CN100506385C - Preparation of composite modified catalyst and method for preparing biological ethane using same - Google Patents
Preparation of composite modified catalyst and method for preparing biological ethane using same Download PDFInfo
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- CN100506385C CN100506385C CNB2006101135834A CN200610113583A CN100506385C CN 100506385 C CN100506385 C CN 100506385C CN B2006101135834 A CNB2006101135834 A CN B2006101135834A CN 200610113583 A CN200610113583 A CN 200610113583A CN 100506385 C CN100506385 C CN 100506385C
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- catalyst
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- ethanol
- biological ethane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a method for preparing composite modified catalyst, used to prepare biological ethane. Wherein, it comprises that preparing composite modified catalyst, and using said catalyst to prepare biological ethane; said catalyst uses HZSM-5 molecule screen as powder, uses emerge method to lead in Zn<2+ and Mn<2+ metal ion, to be baked, compressed, rolled, and screened, to obtain the composite modified Zn/Mn/ZSM-5 catalyst with high catalysis activity. And its application uses biological ethane as material, adds said catalyst, under normal pressure, controls airflow speed, reaction temperature and reaction time; dewaters to obtain biological ethane, while its transformation rate and selectivity are both higher then 95%. The invention has low cost and simple control.
Description
Technical field
The invention belongs to catalyst preparation technology and bioenergy field thereof, particularly a kind of preparation of composite modified catalyst and be used to prepare the method for biological ethane.Relate to specifically a kind ofly utilize the preparation of composite modified catalyst Zn/Mn/ZSM-5 and be used for the technology that the catalysis biological ethanol dehydration prepares biological ethane.
Background technology
Ethene is important basic Organic Chemicals, is the foundation stone of petrochemical industry, and at present, nearly 75% chemical products are raw material with ethene, and its output has been represented a national organic chemical industry's development level.Ethene is widely used in the multiple important organic chemical industry's products such as polyethylene, ethylene oxide/ethylene glycol, dichloroethanes, styrene, ethanol, vinyl acetate, propionic aldehyde and the production of polymer.In recent years, the demand of ethene in continuous increase, the gesture that supply falls short of demand occurred, estimate that China is ten thousand tons of 2500-2600 ethylene requirements in 2010, the year two thousand twenty is ten thousand tons of 3700-4100.
At present, naphtha pyrolysis is still the main method of producing ethene, but this method is that the fossil resource with non-renewable and the beneficial minimizing of H is a raw material, and a large amount of concomitant outputs arranged, purifying products process complexity, the huge costliness of equipment, therefore the researcher prepares ethylene process to catalytic dehydration of ethanol and has carried out research and improve, in fact, by preparing ethylene by dehydrating ethanol also is the main method that the petrochemical industry development prepares ethene before, and some countries comprise that the part medium-sized and small enterprises of China still adopt this technology at present.But traditional ethanol dehydration technique is a catalyst with metal oxides such as activated aluminas mostly, raw material then requires concentration of alcohol greater than 95%, deficiencies such as energy consumption is big, air speed is low, make this method lack the market competitiveness, therefore, be necessary to explore a kind of new catalyst modification technology and be used for the new technology of bio-ethanol dehydration preparation ethene.
The ZSM-5 zeolite is a kind of cationic novel crystallization silicate zeolite of organic amine that contains, because of it has special pore passage structure and catalytic performance, good heat endurance and acid resistance, fabulous hydrophobicity and steam stability and be subjected to the attention of domestic and international petrochemical industry circle, be widely used in alkane aromatization, alkylating aromatic hydrocarbon, very important chemical process such as toluene disproportionation.In document 1 " William R.Silicon-rich HZSM-5 catalyzedconversion of aqueous ethanol to ethylene, Journal of Catalysis, 1989, (117): 19-32 "; Document 2 " petrochemical industry, 1987,16 (14), 746-751 " is gone up " the ethanol dehydration reaction Study on Selectivity on the HZSM-5 molecular sieve " that Pan Lvrang delivers; Document 3 " Kochar N K, Ethylene from Ethanol, Chemical Engineering, 1980,28 (1): 80-81 "; Document 4 " Nguyen.T.M; Mao Le Van;; Conversion of Ethanol in Aqueous solution over ZSM-5 zeolites; Applied Catalysis; 1990, (58): 119-129 "; and document 5 " Mao Le Van, Nguyen T M, Mclaughlin G P.TheBioethanol to Ethylene (B.E.T.E) process, 1989, Applied Catalysis, (48): 265-277 " etc. studied molecular sieve carried out modification, and be used for preparing ethylene by dehydrating ethanol; obtained certain effect; but these modified catalysts are used for the severe reaction conditions that catalytic dehydration of ethanol prepares ethene, and concentration of ethanol had relatively high expectations, be not suitable for the bio-ethanol catalytic dehydration and prepare biological ethane.Therefore the present invention carries out composite modifiedly to HZSM-5 by infusion process, and is used for the bio-ethanol catalytic dehydration and prepares biological ethane, and the reaction condition gentleness has advantages of high catalytic activity, and at present, the research of this respect does not appear in the newspapers as yet.
