CN106563454A - Catalyst for preparing methyl alcohol by adding hydrogen to CO2 and preparation method and application of catalyst - Google Patents
Catalyst for preparing methyl alcohol by adding hydrogen to CO2 and preparation method and application of catalyst Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- 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 catalyst for preparing methyl alcohol by adding hydrogen to CO2 and a preparation method and application of the catalyst. The content of rGO/Cu-ZnO-Al2O, by mass ratio is (0.04-0.2)/1, and the catalyst is prepared through a parallel-flow co-precipitation method. The preparation method is simple, conditions are easy to control, and repeatability is good. Introduction of the reduced graphene oxide rGO overcomes the problems that the CO2 conversion rate of an existing catalyst for synthesizing methyl alcohol by adding hydrogen to CO2 is low, and selectivity of methanol alcohol is poor. The catalyst has a composition structure easy to modulate and a higher specific surface area, and dispersity of metal elements in the catalyst is improved. The catalyst is applied to a reaction for synthesizing methyl alcohol by adding hydrogen to CO2, the CO2 conversion rate is remarkably raised, and selectivity of methanol alcohol is remarkably improved.
Description
Technical field
The invention belongs to catalyst technical field, is related to a kind of catalyst and preparation method and application, and in particular to a kind of
For CO2The catalyst and its preparation method of direct hydrogenation methanol and application.
Background technology
With quickly propelling for industrial development, CO2Discharge causes greenhouse effect --- --- climate warming.China is with coal
Based on energy resource consumption big country, while energy utilization rate is low, CO2Reduction of discharging is shouldered heavy responsibilities.CO2There is synthesis first using new technology research
Alcohol, formic acid, Merlon, production synthesis gas, ethanol, fuel oil etc..Methanol has as basic organic chemical industry raw material and power fuel
Have broad application prospects, can be used to prepare the products such as low-carbon alkene, formic acid, methyl formate and acetic acid.Methanol is also liquid simultaneously
State Hydrogen carrier, conversion power consumption are readily transported than pressurized with hydrogen or the low, safety that liquefies.In view of methanol is former as important chemical industry
Material, CO2The process of synthesizing methanol by hydrogenating receives researcher extensive concern.At present, constituted by transformation catalyst and improved and urged
Agent preparation method is come important directions that the performance that improves catalyst is still that researcher is captured.
The advantages of due to low pressure activity height, good combination property, copper-based catalysts have become the catalyst system of most study.
Researcher usually modifies Cu by adding the unit such as Zn, Al, Zr, Mg, Mn, Cr, La, B, In, Ga, Gd, Ce, Y, Ti, Ag, Fe and V
Base catalyst, or it is by preparing catalyst method using the such as difference such as sol-gal process, coprecipitation and azeotropic distillation method or logical
The texture and performance for crossing using processing means such as microwave and ultrasounds to change catalyst, and then improve the activity of catalyst.
Patent CN1329938A is related to a kind of preparation method of catalst for synthesis of methanol, and the catalyst is by CuO, ZnO, Al2O3
Constitute, its preparation process is：Prepared by catalyst masterbatch be divided into two parts, a part makes cupric, zinc-aluminium with co-precipitation
The co-precipitate of compound, another part prepare the co-precipitate containing copper, zinc compound with coprecipitation.Then by two precipitations
Thing mixing, washing, drying, roasting, molding.
Patent CN101444731A discloses a kind of CO2The catalyst of synthesizing methanol by hydrogenating.The catalyst includes Pd, Zn master
Component and carbon nano-tube material accelerator, each component weight/mass percentage composition be Pd2%～25%, Zn55%～90%, carbon nanometer
Tube material 6%～20%.
Patent CN101757943A is related to a kind of CO2Catalyst of synthesizing methanol by hydrogenating and preparation method thereof.With HZSM-5
It is auxiliary agent that molecular sieve makees carrier, cerium zirconium, prepares Cu-Zn-Ce-Zr-HZSM-5 catalyst, and the mol ratio of Cu/Zn is 2～4: 1,
It is 5%～50% for the mass content of 30%～70%, HZSM-5 that the mol ratio of Ce/Zr is 1～3: 1, Cu-Zn mass contents.
