CN101602010A - Molecular sieve catalyst, preparation method and the application in crylic acid preparation by lactic acid dehydration thereof - Google Patents
Molecular sieve catalyst, preparation method and the application in crylic acid preparation by lactic acid dehydration thereof Download PDFInfo
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Abstract
The invention discloses a kind of molecular sieve catalyst, preparation method and its application in crylic acid preparation by lactic acid dehydration.This catalyst is after the ZSM-5 molecular sieve is handled with aqueous slkali, perhaps to adopt infusion process to support phosphate again, obtains the molecular sieve catalyst of modification then after super-dry, roasting.This catalyst makes the reaction of crylic acid preparation by lactic acid dehydration to realize under lower temperature, and lactic acid conversion ratio and acrylic acid selectivity height, catalyst long service life, the conversion ratio 100% of acid by dehydrating lactic reaction, acrylic acid selectivity is up to 83.9%, has the favorable industrial application prospect.
Description
Technical field
The invention belongs to Preparation of Catalyst and chemical technology field, particularly a kind of molecular sieve catalyst and preparation and its application in crylic acid preparation by lactic acid dehydration.
Background technology
Acrylic acid is important high polymer monomer and industrial chemicals, is widely used in fields such as weaving, chemical fibre, plastics, light industry, water treatment, oil recovery, metallurgy, the huge market demand and always present ascendant trend in recent years.
Current, acrylic acid is synthetic by petroleum chemicals substantially, and depolarization other company adopts outside acrylonitrile hydrolysis method and the Reppe method, and it all is the propylene two-step oxidizing process that most companies produce acrylic acid.Because propylene is mainly derived from the petroleum refining industry, propylene oxidation is produced acrylic acid has great dependence for petroleum resources.Therefore, in short supply day by day along with petroleum resources in the global range, exploitation acrylic acid production technology that make new advances, that do not rely on petroleum resources has been the task of top priority as early as possible.
Advantages such as the biorefinery technology has environmental friendliness for petroleum refining, raw material is renewable have vast potential for future development.Therefore, the maturation along with the lactic fermentation technology is subject to people's attention day by day by crylic acid preparation by lactic acid dehydration.Just having had with lactic acid in nineteen fifties is the acrylic acid report of feedstock production, and Holmen etc. (USP2859240) have studied the sulfate and the phosphate catalyst of a series of alkali metal and alkaline-earth metal, finds CaSO the most effectively
4/ Na
2SO
4Composite catalyst, this catalyst obtains acrylic acid yield at 400 ℃ of following catalysis acid by dehydrating lactic can reach 68%; It is active component with dibastic sodium phosphate and potassium hydrogen phosphate etc. that Sawicki etc. (USP4729978) have reported a kind of, and with silica gel, titanium dioxide and aluminium oxide are the catalyst of carrier, and it is 58% that this catalyst generates acrylic acid yield at 350 ℃ of following catalysis acid by dehydrating lactic.The document is pointed out simultaneously, and too high or low excessively pH value all can cause reaction to tend to lactic acid decarboxylation generation acetaldehyde, thereby causes the acrylic acid selectivity to descend; Paparizos (US4786756) etc. are with the AlPO of modification
4Be catalyst, acrylic acid yield is 43%; Hongjuan Wang etc. has prepared a kind of NaY zeolite molecular sieve catalyst that has added a small amount of rare earth metal composition, and they studies show that, adds a spot of rare earth metal and help to improve acid by dehydrating lactic and generate acrylic acid selectivity in the NaY zeolite catalyst.
Above-mentioned all kinds of catalyst generates acrylic acid reaction to acid by dehydrating lactic and all has certain catalytic activity, but the acrylic acid yield is generally not high.
Molecular sieve is owing to have unique pore passage structure and surface acidity and good heat endurance, thereby obtained using widely at catalytic field.Utilize the finishing means that molecular sieve is carried out the adjusting of pore size, shape selectivity and surface acid alkalescence, can obtain being applicable to the good modified molecular sieve catalyst of catalytic performance of differential responses.