Summary of the invention
The purpose of this invention is to provide the preparation of composite modified catalyst and be used to prepare the method for biological ethane, comprise the preparation of composite modified catalyst and the method that composite modified catalyst is used to prepare biological ethane.
The preparation of described composite modified catalyst is characterized in that, this composite modified catalyst be a kind of be the solid acid catalyst of main component with the HZSM-5 molecular sieve.Be to be former powder, introduce Zn respectively by dipping method with the HZSM-5 molecular sieve
2+And Mn
2+Metal ion, then in Muffle furnace after the roasting, the composite modified Zn/Mn/ZSM-5 catalyst that obtains having advantages of high catalytic activity through compressing tablet, after milling, sieving; Concrete processing step comprises:
1) get commodity HZSM-5 type molecular sieve and make former powder, its sial weight ratio is 25-150.
2) introduce the bimetallic ion Zn
2+And Mn
2+Carry out composite modified: place 0.1-10wt% to contain Zn in the former powder of HZSM-5
2+In the solution, 30-100 ℃ is stirred after the 0.5-5h, in 60-200 ℃ of dry 5-20h, obtains Zn/ZSM-5; The Mn that contains with 0.5-15wt%
2+Solution adds among the Zn/ZSM-5, places after the 0.1-5h, at 50-200 ℃ of dry 5-20h, obtains the Zn/Mn/ZSM-5 catalyst for 5-50 ℃.
3) with the Zn/Mn/ZSM-5 catalyst 100-800 ℃ of roasting 5-20h in Muffle furnace that obtains, obtain powdery composite modified catalyst Zn/Mn/ZSM-5, then by the tablet press machine compressing tablet, mill, sieve after, getting the 20-120 order is the composite modified Zn/Mn/ZSM-5 catalyst of moulding.
The method that described composite modified catalyst is used to prepare biological ethane is to be raw material with the bio-ethanol, is catalyst with the composite modified Zn/Mn/ZSM-5 of claim 1 preparation; At flow is in the bio-ethanol of 1～100ml/h, adds catalyst 1-15g; Under normal pressure, feed CO
2Or N
2Deng inert gas, air velocity is 0.1-2.0L/min, reaction velocity 0.8-7.0h
-1, temperature is 100-400 ℃, reaction 0.5-10h; Through obtaining biological ethane after the dehydration.
Described bio-ethanol mainly with starch, corn, molasses, potato do, recyclability resource living beings such as cassava, straw are that raw material is made by brewageing fermentation.
Described bio-ethanol concentration is 5-95wt%.
The invention has the beneficial effects as follows that preparing biological ethane by the bio-ethanol dehydration under catalyst action is to be raw material with the renewable resource, does not exist the dependence to the petrochemical industry resource; It is few to have accessory substance in addition, and the conversion ratio of reaction and selectivity all can reach more than 95%.Ethene purity height, small investment, equipment is simple, and technology is easy to advantages such as control.With the raw material of living beings as ethylene production, be to the replenishing of oil ethene, meet the strategy of sustainable development simultaneously again.Present this method has obtained people's extensive concern.
Operating process of the present invention is simple, be easy to control, reaction condition gentleness, cost are lower, has the favorable industrial application prospect.
Description of drawings
The XRD spectra of former powder of Fig. 1 .ZSM-5 and modified catalyst Zn/Mn/ZSM-5.
The SEM figure of the former powder of Fig. 2 ZSM-5.
The SEM figure of Fig. 3 modified catalyst Zn/Mn/ZSM-5.
The specific embodiment
The purpose of this invention is to provide the preparation of composite modified catalyst and be used to prepare the method for biological ethane.