CO2Synthesizing methanol by hydrogenating catalyst performance is affected by preparation procedure, pretreatment, reaction raw materials proportioning etc..With CuO-
ZnO-Al2O3Specific surface area of catalyst is less, is easily poisoned, and activity is relatively low, further need to improve.Catalyst microstructure, component are brilliant
Granularity, the catalysis activity that its catalyst certainly will be had influence on of component interphase interaction.In open report document, stone is not yet referred to
Black alkene is applied to CO2In synthesizing methanol by hydrogenating reaction.
Graphene can regard the monoatomic layer graphite material being stripped as, and basic structure is sp2The class that hydbridized carbon atoms are formed
Hexa-atomic ring element, and two dimensional crystal is formed by infinite expanding, it is the material of material-monoatomic thickness most thin in the world at present
Material.Redox graphene (rGO) can also form controllable chemical imperfection, such as surface hydroxyl, carbonyl by functionalisation of surfaces
Base, epoxy radicals etc., these chemical imperfections as the nuclearing centre of metal growth, can reach the purpose of control metal growth.Mirror
There is unique pore structure, high surface area, adsorption/desorption mild condition, safety, low cost, life-span length in rGO,
It is intended for CO2In preparing methanol by hydrogenation catalysts, to H2With good adsorption, H atom is made more preferably to be adsorbed in metal
Surface, while rGO is to CO2There is good adsorption, greatly enhance carrier function, so as to improve the performance of catalyst.
In CO2In terms of synthesizing methanol by hydrogenating, the catalyst of document and patent report all achieves preferably progress, such as higher
Catalysis activity, but catalyst often preparation process is loaded down with trivial details, repeatable difference, anti-poisoning performance is poor, mechanical strength is low, produces into
This higher, catalyst easy in inactivation.The problem that catalyst performance need to be solved is：Catalyst activity is improved, while improving methanol
Selectivity and methanol yield.
The content of the invention
The purpose of the present invention is to overcome prior art defect to provide one kind for CO2Hydrogenation directly the catalyst of methanol processed,
Its preparation method and application.
Catalyst preparation materials of the present invention are cheap and easy to get, using the preparation process is simple of coprecipitation, cycle is short, repeatability
It is good.
The copper-based catalysts that the present invention is prepared using coprecipitation, the introducing of novelty is with the Graphene material for being easy to modulation
Material.With redox graphene and composite Cu-ZnO-Al2O3The catalyst that metal-oxide is formed, easily adjusts with composition structure
Become, specific surface area is high, heat stability high, alkalescence is relatively strong, can realize being uniformly distributed and interaction modulation etc. for metallic element
Advantage, shows good activity in synthesizing methanol by hydrogenating carbon dioxide reaction.
The present invention for CO2The catalyst of the direct methanol processed of hydrogenation, catalyst contain Cu element Zn elements, Al elements and
Redox graphene rGO, metallic element are present with simple substance or oxide form, are Cu, ZnO, Al2O3, raw materials used proportioning
(mass ratio) Cu: ZnO: Al2O3=4-7: 3: 3, rGO: Cu-ZnO-Al2O3=(0.04-0.2): 1, catalyst is with mass fraction
Meter, Cu contents be 5～45%, Zn contents be 1～30%, Al content be 1～30%, redox graphene rGO contents be 2～
50%.
Redox graphene rGO in catalytic component is graphene oxide GO prepared by improved Hummers methods, is led to
Cross hydrazine hydrate reduction to be obtained.Improved catalyst performance index has reached CO2Conversion per pass 15%-28%, methanol are selected
Property 30%-55%, methanol yield is 5-15%.
The present invention for CO2The preparation method of directly catalyst for methanol processed is hydrogenated with, is prepared by following steps：
(1) graphene oxide GO ultrasonic disperse 30min are weighed in proportion, and deionized water dissolving is designated as solution A.
