CN104801337A - Ethanol catalyst prepared from synthesis gas and dimethyl ether with one-step method as well as preparation method of ethanol catalyst - Google Patents
Ethanol catalyst prepared from synthesis gas and dimethyl ether with one-step method as well as preparation method of ethanol catalyst Download PDFInfo
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Abstract
The invention relates to a novel efficient ethanol catalyst prepared from synthesis gas and dimethyl ether with a one-step method as well as a preparation method of the ethanol catalyst. The main components of the catalyst comprise an efficient Cu-based hydrogenation catalyst and a core-shell catalyst which adopts an octatomic ring structure and all kinds of molecular sieves, and VIII, IB and IIB transition metal chlorides and nitrate in the periodic table of elements are used as promoters to be introduced into the Cu-based core catalyst. The molecular sieve shell catalyst adopts a porous structure after micro-mesoporous treatment, the reaction fluid diffusion and heat diffusion velocity is increased, carbon deposition is prevented, and the catalyst activity is improved. A reaction raw material, namely, dimethyl ether, firstly has a carbonylation reaction on the molecular sieve shell catalyst to produce methyl acetate, the methyl acetate and hydrogen are quickly diffused to the Cu-based core catalyst via micro-mesoporous passages to produce ethanol, the ethanol is quickly diffused, and the ethanol is prepared from synthesis gas and dimethyl ether with the one-step method. The ethanol selectivity is high, the catalyst cost is high, and the industrial application prospect is bright.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method, particularly relate to a kind of synthesis gas, alcohol catalysis agent prepared by single step dimethyl ether process and preparation method thereof.
Background technology
Ethanol is the substitute that following oil is good, and doing with ethanol the exhaust emission that oxygenation agent also can reduce by more than 20%, is a kind of energy of clean and effective.Other purposes of ethanol are also very extensive simultaneously, and global demand amount is increased sharply year by year.The Chinese government and scientific and technological circle recognize that exploitation alcohol fuel is to the importance solving oil critical shortage and Environment control, it is classified as great basic research, drop into a large amount of manpower and materials to develop, and achieve the target promoting the use of vehicle-use alcohol gasoline in the whole scopes such as Heilungkiang, Jilin, Liaoning, Henan and Anhui Province.
At present, commercial ethanol production process is mainly fermentation method and ethylene hydration method, and two kinds of methods all exist larger drawback.Fermentation method is mainly raw material with cereal crops; ethanol per ton about consumes 3-5 ton-grain food crop, and the alcohol fuel strategy in the whole world causes ethanol demand to be increased sharply, and provision price will be caused to skyrocket; even cause grain resource constantly in short supply, the further deterioration of aggravation world food crisis.And industrial ethylene hydration method prepares ethanol primarily of petroleum path ethylene catalyst hydration of setting out, and faces very large difficulty under the background of oil crisis undoubtedly.So adopt non-food living beings or more cheap coal resources to be that raw material is produced ethanol and become a new challenge.Especially, greatly develop the background of Coal Chemical Industry in China under, the route producing ethanol with Coal Chemical Industry Route has good development prospect.
In the recent period, Japanese Tsubaki team propose a kind of with dimethyl ether with synthesis gas for raw material, employing " dual bed catalyst " two-step method prepares the new method of ethanol.First the method is that DME generates methyl acetate by molecular sieve catalyst carbonylation, and then methyl acetate hydrogenation reaction on Cu is catalyst based generates ethanol.Effectively overcome the problem that synthesis gas directly prepares ethanol selectivity difference.But reaction needed is filled two-stage catalytic agent and is reduced space-time yield, is unfavorable for industrial applications; Adopt a point mode for bed filling, the synergy between two catalyst activity positions also receives very big restriction, causes overall catalytic activity lower; H-MOR molecular sieve carbon distribution in course of reaction of microcellular structure is serious, causes the catalyst activity life-span low.
