CN106622252A - Catalyst for production of methanol by CO2 hydrogenation - Google Patents
Catalyst for production of methanol by CO2 hydrogenation Download PDFInfo
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- CN106622252A CN106622252A CN201611059525.8A CN201611059525A CN106622252A CN 106622252 A CN106622252 A CN 106622252A CN 201611059525 A CN201611059525 A CN 201611059525A CN 106622252 A CN106622252 A CN 106622252A
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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
- 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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- 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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- 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 discloses a catalyst for production of methanol by CO2 hydrogenation. The invention is intended to overcome the problems of low CO2 conversion ratio and low methanol selectivity in a CO2 hydrogenation methanol synthesis process and studies a catalyst with Cu, ZnO, ZrO2 and graphene oxide (GO) as main components. The content, calculated in mass ratio, namely GO/Cu-ZnO-ZrO2, is (0.04-0.16)/1, and the catalyst is prepared by adopting a parallel flow coprecipitation method. The preparation process is simple, conditions are easy to control, and repeatability is good. The catalyst disclosed by the invention has the advantages of easily adjustable and variable composition and structure, larger specific surface area, dispersed active components and good catalytic activity. In a CO2 hydrogenation methanol synthesis reaction, the CO2 conversion ratio and methanol selectivity are improved, CO2 emission reduction is achieved, and the catalyst is significant for solving increasingly serious environmental problems.
Description
Technical field
The invention belongs to catalyst technical field, relates in particular to a kind of for CO2The catalysis of direct hydrogenation methyl alcohol
Agent and its preparation method and application.
Background technology
The life that the fast development of modern industry gives people bring it is convenient with it is advanced, at the same time, also generate
Discharge to environmentally undesirable factor, particularly great amount of carbon dioxide so that the concentration of carbon dioxide is sharply increased in air,
CO2Discharge causes greenhouse effects --- --- climate warming.CO2Reduction of discharging is shouldered heavy responsibilities, and how to reduce the discharge of carbon dioxide, drop
Low Carbon Dioxide in Air is a difficult task for a long time.CO2There are synthesizing methanol, formic acid, gather using new technology research
Carbonic ester, production synthesis gas, ethanol, fuel oil etc..Methyl alcohol has wide answering as basic organic chemical industry raw material and power fuel
With prospect, can be used to prepare the products such as low-carbon alkene, formic acid, methyl formate and acetic acid.CO2Synthesizing methanol by hydrogenating catalyst performance
Affected by preparation procedure, pretreatment, reaction raw materials proportioning etc., traditional copper-based specific surface area of catalyst is less, easily poisoning, activity compared with
It is low, need to further improve.
Although in the world to CO2Preparing methanol by hydrogenation technology correlative study report is countless, but the technology wants to realize producing
Industryization is still faced with some technical bottlenecks, wherein, it is most important that the research and development of effective catalyst.CO2The chemical bond energy of molecule is high,
It is difficult to participate in chemical reaction, therefore, CO2Preparing methanol by hydrogenation reaction needs just to be smoothed out in the presence of high performance catalyst.
Conventional methanol synthetic catalyst Cu-ZnO-Al2O3For CO2Catalytic performance is not high in preparing methanol by hydrogenation reaction.It is believed that CO
(or CO2) preparing methanol by hydrogenation Cu-ZnO base catalyst roasting before active presoma should be copper zinc Multiple salts forms, including (Cu,
Zn)2CO3(OH)2(cuprozincite phase), (Cu, Zn)5(CO3)2(OH)6(aurichalcite).Methyl alcohol obtained in traditional coprecipitation
Crystalline phase is the active presoma of CO preparing methanol by hydrogenation, to CO based on cuprozincite phase in synthetic catalyst roasting presoma2Plus
Hydrogen methyl alcohol has certain catalytic performance, but is not optimum activity presoma.Also researcher thinks, due to CO2Hydrogenation
With substantial amounts of water generating in methyl alcohol product, and Al2O3With hydrophily, cause catalyst easily by hydrone
Affect, such as mechanical strength declines, active sites are modified.Therefore, copper-zinc-based catalyst is improved in CO2In preparing methanol by hydrogenation reaction
The research of catalytic performance be concentrated mainly on improvement method for preparing catalyst and in auxiliary agent, the selection of carrier, it is therefore an objective to can
Effective control CO2The formation of preparing methanol by hydrogenation catalyst activity presoma crystalline phase, improves catalyst catalytic performance and hydrothermally stable
Property.