The present invention after the ZSM-5 molecular sieve is handled with aqueous slkali, perhaps adopts infusion process to support phosphate again, obtains the molecular sieve catalyst of modification then after super-dry, roasting.This catalyst can realize that under lower temperature acid by dehydrating lactic generates acrylic acid reaction, and has advantages of high catalytic activity.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 high molecular sieve catalyst of a kind of catalytic activity.
Another object of the present invention provides above-mentioned Preparation of catalysts method.
A further object of the invention provides the application process of above-mentioned catalyst in crylic acid preparation by lactic acid dehydration.
Molecular sieve catalyst of the present invention is after the ZSM-5 molecular sieve is handled with aqueous slkali, perhaps to adopt infusion process to support phosphate again, obtains the molecular sieve catalyst of modification then after super-dry, roasting; The preceding weight content of phosphate roasting is 0~40% in this molecular sieve catalyst.Described alkali is selected from Na
2CO
3, NaHCO
3, KHCO
3, K
2CO
3, NaOH, KOH or ammoniacal liquor; Described phosphate is selected from NaH
2PO
4, Na
2HPO
4, KH
2PO
4, K
2HPO
4, Ca (H
2PO
4)
2, Mg
3(PO
4)
2, LiH
2PO
4, Li
2HPO
4Or LaPO
4
The preparation method of described molecular sieve catalyst, this preparation method comprise following two kinds 1. and 2., processing step perhaps 1.~3.:
1. be that 10~300: 1 ZSM-5 molecular sieve is at 200~800 ℃ of roasting 0.5~8hr with silica alumina ratio;
2. baked ZSM-5 molecular sieve is handled 1~24hr with the aqueous slkali of concentration 0.1~15M down at 20~100 ℃, wherein every gram ZSM-5 molecular sieve adds the 5ml aqueous slkali; The suction filtration after washing, and, obtain ZSM-5 molecular sieve through basification in 50~150 ℃ of oven dry down;
3. preparation supports phosphatic molecular sieve catalyst: will place concentration through the ZSM-5 of basification is the phosphate solution of 1~40wt%, 20~90 ℃ are stirred after 1~24hr, system is spin-dried for, solid is in 80~150 ℃ of drying 5~20hr, 300~600 ℃ of roasting 0.5~5hr obtain supporting phosphatic molecular sieve catalyst; The preceding weight content of phosphate roasting is 0~40% in this catalyst.
Step 2. in used alkali be selected from Na
2CO
3, NaHCO
3, KHCO
3, K
2CO
3, NaOH, KOH or ammoniacal liquor, wherein, NaOH and ammoniacal liquor are preferable selection, NaOH the best especially, suitable NaOH concentration is 0.5~1.5M.
Step 3. in used phosphate be selected from NaH
2PO
4, Na
2HPO
4, KH
2PO
4, K
2HPO
4, Ca (H
2PO
4)
2, Mg
3(PO
4)
2, LiH
2PO
4, Li
2HPO
4Or LaPO
4, wherein, NaH
2PO
4Be optimal selection, its in catalyst before the roasting weight content be 10~30% o'clock comparatively suitable.
The application of described molecular sieve catalyst in crylic acid preparation by lactic acid dehydration is under normal pressure, and the material acid aqueous solution without the vaporization preheating, is directly injected fixed bed reactors, feeds inert gas simultaneously in reactor; Gas reacts by beds, through obtaining acrylic acid after the dehydration; 300 ℃~500 ℃ of reaction temperatures, reaction velocity 0.2~4h
-1, inert gas flow velocity 10~100ml/min, lactic acid aqueous solution concentration 10~90wt%; The recommendation inert gas is CO
2Or N
2
Utilize the catalyst crylic acid preparation by lactic acid dehydration reaction among the present invention, lactic acid conversion ratio and acrylic acid selectivity height, the conversion ratio of lactic acid is 100%, acrylic acid selectivity is up to 83.9%.In addition, utilize that the catalyst acid by dehydrating lactic reaction for preparing among the present invention can be carried out, side reaction is few under normal pressure and lower temperature, the catalyst long service life, energy consumption is low, technical process is simple and easy to control, and the favorable industrial application prospect is arranged.
The specific embodiment
The present invention is further described by the following examples, but can not limit content of the present invention.