Core-shell structure material presents the Wuli-Shili-Renli system approach of many novelties due to the structure of its uniqueness, becomes the study hotspot that researcher pays close attention to.Core-shell composite material is normally made up of kernel and shell two parts, and its character is controlled by the characteristic such as kind, character, shell thickness of inner nuclear material and Shell Materials respectively.The advantage of the functional materials such as its set nano material, porous material, crystalline material is in one, by special structure, realize a lot of complex function or brand-new function, can also be according to actual needs, characteristic for unlike material carries out compound, shows good application prospect at numerous areas such as catalysis, biology, medical science, optical, electrical, magnetic.
Nucleocapsid catalyst has played important function at catalytic field.The wherein nucleocapsid catalyst of molecular screen membrane coated metal oxide formation; because the pore structure of molecular sieve uniqueness and catalytic performance and core catalyst organically combine; shape selective catalysis can be realized; multistep reaction series connection can be realized again the multifunction of catalyst; improve the activity, selective of catalyst; can the features such as inner active component be protected simultaneously, be subject to extensive concern in heterogeneous catalysis research field at present.But micro porous molecular sieve permeability is poor, reduces the inside and outside diffusion velocity of reaction medium thus affect catalytic efficiency, being unfavorable for that reaction heat is removed fast simultaneously, causing focus to be assembled, causing carbon distribution to reduce catalyst activity and catalyst life.
Design the difunctional nucleocapsid catalyst that a kind of permeability is good, ethanol prepared by synthesis gas and dimethyl ether two-step method and be improved as a step and efficiently prepare ethanol and have great importance.
Summary of the invention
The object of the present invention is to provide a kind of synthesis gas, alcohol catalysis agent prepared by single step dimethyl ether process and preparation method thereof, catalyst principal component of the present invention is the nucleocapsid catalyst of Cu base efficient hydrogenation catalyst and the composition of all kinds molecular sieve with octatomic ring structure, improve catalyst activity, realize synthesis gas, single step dimethyl ether process prepares ethanol, there is ethanol selectivity high, catalyst cost is low, and prospects for commercial application is good.
The object of the invention is to be achieved through the following technical solutions:
Alcohol catalysis agent prepared by a kind of synthesis gas, single step dimethyl ether process, described constituent catalysts is the nucleocapsid catalyst of Cu base efficient hydrogenation catalyst and the composition of all kinds molecular sieve with octatomic ring structure, and Cu base catalyst nucleus introduces period of element Table VIII, IB, IIB group 4 transition metal chloride and nitrate as co-catalyst; Molecular sieve shell catalyst is micro--meso-hole structure.
Alcohol catalysis agent prepared by described a kind of synthesis gas, single step dimethyl ether process, the reaction that described catalyst is suitable for is dimethyl ether first carbonylation generation methyl acetate, and the further hydrogenation reaction of methyl acetate generates ethanol.
Alcohol catalysis agent prepared by described a kind of synthesis gas, single step dimethyl ether process, described " core " catalyst is Cu base efficient hydrogenation catalyst, and co-catalyst is period of element Table VIII, IB, IIB group 4 transition metal chloride and nitrate.
Alcohol catalysis agent prepared by described a kind of synthesis gas, single step dimethyl ether process, described lamella catalyst is the types of molecules sieve of octatomic ring structure, molecular sieve adopts in-situ synthesis, and namely list/bimodulus version synthetic method, post synthesis method and crystallization of pore wall method or outgrowth method or hydro-thermal recombination method or alkali treatment method or mechanical mixing or investment and nanoclusters self-assembly obtain micro--meso-hole structure.
Alcohol catalysis agent prepared by described a kind of synthesis gas, single step dimethyl ether process, described catalyst, the load capacity of Cu is 0-30%, (weight), and cocatalyst component is with 0 ~ 2%(weight) for good.
