kind of widely used catalyst material, shows excellent catalytic cracking (US 4983276), (US 4992615 in the alkylation of catalysis benzene; US 5334795; Studies in Surface Science and Catalysis, 1999, the catalytic performance such as 121:53).But with Beta, Y molecular sieve is compared, and the sour density of MCM-22 molecular sieve is lower, acid strength a little less than, the application of this molecular sieve is restricted in need to be than the reaction of highly acid catalysis.By research, researcher has found that some can improve the method for modifying of acidic zeolite, such as loading cation, optimization deamination technique, the modification of benefit aluminium etc.
The people such as Shen Zhihong (chemistry of fuel journal, 2009,33:363) the method for use ion-exchange or incipient impregnation, the USY molecular sieve is immersed in the nitrate solution of Cr, 85 degrees centigrade exchange respectively 0.5 hour or room temperature dipping 4 hours, and the CrUSY molecular sieve for preparing after the roasting has B acid density and the B acid strength higher than the USY molecular sieve of routine.
The people such as Zhao Yan (Chemical Engineering, 2000,28:46) find by research, Beta molecular sieve after the ammonia exchange, if deamination under higher temperature, Beta molecular sieve have obvious framework dealumination phenomenon, the non-framework aluminum of formation can be moved on the acidic site on molecular sieve surface, thereby cause rich surface aluminium, and acidity weakens.The people such as Yang Xingbin (catalysis journal, 1997,18:397) optimized the deamination temperature program(me) by examination, to under 270 and 290 degrees centigrade respectively behind the constant temperature deamination the more standby Beta sieve sample of temperature programming Study of Deamination carry out TPD and characterize and find, sample surfaces is except two kinds of acidic sites that the standby sample of traditional Study of Deamination occurs and have, the acidic site that a moderate strength also occurred, the acid amount is larger, and adjustable sex change is strong.
The people such as Xie Zaiku (Journal of Catalysis, 2002, the 205:58) NaAlO of use 0.03 and 0.33 mol/L 2Solution was in 80 to 90 degrees centigrade of lower treatments B eta molecular sieves 4 hours, strong, weak acid amount in the Beta molecular sieve after the processing all increase to some extent, Bronsted is acid to be strengthened, and shows higher catalytic activity in the disproportionation of catalysis toluene and C9 aromatic hydrocarbons and transalkylation reaction process.
Summary of the invention
The method that the purpose of this invention is to provide a kind of MCM-22 of raising molecular sieve catalyst acidity, the method is by adopting Al (NO 3) 3Na-type MCM-22 molecular sieve catalyst after the solution-treated roasting, compare with untreated MCM-22 molecular sieve catalyst, prepared sample shows the activity that higher catalyzed alkene transforms in the alkylation process of catalysis benzene and liquefied gas.
The present invention specifically provides a kind of method of the MCM-22 of raising molecular sieve catalyst acidity, and concrete steps are as follows:
With the Al (NO of the Na-type MCM-22 molecular sieve after the roasting with 0.01 ~ 1.0 mol/L 3) 3Solution is 50 ~ 250 degrees centigrade of lower processing 5 ~ 180 hours, with the residual Al (NO of deionized water eccysis 3) 3, through centrifugation and dry.Resulting product exchanges with ammonium nitrate solution, filter, and with after deionized water washing, the drying, roasting becomes H-type molecular sieve catalyst.
The method of raising MCM-22 molecular sieve catalyst acidity provided by the invention, described Al (NO 3) 3Solution concentration is preferably 0.03 ~ 0.5 mol/L (optimum option is 0.05 ~ 0.2 mol/L).
The method of raising MCM-22 molecular sieve catalyst acidity provided by the invention, described Al (NO 3) 3The temperature of solution-treated is preferably 80 ~ 180 degrees centigrade.
The method of raising MCM-22 molecular sieve catalyst acidity provided by the invention, described Al (NO 3) 3The time of solution-treated is preferably 10～120 hours (optimum option is 24 ~ 100 hours).
The method of raising provided by the invention MCM-22 molecular sieve catalyst acidity, it is in preparation process, it is neutral that the solution that adopts is, and avoided acidity or alkaline solution on the impact of framework of molecular sieve structure, simultaneously Effective Raise the sour density of molecular sieve.Prepared MCM-22 molecular sieve catalyst is used for the alkylated reaction of benzene and liquefied gas, shows than the higher catalytic activity of undressed MCM-22 molecular sieve catalyst.
Description of drawings
Fig. 1 is through Al (NO 3) 3Propylene conversion temporal evolution relation in MCM-22 molecular sieve catalytic benzene and the liquefied gas alkylation process before and after the solution-treated, wherein, reaction condition: benzene/(propylene+butylene) (mol ratio)=2, P=3.4 MPa, t=200 degree centigrade, WHSV (propylene+butylene)=3 per hour;
Fig. 2 is through Al (NO 3) 3Butene conversion temporal evolution relation in MCM-22 molecular sieve catalytic benzene and the liquefied gas alkylation process before and after the solution-treated, wherein, reaction condition: benzene/(propylene+butylene) (mol ratio)=2, P=3.4 MPa, t=200 degree centigrade, WHSV (propylene+butylene)=3 per hour.
The specific embodiment
Following examples will be further described the present invention, but not thereby limiting the invention.
Comparative Examples 1
Get the Na-type MCM-22 molecular sieve after template is removed in the 20g roasting, in 400 ml concns be in the ammonium nitrate solution of 0.8 mol/L 80 degrees centigrade of lower exchanges 2 hours, double, after the filtration washing oven dry, 540 degrees centigrade of lower roastings obtain hydrogen type molecular sieves.With the molecular sieve compressing tablet and be broken into 20～40 purpose particles, be designated as Cat-A.Propylene and butene conversion are seen Fig. 1 and Fig. 2 over time on the gained catalyst sample.
Embodiment 1