Comprise the preparation of composite modified catalyst and the method that composite modified catalyst is used to prepare biological ethane.Described composite modified catalyst be a kind of be the solid acid catalyst of main component with the HZSM-5 molecular sieve.Be to be former powder, introduce Zn respectively by dipping method with the HZSM-5 molecular sieve
2+And Mn
2+Metal ion, then in Muffle furnace after the roasting, the composite modified Zn/Mn/ZSM-5 catalyst that obtains having advantages of high catalytic activity through compressing tablet, after milling, sieving;
The method that described composite modified catalyst is used to prepare biological ethane is to be raw material with the bio-ethanol, is catalyst with the composite modified Zn/Mn/ZSM-5 of oneself preparation; In bio-ethanol, add catalyst, under normal pressure, feed inert gas, at certain air velocity, reaction velocity, under the reaction temperature, the reaction certain hour; Through obtaining biological ethane after the dehydration, the conversion ratio of reaction and selectivity all can reach more than 95% again.
Below in conjunction with description of drawings, the present invention is further described to exemplify embodiment again.
Fig. 1 is the XRD spectra of former powder of unmodified ZSM-5 and modified catalyst Zn/Mn/ZSM-5.From figure as can be seen: each molecular sieve spectrum shape is basic identical, and just diffraction peak and intensity have difference slightly, is 7.9 ° and 24.4 ° at 2 θ and locates, and the strong difference in modified catalyst Zn/Mn/ZSM-5 peak slightly descends and slightly increases.This shows Zn2 after the modification
+And Mn
2+Replace the Al in the ZSM-5 framework of molecular sieve
3+And enter in the skeleton.
Fig. 2 and Fig. 3 are respectively the SEM figure of former powder of ZSM-5 and modified catalyst Zn/Mn/ZSM-5, and as can be seen from Figure 3: compare with Fig. 2, at ZSM-5 plane of crystal some granules that evenly are scattered here and there, this explanation Zn and Mn are dispersed on the ZSM-5 molecular sieve after the modification.
Embodiment 1
Reactor is fixed bed reactors, and catalyst is composite modified Zn/Mn/ZSM-5 and the former powder of unmodified ZSM-5.At 400 ℃, air speed is 2.4h
-1The time, the former powder catalysis ethanol dehydration of ZSM-5 conversion ratio is 95.54%, ethylene selectivity is 12.13%; Through the ZSM-5 after composite modified, ethanol dehydration conversion ratio 99.97%, ethylene selectivity are 49.58%.As seen, to obviously be better than former powder through composite modified ZSM-5 effect.
Embodiment 2
To the sial weight ratio is that 25 ZSM-5 catalyst carries out modification, the former powder of HZSM-5 is placed contain Zn
2+Be 2wt%, Mn
2+In 4wt% solution, modification time 1h, 80 ℃ of modification temperatures, sintering temperature is 550 ℃, obtains composite modified Zn/Mn/ZSM-5 catalyst.In the fixed bed reactors of development voluntarily, add the 4.0gZn/Mn/ZSM-5 catalyst, be 250 ℃ in temperature, air speed is under the 1.0h-1, and bio-ethanol is carried out dehydration experiment, and ethanol conversion is 99.84%, and ethylene selectivity can reach 90%.
Embodiment 3
To the sial weight ratio is that 25 ZSM-5 catalyst carries out modification, the former powder of HZSM-5 is placed contain Zn
2+Be 1wt%, Mn
2+In 6wt% solution, modification time 1h, modification temperature are 40 ℃, when sintering temperature is 550 ℃, obtain composite modified Zn/Mn/ZSM-5 catalyst.In the fixed bed reactors of development voluntarily, add the 4.0gZn/Mn/ZSM-5 catalyst, be 250 ℃ in temperature, air speed is 1.0h
-1Down, bio-ethanol is carried out dehydration experiment, ethanol conversion is 99.56%, and ethylene selectivity can reach 90%.
Embodiment 4
To the sial weight ratio is that 25 ZSM-5 catalyst carries out modification, the former powder of HZSM-5 is placed contain Zn
2+Be 2wt%, Mn
2+In 5wt% solution, modification time 1h, modification temperature are 40 ℃, when sintering temperature is 550 ℃, obtain composite modified Zn/Mn/ZSM-5 catalyst.In the fixed bed reactors of development voluntarily, add 4.0g Zn/Mn/ZSM-5 catalyst, at 250 ℃ of temperature, air speed 1.0h
-1Down, bio-ethanol is carried out dehydration experiment, this composite modified catalyst is moved 72h continuously, activity of such catalysts does not have to change substantially, shows this catalyst good stable and the long cycle of operation.