A preparation method for alcohol catalysis agent prepared by synthesis gas, single step dimethyl ether process, described method comprises following process:
Preparation has the nuclear material of high-activity hydrogenation catalyst, then that molecular screen membrane hydro-thermal method is coated with on catalyst nucleus uniformly; Catalyst is with copper nitrate and copper chloride for copper source, and carrier obtains Cu base supported catalyst with silica, zinc oxide, zirconia by infusion process, coprecipitation again; Catalyst single mode version method application hexadecyltrimethylammonium chloride is template, with alkoxy silane, high-purity silicon powder, high-purity gas-phase silica, Ludox for silicon source, sodium metaaluminate is aluminium source, zeolite synthetic is hydrothermal crystallizing 10-20 hour at 100-150 DEG C, through cooling, washing, drying, finally at 350-800 DEG C, calcine 4-12 hour, removing template; Micro--meso-hole structure 8 ring the zeolite catalyst of catalyst double-template synthesis adopts large molecule and Small molecular organic formwork respectively as mesoporous and template that is micropore, by modulation two kinds of templates in the ratio of zeolite synthetic and reaction temperature, control micro--mesoporous relative scale; The preparation of catalyst post synthesis method has 8 micro--mesoporous ring molecular sieves; First prepare the 8 ring structure molecular sieves with mesoporous or microcellular structure, then further crystallization is occurred to micropore and mesopore molecular sieve under structure directing agent effect, realize two kinds of structure molecular screen composite growth; Catalyst cupport condition is at 60-120 DEG C, pH is at 6-9 scope internal burden, add sodium carbonate, urea precipitation agent, introduce period of element Table VIII, IB, IIB group 4 transition metal chloride and nitrate as co-catalyst, then through overaging, washing, drying, that calcining obtains Cu is catalyst based.
Advantage of the present invention and effect are:
Catalyst principal component of the present invention is the nucleocapsid catalyst of Cu base efficient hydrogenation catalyst and the composition of all kinds molecular sieve with octatomic ring structure, and Cu base catalyst nucleus introduces period of element Table VIII, IB, IIB group 4 transition metal chloride and nitrate as co-catalyst.Molecular sieve shell catalyst obtains loose structure through micro--mesoporousization process, improves reacting fluid diffusion and Speed of diffusion, prevents carbon distribution from improving catalyst activity.Reaction raw materials dimethyl ether is carbonylation generation methyl acetate on molecular sieve lamella catalyst first, methyl acetate and hydrogen are diffused rapidly on Cu base catalyst nucleus by micro-mesopore orbit and generate ethanol, go out in rapid diffusion, realize synthesis gas, single step dimethyl ether process prepares ethanol.It is high that the present invention has ethanol selectivity, and catalyst cost is low, has good prospects for commercial application.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail.
The concrete implementation step that this explanation synthesis gas and single step dimethyl ether process prepare the new technology of ethanol and the preparation method of catalyst thereof is:
Design a kind of molecular sieve cladded type nucleocapsid catalyst with high-permeability, Cu base catalyst nucleus introduces period of element Table VIII, IB, IIB group 4 transition metal chloride and nitrate as co-catalyst.Molecular sieve shell catalyst obtains loose structure through micro--mesoporousization process, improves reacting fluid diffusion and Speed of diffusion, prevents carbon distribution from improving catalyst activity.Reaction raw materials dimethyl ether is carbonylation generation methyl acetate on molecular sieve lamella catalyst first, methyl acetate and hydrogen are diffused rapidly on Cu base catalyst nucleus by micro-mesopore orbit and generate ethanol, go out in rapid diffusion, realize synthesis gas, single step dimethyl ether process prepares ethanol.Catalyst " core " catalyst is Cu base efficient hydrogenation catalyst, and co-catalyst is period of element Table VIII, IB, IIB group 4 transition metal chloride and nitrate.