Getting the Na-type MCM-22 molecular sieve that template is removed in the 20g roasting, is the Al (NO of 0.05 mol/L in 200 ml concns 3) 3In stainless steel cauldron, processed 72 hours under 175 degrees centigrade in the solution, filter, wash and drying; With product 400 ml concns be in the ammonium nitrate solution of 0.8 mol/L 80 degrees centigrade of lower exchanges 2 hours, double, after the filtration washing oven dry, 540 degrees centigrade of lower roastings obtain hydrogen type molecular sieves.With the molecular sieve compressing tablet and be broken into 20～40 purpose particles, be designated as Cat-B.Propylene and butene conversion are seen Fig. 1 and Fig. 2 over time on the gained catalyst sample.
Embodiment 2
Getting the Na-type MCM-22 molecular sieve that template is removed in the 20g roasting, is the Al (NO of 0.1 mol/L in 200 ml concns 3) 3In stainless steel cauldron, processed 72 hours under 175 degrees centigrade in the solution, filter, wash and drying; With product 400 ml concns be in the ammonium nitrate solution of 0.8 mol/L 80 degrees centigrade of lower exchanges 2 hours, double, after the filtration washing oven dry, 540 degrees centigrade of lower roastings obtain hydrogen type molecular sieves.With the molecular sieve compressing tablet and be broken into 20～40 purpose particles, be designated as Cat-C.Propylene and butene conversion are seen Fig. 1 and Fig. 2 over time on the gained catalyst sample.
Embodiment 3
Getting the Na-type MCM-22 molecular sieve that template is removed in the 20g roasting, is the Al (NO of 0.2 mol/L in 200 ml concns 3) 3In stainless steel cauldron, processed 72 hours under 175 degrees centigrade in the solution, filter, wash and drying; With product 400 ml concns be in the ammonium nitrate solution of 0.8 mol/L 80 degrees centigrade of lower exchanges 2 hours, double, after the filtration washing oven dry, 540 degrees centigrade of lower roastings obtain hydrogen type molecular sieves.With the molecular sieve compressing tablet and be broken into 20～40 purpose particles, be designated as Cat-D.Propylene and butene conversion are seen Fig. 1 and Fig. 2 over time on the gained catalyst sample.
Embodiment 4
Getting the Na-type MCM-22 molecular sieve that template is removed in the 20g roasting, is the Al (NO of 0.2 mol/L in 200 ml concns 3) 3In stainless steel cauldron, processed 72 hours under 120 degrees centigrade in the solution, filter, wash and drying; With product 400 ml concns be in the ammonium nitrate solution of 0.8 mol/L 80 degrees centigrade of lower exchanges 2 hours, double, after the filtration washing oven dry, 540 degrees centigrade of lower roastings obtain hydrogen type molecular sieves.With the molecular sieve compressing tablet and be broken into 20～40 purpose particles, be designated as Cat-E.
Embodiment 5
Getting the Na-type MCM-22 molecular sieve that template is removed in the 20g roasting, is the Al (NO of 0.2 mol/L in 200 ml concns 3) 3In stainless steel cauldron, processed 72 hours under 200 degrees centigrade in the solution, filter, wash and drying; With product 400 ml concns be in the ammonium nitrate solution of 0.8 mol/L 80 degrees centigrade of lower exchanges 2 hours, double, after the filtration washing oven dry, 540 degrees centigrade of lower roastings obtain hydrogen type molecular sieves.With the molecular sieve compressing tablet and be broken into 20～40 purpose particles, be designated as Cat-F.
Embodiment 6
Getting the Na-type MCM-22 molecular sieve that template is removed in the 20g roasting, is the Al (NO of 0.2 mol/L in 200 ml concns 3) 3In stainless steel cauldron, processed 24 hours under 175 degrees centigrade in the solution, filter, wash and drying; With product 400 ml concns be in the ammonium nitrate solution of 0.8 mol/L 80 degrees centigrade of lower exchanges 2 hours, double, after the filtration washing oven dry, 540 degrees centigrade of lower roastings obtain hydrogen type molecular sieves.With the molecular sieve compressing tablet and be broken into 20～40 purpose particles, be designated as Cat-G.
Embodiment 7
Getting the Na-type MCM-22 molecular sieve that template is removed in the 20g roasting, is the Al (NO of 0.2 mol/L in 200 ml concns 3) 3In stainless steel cauldron, processed 48 hours under 175 degrees centigrade in the solution, filter, wash and drying; With product 400 ml concns be in the ammonium nitrate solution of 0.8 mol/L 80 degrees centigrade of lower exchanges 2 hours, double, after the filtration washing oven dry, 540 degrees centigrade of lower roastings obtain hydrogen type molecular sieves.With the molecular sieve compressing tablet and be broken into 20～40 purpose particles, be designated as Cat-H.
Embodiment 8
Getting the Na-type MCM-22 molecular sieve that template is removed in the 20g roasting, is the Al (NO of 0.2 mol/L in 200 ml concns 3) 3In stainless steel cauldron, processed 100 hours under 175 degrees centigrade in the solution, filter, wash and drying; With product 400 ml concns be in the ammonium nitrate solution of 0.8 mol/L 80 degrees centigrade of lower exchanges 2 hours, double, after the filtration washing oven dry, 540 degrees centigrade of lower roastings obtain hydrogen type molecular sieves.With the molecular sieve compressing tablet and be broken into 20～40 purpose particles, be designated as Ca-I.
Comparative Examples 1 and embodiment 1 ~ 3 reaction evaluating:
The reactivity worth evaluation of catalyst is carried out at the fixed bed reactors of routine, and tube inner diameter is 12 millimeters, and length is 32 centimetres, catalyst loading amount 1 gram.Catalyst is at N 2Then the lower 500 degrees centigrade of preliminary treatment of atmosphere 1 hour are cooled to reaction temperature.Product is carried out quantitative analysis by Varian 3800 type gas chromatographs, uses PONA chromatographic column, fid detector, and the butane that does not participate in reacting in the reactant calculates the conversion ratio of propylene and butylene as interior mark.Propylene (X Proplene) and butylene (X Butylene) the conversion ratio computational methods as follows:
X propylene = ( ( x propylene / y bu tan e ) - ( x ′ propylene / y ′ bu tan e ) ) ( x propylene / y bu tan e ) - - - ( 1 )
X butylene = ( ( x butylene / y bu tan e ) - ( x ′ butylene / y ′ bu tan e ) ) ( x butylene / y bu tan e ) - - - ( 2 )
Wherein, x Propylene, x Butylene, y ButaneRepresent respectively the percetage by weight of reaction mass inner propene, butylene and butane, x ' Propylene, x ' Butylene, y ' ButaneRepresent respectively the percetage by weight of gas-phase product inner propene, butylene and butane.Can be found out by Fig. 1 data, compare with Comparative Examples that increase through the acid of the MCM-22 molecular sieve after modification amount, the activity that catalyzing propone and butylene transform and stability all obviously improve.