[embodiment 1]
Get silica alumina ratio and be 40 ZSM-5 molecular sieve, with it at 550 ℃ of roasting 5hr;
The ammonia spirit of preparation 30ml 9M is to wherein adding the baked ZSM-5 molecular sieve of 6g, stirring at room 2hr, suction filtration, washing, 120 ℃ of dryings; The biphosphate sodium water solution of preparation 7ml 15wt% adds above-mentioned molecular sieve through basification wherein, stirring at room dipping 8hr, and 60 ℃ are spin-dried for, and 120 ℃ of dryings obtain modified molecular screen JZSM-7;
The above-mentioned catalyst JZSM-7 that makes of the 3 grams internal diameter of packing into is 10 millimeters, highly is that catalyst all loads the little porcelain ball or the quartz sand of inertia up and down in 500 millimeters the fixed bed reactors.375 ℃ of reaction temperatures, nitrogen flow rate 50ml/min, air speed 1h
-1, water and lactic acid weight ratio are 1: 1 in the raw material.Under these conditions, the conversion ratio of catalyst JZSM-7 catalysis crylic acid preparation by lactic acid dehydration is 100%, and acrylic acid selectivity is 68.8%.
[embodiment 2]
Get silica alumina ratio and be 50 ZSM-5 molecular sieve, with it at 550 ℃ of roasting 5hr;
The NaOH aqueous solution of preparation 30ml 0.5M, to wherein adding the baked ZSM-5 molecular sieve of 6g, 80 ℃ are stirred 8hr, suction filtration, washing, 120 ℃ of dryings obtain modified molecular screen JZSM-10;
The above-mentioned catalyst JZSM-10 that makes of the 3 grams internal diameter of packing into is 10 millimeters, highly is that catalyst all loads the little porcelain ball or the quartz sand of inertia up and down in 500 millimeters the fixed bed reactors.350 ℃ of reaction temperatures, nitrogen flow rate 30ml/min, air speed 1h
-1, water and lactic acid weight ratio are 1: 1 in the raw material.Under these conditions, the conversion ratio of catalyst JZSM-10 catalysis crylic acid preparation by lactic acid dehydration is 100%, and acrylic acid selectivity is 71%.
[embodiment 3]
Get silica alumina ratio and be 50 ZSM-5 molecular sieve, with it at 550 ℃ of roasting 5hr;
The NaOH aqueous solution of preparation 30ml 0.5M, to wherein adding the baked ZSM-5 molecular sieve of 6g, 80 ℃ are stirred 8hr, suction filtration, washing, 120 ℃ of dryings; The biphosphate sodium water solution of preparation 7ml 11wt% adds above-mentioned molecular sieve through basification wherein, stirring at room dipping 8hr, and 60 ℃ are spin-dried for, and 120 ℃ of dryings obtain modified molecular screen JZSM-13;
The above-mentioned catalyst JZSM-13 that makes of the 3 grams internal diameter of packing into is 10 millimeters, highly is that catalyst all loads the little porcelain ball or the quartz sand of inertia up and down in 500 millimeters the fixed bed reactors.375 ℃ of reaction temperatures, nitrogen flow rate 50ml/min, air speed 1h
-1, water and lactic acid weight ratio are 1: 1 in the raw material.Under these conditions, the conversion ratio of catalyst JZSM-13 catalysis crylic acid preparation by lactic acid dehydration is 100%, and acrylic acid selectivity is 74%.
[embodiment 4]
Get silica alumina ratio and be 60 ZSM-5 molecular sieve, with it at 550 ℃ of roasting 5hr;
The NaOH aqueous solution of preparation 30ml 1.0M, to wherein adding the baked ZSM-5 molecular sieve of 6g, 80 ℃ are stirred 8hr, suction filtration, washing, 120 ℃ of dryings obtain modified molecular screen JZSM-14;
The above-mentioned catalyst JZSM-14 that makes of the 3 grams internal diameter of packing into is 10 millimeters, highly is that catalyst all loads the little porcelain ball or the quartz sand of inertia up and down in 500 millimeters the fixed bed reactors.375 ℃ of reaction temperatures, nitrogen flow rate 50ml/min, air speed 1h
-1, water and lactic acid weight ratio are 1: 1 in the raw material.Under these conditions, the conversion ratio of catalyst JZSM-14 catalysis crylic acid preparation by lactic acid dehydration is 100%, and acrylic acid selectivity is 72.6%.