Catalyst lamella catalyst is all kinds molecular sieve of octatomic ring structure, and molecular sieve adopts in-situ synthesis (list/bimodulus version synthetic method), post synthesis method (crystallization of pore wall method, outgrowth method, hydro-thermal recombination method, alkali treatment method, mechanical mixing, investment) and nanoclusters self-assembly to obtain micro--meso-hole structure.Catalyst has the preparation of the nuclear material of high-activity hydrogenation catalyst, then that molecular screen membrane hydro-thermal method is coated with on catalyst nucleus uniformly.The catalyst nucleus of catalyst, wherein the load capacity of Cu is 0-30%, (weight), and cocatalyst component is with 0 ~ 2%(weight) for good.Catalyst nucleus in catalyst, with copper nitrate and copper chloride for copper source, carrier can obtain Cu base supported catalyst with silica, zinc oxide, zirconia by infusion process, coprecipitation again.Shell catalyst in catalyst, single mode version method application hexadecyltrimethylammonium chloride is template, with alkoxy silane, high-purity silicon powder, high-purity gas-phase silica, Ludox for silicon source, sodium metaaluminate is aluminium source, and zeolite synthetic is hydrothermal crystallizing 10-20 hour at 100-150 DEG C.Through cooling, washing, drying, finally at 350-800 DEG C, calcine 4-12 hour, removing template.Shell catalyst in catalyst, micro--meso-hole structure 8 ring the zeolite catalyst of double-template synthesis adopts large molecule and Small molecular organic formwork respectively as mesoporous and template that is micropore, by modulation two kinds of templates in the ratio of zeolite synthetic and reaction temperature, control micro--mesoporous relative scale.Shell catalyst in catalyst, post synthesis method preparation has 8 micro--mesoporous ring molecular sieves.First prepare the 8 ring structure molecular sieves with mesoporous or microcellular structure, then further crystallization is occurred to micropore and mesopore molecular sieve under structure directing agent effect, realize two kinds of structure molecular screen composite growth.Catalyst nucleus in catalyst, loading condition is at 60-120 DEG C, pH is within the scope of 6-9, load, suitably add the precipitating reagent such as sodium carbonate, urea, introduce period of element Table VIII, IB, IIB group 4 transition metal chloride and nitrate as co-catalyst, then through overaging, washing, drying, that calcining obtains efficient Cu is catalyst based.Carbonylation, hydrogenation reaction, it is tired of this temperature is at 150-240 DEG C.
Embodiment 1
Adopt copper nitrate and zinc nitrate to be raw material, take sodium carbonate as precipitating reagent, coprecipitation prepares Cu/ZnO catalyst, Cu:Zn=1:1 (mol ratio).Solution ph controls 8.8, and temperature is 60 DEG C, 12 hours presbyopic time, 120 DEG C of dryings 10 hours, 400 DEG C of calcinings, granulation 20-40 order.Ludox is silicon source and NaAlO
2be placed in hydrothermal synthesis reaction still with solution such as NaOH, catalyst nucleus immersed in this mixed solution.Hydrothermal synthesis reaction 48 hours, shows to form one deck micropore Na-MOR molecular screen membrane at Cu/ZnO, finally by ion-exchange Na-MOR is become mesoporous H-MOR thus obtains " Cu/ZnOH-MOR " nucleocapsid catalyst.Get 2g and carry out activity rating on fixed bed reactors.Dimethyl ether conversion per pass is 46%, and ethanol one way is selective is 38%.
Embodiment 2
Core method for preparing catalyst is with case study on implementation 1, and be template by hexadecyltrimethylammonium chloride, white carbon is silicon source, sodium metaaluminate is that reactor is put in aluminium source, immersed by catalyst nucleus in this mixed solution and react, rate of charge is 15SiO
2: Al
2o
3: 9Na
2o:6CTACB:700H
2o.120 DEG C of hydrothermal crystallizing synthetic reactions 48 hours, through cooling, washing, dry.Calcine 8 hours in air atmosphere at last 550 DEG C, remove template, show to form one deck micro--mesoporous Na-MOR molecular screen membrane at Cu/ZnO, finally by ion-exchange Na-MOR become mesoporous H-MOR thus obtain " Cu/ZnOH-MOR " nucleocapsid catalyst.Get 2g and carry out activity rating on fixed bed reactors.Dimethyl ether conversion per pass is 78%, and ethanol one way is selective is 41.5%.