He Jian et al. reports Cu-Zn-Al-Zr composite oxide catalysts for CO2Preparing methanol by hydrogenation reacts.And by its
Compare with industrial Cu-Zn-Al catalyst, while having carried out the test of Cu-Zn-Al-Zr catalyst stabilities and having tested
The materialization of sample in front and back is characterized.As a result show：Under identical reaction conditions, with the methanol yield of Cu-Zn-Al-Zr catalyst
Compared with being significantly improved with Cu-Zn-Al catalyst；In the stability test of 200h, Cu-Zn-Al-Zr catalyst shows preferably
Catalytic stability；The decline of catalyst induction period performance is attributed to the formation grown up with surface deposits of Ni metal crystal grain,
And the micropore distribution in catalyst affects not notable to reaction.Research shows the introducing of Zr so that catalysis activity increases.
At present the catalyst used by synthesizing methanol by hydrogenating carbon dioxide industrially mainly uses Cu/ZnO/Al2O3Catalysis
Agent, but due to Al2O3Hydrophily and Cu/ZnO/Al2O3Catalyst the reunion of catalyst granules and is grown up in reduction process,
Suppress Cu/ZnO/Al2O3Catalytic effect of the catalyst to synthesizing methanol by hydrogenating carbon dioxide.Graphene nanometer sheet is because with uniqueness
Physicochemical properties, such as unique electron transport property, big specific surface area, excellent electric conductivity and thermal conductivity are recognized
To be excellent catalyst carrier and auxiliary agent.Oxygen groups in surface of graphene oxide can play connection Graphene and nanometer
The effect of grain, and make nano particle be dispersed in the surface of Graphene, its good thermal conductivity can suppress catalyst reducing
The reunion of particle and grow up in journey.Yu etc. proposes a kind of metal cation and graphene oxide interaction mechanism in solution,
They think that metal cation has three kinds of interactions with graphene oxide in solution：1) charge interaction：Graphene oxide
On surface carboxyl functional group in the solution deprotonation and it is negatively charged, there is electric charge phase interaction with positively charged metal cation
With；2) coordinate bond：Metal cation is Qi electronic structures, there is unoccupied orbital, and oxygen is former in oxygen-containing functional group in surface of graphene oxide
Son has excess electron, and metal cation has coordinate bond with the oxygen atom of oxygen-containing functional group in surface of graphene oxide；3) sun from
Son-π interacts：The interaction of π keys on Qi electronic metals cation and graphene oxide carbocyclic ring.
Graphene can regard the monoatomic layer graphite material being stripped as, and basic structure is the class that sp2 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.Graphene oxide is the intermediate for being prepared Graphene through chemistry redox method by graphite, and its structure contains comprising substantial amounts of
Oxygen functional group.It has the advantages that cheap, preparation method is simple, stability are high, with the property such as adsorption/desorption mild condition
Matter.Also controllable chemical imperfection, such as surface hydroxyl, carbonyl, epoxy radicals can be formed by functionalisation of surfaces, can be given birth to as metal
Long nuclearing centre, so as to control the growth of metal.CO2The key core of synthesizing methanol by hydrogenating is catalyst.Conventional catalyst
Often preparation process is loaded down with trivial details for agent, repeatable difference, and anti-poisoning performance is poor, mechanical strength is low, and production cost is higher, and catalyst is volatile
It is living.Also it is faced with CO2CO during synthesizing methanol by hydrogenating2Conversion ratio is low, the low bottleneck of methanol selectivity.Therefore, catalyst is improved
Catalysis activity, while it is urgent problem in research to improve reactivity and methanol selectivity.
The content of the invention
The purpose of the present invention is that the defect existed for above-mentioned prior art provides one kind for CO2It is hydrogenated with directly methyl alcohol processed
Catalyst, its preparation method and application.