(2) by component copper, zinc, aluminum atomic molar proportioning, weigh copper source, zinc source and silicon source, being configured to concentration is
The aqueous solution of 1-3mol/L, is designated as B solution, the nitrate of copper source, zinc source and silicon source for metallic element；
(3) with Na2CO3Or K2CO3For precipitant, the aqueous solution that concentration is 1-3mol/L is configured to, C solution is designated as；
(4) using co-precipitation method, by B solution, constant speed is instilled in solution A simultaneously with C solution, and bath temperature is 50-
100 DEG C, drop rate is 100-200mLh-1, regulation pH is 7-8, and mixing speed is 800-1000r/min；
(5) after completion of dropping, after stirring 30min, add hydrazine hydrate 0-10mL, continue stirring 60-120min, at 20-40 DEG C
Aging 8-26h；
(6) product Jing is filtered, washing, is dried, and in 300-400 DEG C of roasting temperature 5 hours, is obtained catalyst and is produced
Product；
The present invention for CO2The catalyst of preparing methanol by hydrogenation its application, comprise the steps：
(1) catalyst is applied in fixed bed reactors, and pressure is 0.1～2.0MPa, and air speed is 1000～3000h-1, first
In H2/N2=5/95 N2+H2Gaseous mixture or pure H2Atmosphere under reduce, 4～24h of reduction treatment, reduction temperature 200～
400℃；
(2) by the amount ratio of material be H2/CO2=(1～3): 1, CO2+H2Gaseous mixture is passed through reactor, reaction condition：Temperature
200～300 DEG C, pressure 12.0-4.0MPa, W/F are 5～20gh/mol.
The preparation method of graphene oxide (GO) is：Graphene oxide is prepared using improvement Hummers methods, is being dried first
Beaker in add concentrated sulphuric acid (H2SO4, 98%) cool down under condition of ice bath.When the temperature of system is less than 5 DEG C, scale stone is added
Ink.Stirring 30min, mix homogeneously are slowly added to potassium permanganate (KMnO4), control reacting liquid temperature is less than 5 DEG C, stirs 1h.
Then beaker is placed in 30 DEG C of waters bath with thermostatic control, continues stirring 1h, be subsequently adding 230mL deionized waters, while adding H2O2
(30% aqueous solution, 25mL), solution are changed into vivid yellow, reaction terminating from brick-red.12h is stood, with dilute HCl (1: 10/ bodies
Product ratio) which is washed, freeze at -18 DEG C, then using freezer dryer after -56 DEG C of dryings, obtain graphite oxide
(GO) sample.Redox graphene rGO is graphene oxide GO prepared by improved Hummers methods, by hydrazine hydrate reduction
It is obtained.After co-precipitation is completed between catalyst raw material, hydrazine hydrate is added into, and is applied in fixed bed reactors, using oxidation
Reduction principle is reacted.Obtain redox graphene rGO.
The present invention will be further described for specific embodiment.
Specific embodiment
Embodiment 1
By Cu/ZnO/Al2O3=4/3/3 mass ratio weighs 6.1gCu (NO3)2·3H2O、4.1gZn(NO3)2·6H2O、
4.4gAl(NO3)3·9H2O, deionized water dissolving are solution A, weigh 7.1g anhydrous Nas CO by the solution of 1mol/L3, deionization
Water dissolution is solution B.Using peristaltic pump while Deca solution A and solution B, drop rate is 150mLh-1, mixing speed is
900r/min, reaction temperature are 70 DEG C of bath temperatures, control pH=7, after completion of dropping, continue stirring 120min, then 30
DEG C aging 12h, filters, 90 DEG C of dried overnights, 350 DEG C of logical N2Roasting 5h, 20～40 mesh pelletizes, obtains final product catalyst sample 1, is denoted as
CuO-ZnO-Al2O3.The reducing condition of catalyst is：H2/N2=5/95,300 DEG C of temperature, pressure 0.1MPa, air speed 2400h-1；
Reaction condition：H2/CO2=3,250 DEG C of temperature, pressure 3.0MPa, W/F are 10gh/mol.The results are shown in Table 1.
Embodiment 2
Graphene oxide is prepared using improvement Hummers methods, concentrated sulphuric acid (H is added first in dry beaker2SO4,
115mL, 98%) cools down under condition of ice bath.When the temperature of system is less than 5 DEG C, crystalline flake graphite (5g) is added.Stirring 30min, mixes
Close uniform, be slowly added to potassium permanganate (KMnO4, 15g), control reacting liquid temperature is less than 5 DEG C, stirs 1h.Then by beaker
It is placed in 30 DEG C of waters bath with thermostatic control, continues stirring 1h, be subsequently adding 230mL deionized waters, while adds H2O2(30% aqueous solution,
25mL), solution is changed into vivid yellow, reaction terminating from brick-red.12h is stood, with dilute HCl (1: 10/ volume ratio, 2L) to which
Washed, freezed at -18 DEG C, then using freezer dryer after -56 DEG C of dryings, obtained graphite oxide (GO) sample.