Embodiment 3
Core method for preparing catalyst is with case study on implementation 1, and TTAB and six alkyl trimethyl ammonium bromides form two template agent, add sodium metaaluminate and Ludox simultaneously.At 120 DEG C of Water Under thermal crystallisations 8 hours, hole Na-MOR molecular screen membrane, finally by ion-exchange Na-MOR become mesoporous H-MOR thus obtain " Cu/ZnOH-MOR " nucleocapsid catalyst.Get 2g and carry out activity rating on fixed bed reactors.Dimethyl ether conversion per pass is 88%, and ethanol one way is selective is 41.8%.
Embodiment 4
Core method for preparing catalyst with case study on implementation 1, by mesoporous H-MOR molecular sieve and TPA
+carry out ion-exchange 20h, then mix with glycerine and together transfer in reactor with core catalyst, at 120 DEG C, carrying out hydrothermal crystallizing 24h, continuing to stir 2h under greenhouse, through washing, dry and roasting, obtain the coated Cu/ZnO nucleocapsid catalyst of micro--composite mesoporous structure H-MOR molecular sieve.Get 2g and carry out activity rating on fixed bed reactors.Dimethyl ether conversion per pass is 65%, and ethanol one way is selective is 37.8%.
Embodiment 5
4.4g copper nitrate is dissolved in 500ml water, takes 50g Ludox (solid content 28%), stirs.Add 200ml concentrated ammonia liquor, 120 DEG C of ammonia still process 4 hours.Through washing, dry, calcining granulation obtains 20-40 object Cu/SiO
2highly effective hydrogenation catalyst nucleus.Shell catalyst preparation method is with case study on implementation 2.Get 2g and carry out activity rating on fixed bed reactors.Dimethyl ether conversion per pass is 38%, and ethanol one way is selective is 32%.
Embodiment 6
Core method for preparing catalyst with case study on implementation 1, by a certain amount of NaAlO
2be dissolved in the aqueous solution containing TPAOH (TPAOH) and NaOH, then add ethyl orthosilicate (TEOS) and stir, stirred at ambient temperature 3 h is until obtain uniform mixed gel. Na in gel
2o:TPAOH:Al
2o
3: SiO
2: H
2to be 10:20:1:200:16000. proceed in self-pressure reactor by gel and mesoporous carbon and catalyst nucleus for the mol ratio of O, crystallization 4 d. cold filtration, washing under 158 ° of C, drying obtains the nucleocapsid catalyst of the coated Cu/ZnO of micro--mesoporous H-ZSM-35.Get 2g and carry out activity rating on fixed bed reactors.Dimethyl ether conversion per pass is 89%, and ethanol one way is selective is 41%.
Claims (6)
1. the alcohol catalysis agent prepared of a synthesis gas, single step dimethyl ether process, it is characterized in that, described constituent catalysts is the nucleocapsid catalyst of Cu base efficient hydrogenation catalyst and the composition of all kinds molecular sieve with octatomic ring structure, and Cu base catalyst nucleus introduces period of element Table VIII, IB, IIB group 4 transition metal chloride and nitrate as co-catalyst; Molecular sieve shell catalyst is micro--meso-hole structure.
2. the alcohol catalysis agent prepared of a kind of synthesis gas according to claim 1, single step dimethyl ether process, it is characterized in that, the reaction that described catalyst is suitable for is dimethyl ether first carbonylation generation methyl acetate, and the further hydrogenation reaction of methyl acetate generates ethanol.