The present invention is modified with Zr, and graphene oxide GO is introduced and promoted Cu-ZnO co-precipitation type catalyst, develops class Zr
The GO/Cu-ZnO-ZrO of modification2Catalyst, can be played connection Graphene and be received using the oxygen groups in surface of graphene oxide
The effect of rice grain, and make nano particle be dispersed in the surface of Graphene, its good thermal conductivity can suppress catalyst also
The reunion of particle and grow up during original.So that the catalyst for preparing has an easy modulation of the Nomenclature Composition and Structure of Complexes, higher specific surface area,
Active component is disperseed.
Simultaneously the present invention adopts coprecipitation, Zr modifications, obtained Cu-ZnO-ZrO2In ternary system, ZnO lattices are solvable
Solution enters a certain amount of ionic radius and Zn2+(0.074nm) the higher Zn of close but valence state4+Ion (ionic radius is 0.077nm),
The cation for inducing out corresponding valency amount simultaneously is vacant, and the latter is diffusible to move to ZnO crystalline surfaces, and can be by being packed into equivalence
The low-valent metal Cu of amount+Ion contributes to Cu to reach the compensation of valence state and electric charge2The generation of O interface phase.
Oxygen atom has excess electron, metal cation such as Zr in oxygen-containing functional group in surface of graphene oxide2+、Cu2+、Zn2+
Coordinate bond is there is with the oxygen atom of oxygen-containing functional group in surface of graphene oxide, in addition cation interacts with π keys, necessarily
The catalysis activity of the composite catalyst is promoted in degree.
Interaction between metal ion, and the architectural feature that Graphene is special, the composite Cu-ZnO-ZrO of preparation2Catalysis
Agent, also has the advantages that heat endurance is high, alkalescence is relatively strong, can realize being uniformly distributed and interaction modulation for metallic element,
And catalyst preparation materials are cheap and easy to get, using the preparation process is simple of coprecipitation, cycle is short, reproducible.In dioxy
Change in the reaction of carbon synthesizing methanol by hydrogenating and show good activity.Its performance indications is CO2Conversion per pass more than 20%, first
Alcohol selectivity 41%-53%, methanol yield is 8-15%.
The present invention for CO2The catalyst of the direct methyl alcohol processed of hydrogenation, catalyst contain Cu element Zn elements, Zr elements and
Graphene oxide GO, metallic element exists with simple substance or oxide form, raw materials used proportioning (mass ratio), GO：Cu-ZnO-
ZrO2=(0.04-0.16)/1, wherein Cu: ZnO: ZrO2Mass ratio is 4/3/3.
Realize that technical scheme is specific as follows：
One kind is used for CO2The preparation method of directly catalyst for methanol processed is hydrogenated with, is prepared by following steps：
(1) catalyst composition metallic element is dissolved in deionized water in the form of nitrate, and copper source, zinc source are weighed in proportion
With zirconium source, the aqueous solution that concentration is 1～3mol/L is configured to, both are mixed, ultrasonic disperse 30min is designated as B solution；Copper source
It is preferred that copper nitrate, the preferred zinc nitrate in zinc source, the preferred zirconyl nitrate in zirconium source；
(2) carbonate deposition agent is prepared, carbonate can be Na2CO3, deionized water dissolving, it is 1- to be configured to concentration
The aqueous solution of 3mol/L, is designated as C solution；
(3) deionized water with B solution equal volume amounts is measured, solution A is labeled as；
(4) using co-precipitation method, by solution B and solution C, simultaneously constant speed is instilled in solution A, and bath temperature is 70 DEG C,
Drop rate is controlled for 100-200mLh-1, pH is 7-8, and mixing speed is 900r/min；
(5) after completion of dropping, continue to stir 60-120min, in 20-40 DEG C of aging 8-26h.
(6), from filtering, washing, gained filter cake is in 80-120 DEG C of dried overnight, and 300-400 DEG C of roasting 5 is little for product Jing
When, obtained powder sample is designated as D；
(7) sample D is ground, compressing tablet is granulated to 20-40 mesh particles, obtains catalyst sample.