0.16g GO ultrasonic disperse 30min are weighed, deionized water dissolving is solution A.By Cu/ZnO/Al2O3=4/3/3 matter
Amount ratio weighs 6.1gCu (NO3)2·3H2O、4.1gZn(NO3)2·6H2O、4.4gAl(NO3)3·9H2O, deionized water dissolving is
Solution B, weighs 7.1g anhydrous Nas CO by the solution of 1mol/L3, deionized water dissolving is solution C.Using peristaltic pump while Deca
With solution C in solution A, drop rate is 150mLh to solution B-1, mixing speed is 900r/min, and reaction temperature is 70 DEG C of water
Bath temperature, controls pH=7, after completion of dropping, stirs 30min, then adds hydrazine hydrate 1.6mL, continues stirring 120min, then
In 30 DEG C of aging 12h, filtration, 60 DEG C of dried overnights, 350 DEG C of logical N2Roasting 5h, 20～40 mesh pelletizes, obtains final product catalyst sample 2,
It is denoted as 4%rGO/CuO-ZnO-Al2O3.The reducing condition of catalyst is：H2/N2=5/95,300 DEG C of temperature, pressure 0.1MPa,
Air speed 2400h-1；Reaction condition：H2/CO2=3,250 DEG C of temperature, pressure 3.0MPa, W/F are 10gh/mol.The results are shown in Table 1.
Embodiment 3
Graphene oxide is prepared using improvement Hummers methods, concentrated sulphuric acid (H is added first in dry beaker2SO4,
115mL, 98%) cools down under condition of ice bath.When the temperature of system is less than 5 DEG C, crystalline flake graphite (5g) is added.Stirring 30min, mixes
Close uniform, be slowly added to potassium permanganate (KMnO4, 15g), control reacting liquid temperature is less than 5 DEG C, stirs 1h.Then by beaker
It is placed in 30 DEG C of waters bath with thermostatic control, continues stirring 1h, be subsequently adding 230mL deionized waters, while adds H2O2(30% aqueous solution,
25mL), solution is changed into vivid yellow, reaction terminating from brick-red.12h is stood, with dilute HCl (1: 10/ volume ratio, 2L) to which
Washed, freezed at -18 DEG C, then using freezer dryer after -56 DEG C of dryings, obtained graphite oxide (GO) sample.
0.28g GO ultrasonic disperse 30min are weighed, deionized water dissolving is solution A.By Cu/ZnO/Al2O3=4/3/3 matter
Amount ratio weighs 6.1gCu (NO3)2·3H2O、4.1gZn(NO3)2·6H2O、4.4gAl(NO3)3·9H2O, deionized water dissolving is
Solution B, weighs 7.1g anhydrous Nas CO by the solution of 1mol/L3, deionized water dissolving is solution C.Using peristaltic pump while Deca
With solution C in solution A, drop rate is 150mLh to solution B-1, mixing speed is 900r/min, and reaction temperature is 70 DEG C of water
Bath temperature, controls pH=7, after completion of dropping, stirs 30min, then adds hydrazine hydrate 2.8mL, continues stirring 120min, then
In 30 DEG C of aging 12h, filtration, 60 DEG C of dried overnights, 350 DEG C of logical N2Roasting 5h, 20～40 mesh pelletizes, obtains final product catalyst sample 3,
It is denoted as 7%rGO/CuO-ZnO-Al2O3.The reducing condition of catalyst is：H2/N2=5/95,300 DEG C of temperature, pressure 0.1MPa,
Air speed 2400h-1；Reaction condition：H2/CO2=3,250 DEG C of temperature, pressure 3.0MPa, W/F are 10gh/mol.The results are shown in Table 1.
Embodiment 4
Graphene oxide is prepared using improvement Hummers methods, concentrated sulphuric acid (H is added first in dry beaker2SO4,
115mL, 98%) cools down under condition of ice bath.When the temperature of system is less than 5 DEG C, crystalline flake graphite (5g) is added.Stirring 30min, mixes
Close uniform, be slowly added to potassium permanganate (KMnO4, 15g), control reacting liquid temperature is less than 5 DEG C, stirs 1h.Then by beaker
It is placed in 30 DEG C of waters bath with thermostatic control, continues stirring 1h, be subsequently adding 230mL deionized waters, while adds H2O2(30% aqueous solution,
25mL), solution is changed into vivid yellow, reaction terminating from brick-red.12h is stood, with dilute HCl (1: 10/ volume ratio, 2L) to which
Washed, freezed at -18 DEG C, then using freezer dryer after -56 DEG C of dryings, obtained graphite oxide (GO) sample.