3. the alcohol catalysis agent prepared of a kind of synthesis gas according to claim 1, single step dimethyl ether process, it is characterized in that, described " core " catalyst is Cu base efficient hydrogenation catalyst, and co-catalyst is period of element Table VIII, IB, IIB group 4 transition metal chloride and nitrate.
4. the alcohol catalysis agent prepared of a kind of synthesis gas according to claim 1, single step dimethyl ether process, it is characterized in that, described lamella catalyst is the types of molecules sieve of octatomic ring structure, molecular sieve adopts in-situ synthesis, and namely list/bimodulus version synthetic method, post synthesis method and crystallization of pore wall method or outgrowth method or hydro-thermal recombination method or alkali treatment method or mechanical mixing or investment and nanoclusters self-assembly obtain micro--meso-hole structure.
5. the alcohol catalysis agent prepared of a kind of synthesis gas according to claim 1, single step dimethyl ether process, it is characterized in that, described catalyst, the load capacity of Cu is 0-30%, (weight), and cocatalyst component is with 0 ~ 2%(weight) for good.
6. the preparation method of alcohol catalysis agent for preparing of synthesis gas, single step dimethyl ether process, it is characterized in that, described method comprises following process:
Preparation has the nuclear material of high-activity hydrogenation catalyst, then that molecular screen membrane hydro-thermal method is coated with on catalyst nucleus uniformly; Catalyst is with copper nitrate and copper chloride for copper source, and carrier obtains Cu base supported catalyst with silica, zinc oxide, zirconia by infusion process, coprecipitation again; Catalyst single mode version method application hexadecyltrimethylammonium chloride is template, with alkoxy silane, high-purity silicon powder, high-purity gas-phase silica, Ludox for silicon source, sodium metaaluminate is aluminium source, zeolite synthetic is hydrothermal crystallizing 10-20 hour at 100-150 DEG C, through cooling, washing, drying, finally at 350-800 DEG C, calcine 4-12 hour, removing template; Micro--meso-hole structure 8 ring the zeolite catalyst of catalyst double-template synthesis adopts large molecule and Small molecular organic formwork respectively as mesoporous and template that is micropore, by modulation two kinds of templates in the ratio of zeolite synthetic and reaction temperature, control micro--mesoporous relative scale; The preparation of catalyst post synthesis method has 8 micro--mesoporous ring molecular sieves; First prepare the 8 ring structure molecular sieves with mesoporous or microcellular structure, then further crystallization is occurred to micropore and mesopore molecular sieve under structure directing agent effect, realize two kinds of structure molecular screen composite growth; Catalyst cupport condition is at 60-120 DEG C, pH is at 6-9 scope internal burden, add sodium carbonate, urea precipitation agent, introduce period of element Table VIII, IB, IIB group 4 transition metal chloride and nitrate as co-catalyst, then through overaging, washing, drying, that calcining obtains Cu is catalyst based.
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| JP2016515039A (en) * | 2013-03-08 | 2016-05-26 | ビーピー ケミカルズ リミテッドＢｐ Ｃｈｅｍｉｃａｌｓ Ｌｉｍｉｔｅｄ | Carbonylation catalysts and processes |
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| CN109569712A (en) * | 2018-08-24 | 2019-04-05 | 南京大学 | One kind being used for CO2The catalyst and its preparation method and purposes of hydrogenating reduction production ethyl alcohol |
| CN109569712B (en) * | 2018-08-24 | 2022-04-22 | 南京大学 | For CO2Catalyst for producing ethanol by hydrogenation reduction and preparation method and application thereof |
| CN111001431A (en) * | 2019-12-06 | 2020-04-14 | 西南化工研究设计院有限公司 | Core-shell catalyst for preparing ethanol from dimethyl ether and synthesis gas by one-step method and preparation method and application thereof |
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Application publication date: 20150729 |