Claims (6)

1. method that improves MCM-22 molecular sieve catalyst acidity is characterized in that concrete steps are as follows:
(1) with the Al (NO of the Na-type MCM-22 molecular sieve after the roasting with 0.01 ~ 1.0 mol/L 3) 3Solution is 50 ~ 250 degrees centigrade of lower processing 5 ~ 180 hours, with the residual Al (NO of deionized water eccysis 3) 3, through centrifugation and dry, obtain required sample;
(2) product with step (1) exchanges with ammonium nitrate solution, filter, and with after deionized water washing, the drying, roasting becomes H-type MCM-22 molecular sieve catalyst.
2. according to the method for the described raising of claim 1 MCM-22 molecular sieve catalyst acidity, it is characterized in that: the A1 (NO in the described step (1) 3) 3The concentration of solution is 0.03 ~ 0.5 mol/L.
3. according to the method for the described raising of claim 1 MCM-22 molecular sieve catalyst acidity, it is characterized in that: use Al (NO in the described step (1) 3) 3The temperature of solution-treated is 80 ~ 180 degrees centigrade.
4. according to the method for the described raising of claim 1 MCM-22 molecular sieve catalyst acidity, it is characterized in that: the usefulness Al (NO in the described step (1) 3) 3The time of solution-treated is 10 ~ 120 hours.
5. according to the method for the described raising of claim 2 MCM-22 molecular sieve catalyst acidity, it is characterized in that: the Al (NO in the described step (1) 3) 3The concentration of solution is 0.05 ~ 0.2 mol/L.
6. according to the method for the described raising of claim 4 MCM-22 molecular sieve catalyst acidity, it is characterized in that: the usefulness Al (NO in the described step (1) 3) 3The time of solution-treated is 24 ~ 100 hours.
CN2012104544284A 2012-11-13 2012-11-13 Method for improving acidity of MCM-22 molecular sieve based catalyst Pending CN102962094A (en)

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Cited By (1)

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CN113559917A (en) * 2021-08-11 2021-10-29 西南化工研究设计院有限公司 Preparation method for preparing carbonic acid dibasic ester composite material catalyst by ester exchange

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CN101543787A (en) * 2008-03-26 2009-09-30 中国科学院大连化学物理研究所 Method for preparing MCM-22molecular sieve catalyst for alkylation desulfurization of gasoline

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CN101347748A (en) * 2007-07-18 2009-01-21 中国石油化工股份有限公司 Regeneration method of aluminum compensation for molecular sieve
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Application publication date: 20130313