The preparation method of wherein graphene oxide (GO) is：Graphene oxide is prepared using improvement Hummers methods, is existed first
The concentrated sulfuric acid (H is added in dry beaker2SO4, 98%) cool down under condition of ice bath.When the temperature of system is less than 5 DEG C, squama is added
Piece graphite.Stirring 30min, is well mixed, and is slowly added to potassium permanganate (KMnO4), control reacting liquid temperature is less than 5 DEG C, stirs
Mix 1h.Then beaker is placed in 30 DEG C of waters bath with thermostatic control, continues to stir 1h, be subsequently adding 230mL deionized waters, while adding
H2O2(30% aqueous solution, 25mL), solution is changed into vivid yellow, reaction terminating from brick-red.Stand 12h, with dilute HCl (1:
10/ volume ratio) it is washed, in -18 DEG C of freezings, then using freeze drier after -56 DEG C of dryings, aoxidized
Graphene (GO).
The application of catalyst of the present invention is：
The application of catalyst of the present invention, is to be used as CO2The catalyst of direct producing light olefins is hydrogenated with, using fixed bed
Reactor.Reducing condition：H2/CO2=(1-3): 1 or pure H2, 200～400 DEG C of temperature, 0.1～2.0MPa of pressure, air speed
1000～3000h-1, 4～24h of reduction treatment；Reaction condition：H2/CO2=(1-3): 1,200～300 DEG C of temperature, pressure 1.0-
4.0MPa, W/F are 5～20gh/mol.
Below by specific embodiment, the present invention will be further described.
Embodiment 1
By Cu/ZnO/ZrO2=4/3/3 mass ratio weighs 6.1gCu (NO3)2·3H2O、5.5gZn(NO3)2·6H2O、
3.3gZrO(NO3)2·2H2O, deionized water dissolving is solution A, and by the solution of 1mol/L 7.1g anhydrous Nas CO are weighed3, deionization
Water dissolves are solution B.Solution A and solution B are added dropwise simultaneously using peristaltic pump, and drop rate is 150mLh-1, mixing speed is
900r/min, reaction temperature is 70 DEG C of bath temperatures, controls pH=7, after completion of dropping, continues to stir 120min, then 30
DEG C aging 12h, filters, 90 DEG C of dried overnights, 350 DEG C of logical N2Roasting 5h, 20～40 mesh granulation, obtains final product catalyst sample 1, is denoted as
CuO-ZnO-ZrO2.The reducing condition of catalyst is：H2/N2=5/95,300 DEG C of temperature, pressure 0.1MPa, air speed 2400h-1；Instead
Answer condition：H2/CO2=3,250 DEG C of temperature, pressure 3.0MPa, W/F is 10gh/mol.The results are shown in Table 1.
Embodiment 2
Graphene oxide is prepared using improvement Hummers methods, the concentrated sulfuric 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
In being placed in 30 DEG C of waters bath with thermostatic control, continue to stir 1h, be subsequently adding 230mL deionized waters, while adding H2O2(30% aqueous solution,
25mL), solution is changed into vivid yellow, reaction terminating from brick-red.12h is stood, with dilute HCI (1: 10/ volume ratio, 2L) to it
Washed, in -18 DEG C of freezings, then using freeze drier after -56 DEG C of dryings, obtained graphite oxide sample.
200mL deionized water dissolvings are measured for solution A.0.20g GO are weighed, while pressing Cu/ZnO/ZrO2=4/3/3 matter
Amount ratio weighs 6.1gCu (NO3)2·3H2O、5.5gZn(NO3)2·6H2O、3.3gZrO(NO3)2·2H2O, both mix spend from
Sub- water dissolves be solution B, ultrasonic disperse 30min.7.1g anhydrous Nas CO are weighed by the solution of 1mol/L3, deionized water dissolving is
Solution C.Solution B is added dropwise simultaneously with solution C in solution A using peristaltic pump, and drop rate is 150mLh-1, mixing speed is
900r/min, reaction temperature is 70 DEG C of bath temperatures, controls pH=7, after completion of dropping, continues to stir 120min, then 30
DEG C aging 12h, filters, 60 DEG C of dried overnights, 350 DEG C of logical N2Roasting 5h, 20～40 mesh granulation, obtains final product catalyst sample 2, is denoted as
4%GO/CuO-ZnO-ZrO2.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 is 10gh/mol.The results are shown in Table 1.