0.4g GO ultrasonic disperse 30min are weighed, deionized water dissolving is solution A.By Cu/ZnO/Al2O3=4/3/3 mass
Than weighing 6.1gCu (NO3)2·3H2O、4.1gZn(NO3)2·6H2O、4.4gAl(NO3)3·9H2O, deionized water dissolving are molten
Liquid B, weighs 7.1g anhydrous Ks by the solution of 1mol/L2CO3, deionized water dissolving is solution C.Using peristaltic pump while Deca solution
With solution C in solution A, drop rate is 150mLh to B-1, mixing speed is 900r/min, and reaction temperature is 70 DEG C of water-bath temperature
Degree, controls pH=7, after completion of dropping, stirs 30min, then adds hydrazine hydrate 4.0mL, continues stirring 120min, then 30
DEG C aging 12h, filters, 60 DEG C of dried overnights, 350 DEG C of logical N2Roasting 5h, 20～40 mesh pelletizes, obtains final product catalyst sample 4, is denoted as
10%rGO/CuO-ZnO-Al2O3.The reducing condition of catalyst is：H2/N2=5/95,300 DEG C of temperature, pressure 0.1MPa, air speed
2400h-1；Reaction condition：H2/CO2=3,250 DEG C of temperature, pressure 3.0MPa, W/F are 10gh/mol.The results are shown in Table 1.
Embodiment 5
Graphene oxide is prepared using improvement Hummers methods, concentrated sulphuric acid (H is added first in dry beaker2SO4,
115mL, 98%) cools down under condition of ice bath.When the temperature of system is less than 5 DEG C, crystalline flake graphite (5g) is added.Stirring 30min, mixes
Close uniform, be slowly added to potassium permanganate (KMnO4, 15g), control reacting liquid temperature is less than 5 DEG C, stirs 1h.Then by beaker
It is placed in 30 DEG C of waters bath with thermostatic control, continues stirring 1h, be subsequently adding 230mL deionized waters, while adds H2O2(30% aqueous solution,
25mL), solution is changed into vivid yellow, reaction terminating from brick-red.12h is stood, with dilute HCl (1: 10/ volume ratio, 2L) to which
Washed, freezed at -18 DEG C, then using freezer dryer after -56 DEG C of dryings, obtained graphite oxide (GO) sample.
0.52g GO ultrasonic disperse 30min are weighed, deionized water dissolving is solution A.By Cu/ZnO/Al2O3=4/3/3 matter
Amount ratio weighs 6.1gCu (NO3)2·3H2O、4.1gZn(NO3)2·6H2O、4.4gAl(NO3)3·9H2O, deionized water dissolving is
Solution B, weighs 7.1g anhydrous Nas CO by the solution of 1mol/L3, deionized water dissolving is solution C.Using peristaltic pump while Deca
With solution C in solution A, drop rate is 150mLh to solution B-1, mixing speed is 900r/min, and reaction temperature is 70 DEG C of water
Bath temperature, controls pH=7, after completion of dropping, stirs 30min, then adds hydrazine hydrate 5.2mL, continues stirring 120min, then
In 30 DEG C of aging 12h, filtration, 60 DEG C of dried overnights, 350 DEG C of logical N2Roasting 5h, 20～40 mesh pelletizes, obtains final product catalyst sample 5,
It is denoted as 13%rGO/CuO-ZnO-Al2O3.The reducing condition of catalyst is：H2/N2=5/95,300 DEG C of temperature, pressure 0.1MPa,
Air speed 2400h-1；Reaction condition：H2/CO2=3,250 DEG C of temperature, pressure 3.0MPa, W/F are 10gh/mol.The results are shown in Table 1.