[embodiment 5]
Get silica alumina ratio and be 60 ZSM-5 molecular sieve, with it at 550 ℃ of roasting 5hr;
The NaOH aqueous solution of preparation 30ml 1.0M, to wherein adding the baked ZSM-5 molecular sieve of 6g, 80 ℃ are stirred 8hr, suction filtration, washing, 120 ℃ of dryings; The biphosphate sodium water solution of preparation 7ml 15wt% adds above-mentioned molecular sieve through basification wherein, stirring at room dipping 8hr, and 60 ℃ are spin-dried for, 120 ℃ of dryings, 430 ℃ of roasting 2hr obtain modified molecular screen JZSM-151;
The above-mentioned catalyst JZSM-151 that makes of the 3 grams internal diameter of packing into is 10 millimeters, highly is that catalyst all loads the little porcelain ball or the quartz sand of inertia up and down in 500 millimeters the fixed bed reactors.375 ℃ of reaction temperatures, nitrogen flow rate 40ml/min, air speed 1h
-1, water and lactic acid weight ratio are 1: 1 in the raw material.Under these conditions, the conversion ratio of catalyst JZSM-151 catalysis crylic acid preparation by lactic acid dehydration is 97.9%, and acrylic acid selectivity is 76.7%.
[embodiment 6]
Get silica alumina ratio and be 60 ZSM-5 molecular sieve, with it at 550 ℃ of roasting 5hr;
The NaOH aqueous solution of preparation 30ml 1.0M, to wherein adding the baked ZSM-5 molecular sieve of 6g, 80 ℃ are stirred 8hr, suction filtration, washing, 120 ℃ of dryings; The biphosphate sodium water solution of preparation 7ml 7wt% adds above-mentioned molecular sieve through basification wherein, stirring at room dipping 8hr, and 60 ℃ are spin-dried for, 120 ℃ of dryings, 430 ℃ of roasting 2hr obtain modified molecular screen JZSM-161;
The above-mentioned catalyst JZSM-161 that makes of the 3 grams internal diameter of packing into is 10 millimeters, highly is that catalyst all loads the little porcelain ball or the quartz sand of inertia up and down in 500 millimeters the fixed bed reactors.375 ℃ of reaction temperatures, nitrogen flow rate 50ml/min, air speed 1h
-1, water and lactic acid weight ratio are 1: 1 in the raw material.Under these conditions, the conversion ratio of catalyst JZSM-161 catalysis crylic acid preparation by lactic acid dehydration is 100%, and acrylic acid selectivity is 83.9%.
[embodiment 7]
Get silica alumina ratio and be 60 ZSM-5 molecular sieve, with it at 550 ℃ of roasting 5hr;
The NaOH aqueous solution of preparation 30ml 1.0M, to wherein adding the baked ZSM-5 molecular sieve of 6g, 80 ℃ are stirred 8hr, suction filtration, washing, 120 ℃ of dryings; The biphosphate sodium water solution of preparation 7ml 4wt% adds above-mentioned molecular sieve through basification wherein, stirring at room dipping 8hr, and 60 ℃ are spin-dried for, 120 ℃ of dryings, 430 ℃ of roasting 2hr obtain modified molecular screen JZSM-142;
The above-mentioned catalyst JZSM-142 that makes of the 3 grams internal diameter of packing into is 10 millimeters, highly is that catalyst all loads the little porcelain ball or the quartz sand of inertia up and down in 500 millimeters the fixed bed reactors.375 ℃ of reaction temperatures, nitrogen flow rate 50ml/min, air speed 1h
-1, water and lactic acid weight ratio are 1: 1 in the raw material.Under these conditions, the conversion ratio of catalyst JZSM-142 catalysis crylic acid preparation by lactic acid dehydration is 100%, and acrylic acid selectivity is 74.6%.