Embodiment 5
, carry out in homemade micro fixed-bed reactor as catalyst with homemade composite modified Zn/Mn/ZSM-5.Add 6.0g Zn/Mn/ZSM-5 catalyst in fixed bed reactors, concentration of alcohol is 10wt%, and reaction temperature is 250 ℃, and air speed is 2.68h
-1, N
2Flow velocity be 0.5L/min, reaction time 3h carries out dehydration experiment to bio-ethanol, ethanol conversion is 99.83%, ethylene selectivity can reach 99.03%.
Embodiment 6
, carry out in homemade micro fixed-bed reactor as catalyst with homemade composite modified Zn/Mn/ZSM-5.Add 2.0g Zn/Mn/ZSM-5 catalyst in fixed bed reactors, concentration of alcohol is 30wt%, and reaction temperature is 250 ℃, and air speed is 2.31h
-1, N
2Flow velocity be 0.5L/min, reaction time 4h carries out dehydration experiment to bio-ethanol, ethanol conversion is 99.87%, ethylene selectivity can reach 99.45%.
Embodiment 7
, carry out in homemade micro fixed-bed reactor as catalyst with homemade composite modified Zn/Mn/ZSM-5.Add 4.0g Zn/Mn/ZSM-5 catalyst in fixed bed reactors, concentration of alcohol is 60wt%, and reaction temperature is 250 ℃, and air speed is 2.31h
-1, CO
2And N
2Flow velocity be respectively 0.5L/min, reaction time 4h carries out dehydration experiment to bio-ethanol, when using CO
2As ethanol conversion is 99.68%, and ethylene selectivity can reach 99.02%; When using N
2As ethanol conversion is 99.87%, and ethylene selectivity can reach 99.45%.
Claims (4)
1. the preparation of a composite modified catalyst is characterized in that, concrete processing step comprises:
1) get commodity HZSM-5 molecular sieve and make former powder, its sial weight ratio is 25;
2) introduce the bimetallic ion Zn
2+And Mn
2+Carry out composite modified: the HZSM-5 molecular screen primary powder is placed to contain Zn earlier
2+Amount X is in the solution of 0.1wt%≤X＜2wt% or 2wt%＜X≤10wt%, under temperature T is 30 ℃≤T＜80 ℃ or 80 ℃＜T≤100 ℃, stirs after the 0.5-5h, in 60-200 ℃ of dry 5-20h, obtains Zn/ZSM-5; Again Zn/ZSM-5 is added Mn
2+Content Y is in the solution of 0.5≤Y＜6wt% or 6wt%＜Y≤15wt%, after 5-50 ℃ is placed 0.1-5h down, at 50-200 ℃ of dry 5-20h, obtains the Zn/Mn/ZSM-5 catalyst;
3) the Zn/Mn/ZSM-5 catalyst that obtains is placed in the Muffle furnace, roasting 5-20h in temperature T is 100 ℃≤T＜550 ℃ or 550 ℃＜T≤800 ℃ scope, obtain powdery composite modified catalyst Zn/Mn/ZSM-5, then by the tablet press machine compressing tablet, mill, sieve after, getting the 20-120 order is the composite modified Zn/Mn/ZSM-5 catalyst of moulding.
2. a composite modified catalyst is used to prepare the method for biological ethane, it is characterized in that this method is to be raw material with the bio-ethanol, and prepared composite modified Zn/Mn/ZSM-5 is a catalyst with claim 1; At flow is in the bio-ethanol of 1～100ml/h, and the amount L that adds catalyst is 1g≤L＜4g or 4g＜L≤15g; Under normal pressure, feed inert gas, air velocity is 0.1-2.0L/min, reaction velocity is 0.8-2.31h
-1Or 2.68-7.0h
-1, temperature T is that 100 ℃≤T≤250 ℃, reaction time t are 0.5h≤t＜4h or 4h＜t≤10h; Through obtaining biological ethane after the dehydration.
3. be used to prepare the method for biological ethane according to the described composite modified catalyst of claim 2, it is characterized in that, described bio-ethanol concentration is 10wt%, 30wt% or 60wt%.
4. be used to prepare the method for biological ethane according to the described composite modified catalyst of claim 2, it is characterized in that, described inert gas is CO
2
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| CN101579637B (en) * | 2009-05-08 | 2012-05-23 | 清华大学 | Method for preparing molecular sieve solid acid catalyst used for preparing ethylene by ethanol dehydration |
| CN105413670B (en) * | 2015-10-22 | 2018-05-29 | 清华大学 | It is a kind of to prepare solid acid catalyst of butylene and preparation method thereof for n-butanol dehydration |
| CN114570417B (en) * | 2022-03-23 | 2023-06-27 | 清华大学 | Catalyst for preparing butene from n-butanol, preparation method thereof and method for preparing butene |
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