Embodiment 6
Graphene oxide is prepared using improvement Hummers methods, concentrated sulphuric acid (H is added first in dry beaker2SO4,
115mL, 98%) cools down under condition of ice bath.When the temperature of system is less than 5 DEG C, crystalline flake graphite (5g) is added.Stirring 30min, mixes
Close uniform, be slowly added to potassium permanganate (KMnO4, 15g), control reacting liquid temperature is less than 5 DEG C, stirs 1h.Then by beaker
It is placed in 30 DEG C of waters bath with thermostatic control, continues stirring 1h, be subsequently adding 230mL deionized waters, while adds H2O2(30% aqueous solution,
25mL), solution is changed into vivid yellow, reaction terminating from brick-red.12h is stood, with dilute HCl (1: 10/ volume ratio, 2L) to which
Washed, freezed at -18 DEG C, then using freezer dryer after -56 DEG C of dryings, obtained graphite oxide (GO) sample.
0.64g GO ultrasonic disperse 30min are weighed, deionized water dissolving is solution A.By Cu/ZnO/Al2O3=4/3/3 matter
Amount ratio weighs 6.1gCu (NO3)2·3H2O、4.1gZn(NO3)2·6H2O、4.4gAl(NO3)3·9H2O, deionized water dissolving is
Solution B, weighs 7.1g anhydrous Nas CO by the solution of 1mol/L3, deionized water dissolving is solution C.Using peristaltic pump while Deca
With solution C in solution A, drop rate is 150mLh to solution B-1, mixing speed is 900r/min, and reaction temperature is 70 DEG C of water
Bath temperature, controls pH=7, after completion of dropping, stirs 30min, then adds hydrazine hydrate 6.4mL, continues stirring 120min, then
In 30 DEG C of aging 12h, filtration, 60 DEG C of dried overnights, 350 DEG C of logical N2Roasting 5h, 20～40 mesh pelletizes, obtains final product catalyst sample 6,
It is denoted as 16%rGO/CuO-ZnO-Al2O3.The reducing condition of catalyst is：H2/N2=5/95,300 DEG C of temperature, pressure 0.1MPa,
Air speed 2400h-1；Reaction condition：H2/CO2=3,250 DEG C of temperature, pressure 3.0MPa, W/F are 10gh/mol.The results are shown in Table 1.
1 catalyst activity of table
Claims (4)
1. it is a kind of to be used for CO2The catalyst of preparing methanol by hydrogenation, it is characterised in that it is first that the catalyst contains Cu element Zn elements, Al
Element and redox graphene rGO, metallic element are present with simple substance or oxide form, are Cu, ZnO, Al2O3, and mass ratio is
Cu∶ZnO∶Al2O3=4-7: 3: 3, rGO: Cu-ZnO-Al2O3=(0.04-0.2): 1, the catalyst in terms of mass fraction, Cu
It is 1～30% that content is 5～45%, Zn contents, and Al content is 1～30%, and redox graphene rGO contents are 2～50%.
2. according to claim 1 a kind of for CO2The catalyst of preparing methanol by hydrogenation, it is characterised in that the reduction-oxidation
Graphene rGO is graphene oxide GO prepared by improved Hummers methods, is obtained by hydrazine hydrate reduction.
3. according to claim 1 a kind of for CO2The preparation method of the catalyst of preparing methanol by hydrogenation, it is characterised in that bag
Include following steps：
(1) graphene oxide GO is weighed in proportion, and ultrasonic disperse 30min, deionized water dissolving are designated as solution A；
(2) catalyst composition metallic element is dissolved in deionized water in the form of nitrate, is made into mixed aqueous solution in proportion, dense
Spend for 1-3mol/L, be designated as B solution；
(3) carbonate deposition agent is prepared, carbonate can be Na2CO3Or K2CO3, deionized water dissolving, it is 1- to be configured to concentration
The aqueous solution of 3mol/L, is designated as C solution；
(4) using co-precipitation method, by B solution, constant speed is instilled in solution A simultaneously with C solution, and bath temperature is 50-100 DEG C,
Drop rate is 100-200mLh-1, regulation pH is 7-8, and mixing speed is 800-1000r/min；
(5) after completion of dropping, after stirring 30min, add hydrazine hydrate 0-10mL, continue stirring 60-120min, it is aging at 20-40 DEG C
8-26h；
(6) product Jing is filtered, washing, is dried, and in 300-400 DEG C of roasting temperature 5 hours, obtains catalyst prod.