[embodiment 8]
Get silica alumina ratio and be 60 ZSM-5 molecular sieve, with it at 550 ℃ of roasting 5hr;
The NaOH aqueous solution of preparation 30ml 1.2M to wherein adding the baked ZSM-5 molecular sieve of 6g, refluxes and stirs 8hr, suction filtration, and washing, 120 ℃ of dryings obtain modified molecular screen JZSM-22;
The above-mentioned catalyst JZSM-22 that makes of the 3 grams internal diameter of packing into is 10 millimeters, highly is that catalyst all loads the little porcelain ball or the quartz sand of inertia up and down in 500 millimeters the fixed bed reactors.350 ℃ of reaction temperatures, nitrogen flow rate 40ml/min, air speed 1h
-1, water and lactic acid weight ratio are 1: 1 in the raw material.Under these conditions, the conversion ratio of catalyst JZSM-22 catalysis crylic acid preparation by lactic acid dehydration is 97.6%, and acrylic acid selectivity is 79.9%.
Claims (10)
1, a kind of molecular sieve catalyst of crylic acid preparation by lactic acid dehydration, it is characterized in that, this catalyst is after the ZSM-5 molecular sieve is handled with aqueous slkali, perhaps to adopt infusion process to support phosphate again, obtains the molecular sieve catalyst of modification then after super-dry, roasting; The preceding weight content of phosphate roasting is 0~40% in this molecular sieve catalyst; Described alkali is selected from Na
2CO
3, NaHCO
3, KHCO
3, K
2CO
3, NaOH, KOH or ammoniacal liquor; Described phosphate is selected from NaH
2PO
4, Na
2HPO
4, KH
2PO
4, K
2HPO
4, Ca (H
2PO
4)
2, Mg
3(PO
4)
2, LiH
2PO
4, Li
2HPO
4Or LaPO
4
2, molecular sieve catalyst as claimed in claim 1 is characterized in that, the silica alumina ratio of described ZSM-5 molecular sieve is 10~300: 1.
3, a kind of preparation method of molecular sieve catalyst as claimed in claim 1 is characterized in that, this method comprise following two kinds 1. and 2., step perhaps 1.~3.:
1. be that 10~300: 1 ZSM-5 molecular sieve is at 200~800 ℃ of roasting 0.5~8hr with silica alumina ratio;
2. baked ZSM-5 molecular sieve is handled 1~24hr with the aqueous slkali of concentration 0.1~15M down at 20~100 ℃, wherein every gram ZSM-5 molecular sieve adds the 5ml aqueous slkali; The suction filtration after washing, and, obtain ZSM-5 molecular sieve through basification in 50~150 ℃ of oven dry down;
3. preparation supports phosphatic molecular sieve catalyst: will place concentration through the ZSM-5 of basification is the phosphate solution of 1~40wt%, 20~90 ℃ are stirred after 1~24hr, system is spin-dried for, solid is in 80~150 ℃ of drying 5~20hr, 300~600 ℃ of roasting 0.5~5hr obtain supporting phosphatic molecular sieve catalyst; The preceding weight content of phosphate roasting is 0~40% in this catalyst.
4, the preparation method of molecular sieve catalyst as claimed in claim 3 is characterized in that described alkali is selected from Na
2CO
3, NaHCO
3, KHCO
3, K
2CO
3, NaOH, KOH or ammoniacal liquor.
5, the preparation method of molecular sieve catalyst as claimed in claim 4 is characterized in that described alkali is that concentration is the NaOH of 0.5~1.5M.
6, the preparation method of molecular sieve catalyst as claimed in claim 3 is characterized in that described phosphate is selected from NaH
2PO
4, Na
2HPO
4, KH
2PO
4, K
2HPO
4, Ca (H
2PO
4)
2, Mg
3(PO
4)
2, LiH
2PO
4, Li
2HPO
4Or LaPO
4
7, the preparation method of molecular sieve catalyst as claimed in claim 6 is characterized in that described phosphate is NaH
2PO
4, its in catalyst before the roasting weight content be 10~30%.
8, the application of a kind of molecular sieve catalyst as claimed in claim 1 in crylic acid preparation by lactic acid dehydration.
9, application as claimed in claim 8 is characterized in that, is under normal pressure, and the material acid aqueous solution without the vaporization preheating, is directly injected fixed bed reactors, feeds inert gas simultaneously in reactor; Gas reacts by the catalytic bed that contains catalyst as claimed in claim 1, through obtaining acrylic acid after the dehydration; 300 ℃~500 ℃ of reaction temperatures, reaction velocity 0.2~4h
-1, inert gas flow velocity 10~100ml/min, lactic acid aqueous solution concentration 10~90wt%.
10, application as claimed in claim 9 is characterized in that, described inert gas is CO
2Or N
2
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Cited By (9)
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CN102029176A (en) * | 2010-11-17 | 2011-04-27 | 南京大学 | Supported molecular sieve catalyst, preparation method and application thereof in dehydration of lactic acid to acrylic acid |
CN102091647A (en) * | 2011-01-14 | 2011-06-15 | 南京大学 | Phosphate modified small-diameter NaY molecular sieve catalyst and preparation method and application thereof |
US8884050B2 (en) | 2012-04-11 | 2014-11-11 | The Procter & Gamble Company | Process for production of acrylic acid or its derivatives from hydroxypropionic acid or its derivatives |
CN104324746A (en) * | 2014-10-13 | 2015-02-04 | 浙江工业大学 | Metal modified ZSM-5 molecular sieve catalyst and its application |
CN104399515A (en) * | 2014-11-25 | 2015-03-11 | 大连理工大学 | High-efficiency composite catalyst for preparing acrylic acid by using lactic acid for catalytic dehydration and preparation method and application of high-efficiency composite catalyst |
CN105268472A (en) * | 2014-07-03 | 2016-01-27 | 中国石油化工股份有限公司 | ZSM-5/silicalite-1 core-shell molecular sieve for shell layer with oriented epitaxial intergrowth |
US9452967B2 (en) | 2012-04-11 | 2016-09-27 | The Procter & Gamble Company | Process for production of acrylic acid or its derivatives |
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CN102029176A (en) * | 2010-11-17 | 2011-04-27 | 南京大学 | Supported molecular sieve catalyst, preparation method and application thereof in dehydration of lactic acid to acrylic acid |
CN102091647A (en) * | 2011-01-14 | 2011-06-15 | 南京大学 | Phosphate modified small-diameter NaY molecular sieve catalyst and preparation method and application thereof |
CN102091647B (en) * | 2011-01-14 | 2012-11-28 | 南京大学 | Phosphate modified small-diameter NaY molecular sieve catalyst and preparation method and application thereof |
US8884050B2 (en) | 2012-04-11 | 2014-11-11 | The Procter & Gamble Company | Process for production of acrylic acid or its derivatives from hydroxypropionic acid or its derivatives |
US9505697B2 (en) | 2012-04-11 | 2016-11-29 | The Procter & Gamble Company | Method for the production of acrylic acid or its derivatives |
US9452967B2 (en) | 2012-04-11 | 2016-09-27 | The Procter & Gamble Company | Process for production of acrylic acid or its derivatives |
CN105268472A (en) * | 2014-07-03 | 2016-01-27 | 中国石油化工股份有限公司 | ZSM-5/silicalite-1 core-shell molecular sieve for shell layer with oriented epitaxial intergrowth |
CN105268472B (en) * | 2014-07-03 | 2018-02-13 | 中国石油化工股份有限公司 | Shell is orientated the core-shell molecular sieves of ZSM 5/silicalite 1 of extension symbiosis |
CN104324746A (en) * | 2014-10-13 | 2015-02-04 | 浙江工业大学 | Metal modified ZSM-5 molecular sieve catalyst and its application |
CN104399515A (en) * | 2014-11-25 | 2015-03-11 | 大连理工大学 | High-efficiency composite catalyst for preparing acrylic acid by using lactic acid for catalytic dehydration and preparation method and application of high-efficiency composite catalyst |
WO2019096761A1 (en) | 2017-11-17 | 2019-05-23 | Purac Biochem Bv | Process for the production of methyl acrylate from methyl lactate |
US11130727B2 (en) | 2017-11-17 | 2021-09-28 | Purac Biochem Bv | Process for the production of methyl acrylate from methyl lactate |
CN114768865A (en) * | 2022-05-24 | 2022-07-22 | 陈天然 | Catalyst for preparing 6-aminocapronitrile from cyclohexanone oxime and application thereof |
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