4. required according to right 1 a kind of for CO2The application of the catalyst of preparing methanol by hydrogenation, it is characterised in that including following step
Suddenly：
(1) catalyst is applied in fixed bed reactors, and pressure is 0.1～2.0MPa, and air speed is 1000～3000h-1, first
In volume ratio H2/N2=5/95 N2+H2Gaseous mixture or pure H2Atmosphere under reduce, 4～24h of reduction treatment, reduction temperature
200～400 DEG C；
(2) by the amount ratio of material be H2/CO2=(1～3): 1, CO2+H2Gaseous mixture is passed through reactor, reaction condition：Temperature 200～
300 DEG C, pressure 12.0-4.0MPa, W/F are 5～20gh/mol.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106925315A (en) * | 2017-03-09 | 2017-07-07 | 盐城复华环保产业开发有限公司 | A kind of catalyst and preparation method thereof and the application in carbon dioxide synthesis of low-carbon alcohol |
| CN107042101A (en) * | 2017-06-02 | 2017-08-15 | 宁夏大学 | A kind of hydrogenation of carbon dioxide catalyst for methanol of doped graphene |
| CN108889302A (en) * | 2018-07-20 | 2018-11-27 | 太原理工大学 | CO and CO2Cu base catalyst of synthesizing methanol by hydrogenating and its preparation method and application |
| CN109317192A (en) * | 2018-09-30 | 2019-02-12 | 宁夏大学 | A kind of CO2The nucleocapsid catalyst of hydrogenation coupled preparing low-carbon olefins and its preparation |
| CN110681383A (en) * | 2018-07-06 | 2020-01-14 | 中国石油化工股份有限公司 | Multi-component methanol synthesis catalyst and preparation method thereof |
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| CN115007160A (en) * | 2022-07-05 | 2022-09-06 | 国网河南省电力公司电力科学研究院 | Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102658151A (en) * | 2012-04-28 | 2012-09-12 | 上海华谊（集团）公司 | Preparation method of methanol catalyst master body by carbon dioxide (CO2) hydrogenation |
| CN104959143A (en) * | 2015-06-12 | 2015-10-07 | 中国科学院上海高等研究院 | Catalyst for methanol synthesis via CO2 hydrogenation on slurry bed reactor, preparation method and application |
-
2016
- 2016-11-11 CN CN201610991636.6A patent/CN106563454A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102658151A (en) * | 2012-04-28 | 2012-09-12 | 上海华谊（集团）公司 | Preparation method of methanol catalyst master body by carbon dioxide (CO2) hydrogenation |
| CN104959143A (en) * | 2015-06-12 | 2015-10-07 | 中国科学院上海高等研究院 | Catalyst for methanol synthesis via CO2 hydrogenation on slurry bed reactor, preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| VARISARA DEERATTRAKUL等: "CO2 hydrogenation to methanol using Cu-Zn catalyst supported on reduced graphene oxide nanosheets", 《JOURNAL OF CO2 UTILIZATION》 * |
| 孙玉海等: "石墨烯负载铂催化剂对肉桂醛选择性加氢性能影响", 《中国科技论文》 * |
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| CN106925315B (en) * | 2017-03-09 | 2019-08-06 | 盐城复华环保产业开发有限公司 | A kind of catalyst and preparation method thereof and the application in carbon dioxide synthesis of low-carbon alcohol |
| CN107042101A (en) * | 2017-06-02 | 2017-08-15 | 宁夏大学 | A kind of hydrogenation of carbon dioxide catalyst for methanol of doped graphene |
| CN110681383A (en) * | 2018-07-06 | 2020-01-14 | 中国石油化工股份有限公司 | Multi-component methanol synthesis catalyst and preparation method thereof |
| CN108889302A (en) * | 2018-07-20 | 2018-11-27 | 太原理工大学 | CO and CO2Cu base catalyst of synthesizing methanol by hydrogenating and its preparation method and application |
| CN109317192A (en) * | 2018-09-30 | 2019-02-12 | 宁夏大学 | A kind of CO2The nucleocapsid catalyst of hydrogenation coupled preparing low-carbon olefins and its preparation |
| CN109317192B (en) * | 2018-09-30 | 2021-04-27 | 宁夏大学 | CO (carbon monoxide)2Core-shell catalyst for preparing low-carbon olefin by hydrogenation coupling and preparation thereof |
| CN111530467A (en) * | 2019-10-23 | 2020-08-14 | 宁夏大学 | Carbon modified copper-based catalyst and preparation method and application thereof |
| CN115007160A (en) * | 2022-07-05 | 2022-09-06 | 国网河南省电力公司电力科学研究院 | Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method and application thereof |
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