Embodiment 3
Graphene oxide is prepared using improvement Hummers methods, the concentrated sulfuric 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
In being placed in 30 DEG C of waters bath with thermostatic control, continue to stir 1h, be subsequently adding 230mL deionized waters, while adding 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 it
Washed, in -18 DEG C of freezings, then using freeze drier after -56 DEG C of dryings, obtained graphite oxide sample.
200mL deionized water dissolvings are measured for solution A.0.35g GO are weighed, while pressing Cu/ZnO/ZrO2=4/3/3 matter
Amount ratio weighs 6.1gCu (NO3)2·3H2O、5.5gZn(NO3)2·6H2O、3.3gZrO(NO3)2·2H2O, both mix spend from
Sub- water dissolves be solution B, ultrasonic disperse 30min.7.1g anhydrous Nas CO are weighed by the solution of 1mol/L3, deionized water dissolving is
Solution C.Solution B is added dropwise simultaneously with solution C in solution A using peristaltic pump, and drop rate is 150mLh-1, mixing speed is
900r/min, reaction temperature is 70 DEG C of bath temperatures, controls pH=7, after completion of dropping, continues to stir 120min, then 30
DEG C aging 12h, filters, 60 DEG C of dried overnights, 350 DEG C of logical N2Roasting 5h, 20～40 mesh granulation, obtains final product catalyst sample 3, is denoted as
7%GO/CuO-ZnO-ZrO2.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 is 10gh/mol.The results are shown in Table 1.
Embodiment 4
Graphene oxide is prepared using improvement Hummers methods, the concentrated sulfuric 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
In being placed in 30 DEG C of waters bath with thermostatic control, continue to stir 1h, be subsequently adding 230mL deionized waters, while adding 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 it
Washed, in -18 DEG C of freezings, then using freeze drier after -56 DEG C of dryings, obtained graphite oxide sample.
200mL deionized water dissolvings are measured for solution A.0.50g GO are weighed, while pressing Cu/ZnO/ZrO2=4/3/3 matter
Amount ratio weighs 6.1gCu (NO3)2·3H2O、5.5gZn(NO3)2·6H2O、3.3gZrO(NO3)2·2H2O, both mix spend from
Sub- water dissolves be solution B, ultrasonic disperse 30min.7.1g anhydrous Nas CO are weighed by the solution of 1mol/L3, deionized water dissolving is
Solution C.Solution B is added dropwise simultaneously with solution C in solution A using peristaltic pump, and drop rate is 150mLh-1, mixing speed is
900r/min, reaction temperature is 70 DEG C of bath temperatures, controls pH=7, after completion of dropping, continues to stir 120min, then 30
DEG C aging 12h, filters, 60 DEG C of dried overnights, 350 DEG C of logical N2Roasting 5h, 20～40 mesh granulation, obtains final product catalyst sample 4, is denoted as
10%GO/CuO-ZnO-ZrO2.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 is 10gh/mol.The results are shown in Table 1.
Embodiment 5
Graphene oxide is prepared using improvement Hummers methods, the concentrated sulfuric 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
In being placed in 30 DEG C of waters bath with thermostatic control, continue to stir 1h, be subsequently adding 230mL deionized waters, while adding 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 it
Washed, in -18 DEG C of freezings, then using freeze drier after -56 DEG C of dryings, obtained graphite oxide sample.
200mL deionized water dissolvings are measured for solution A.0.65g GO are weighed, while pressing Cu/ZnO/ZrO2=4/3/3 matter
Amount ratio weighs 6.1gCu (NO3)2·3H2O、5.5gZn(NO3)2·6H2O、3.3gZrO(NO3)2·2H2O, both mix spend from
Sub- water dissolves be solution B, ultrasonic disperse 30min.7.1g anhydrous Nas CO are weighed by the solution of 1mol/L3, deionized water dissolving is
Solution C.Solution B is added dropwise simultaneously with solution C in solution A using peristaltic pump, and drop rate is 150mLh-1, mixing speed is
900r/min, reaction temperature is 70 DEG C of bath temperatures, controls pH=7, after completion of dropping, continues to stir 120min, then 30
DEG C aging 12h, filters, 60 DEG C of dried overnights, 350 DEG C of logical N2Roasting 5h, 20～40 mesh granulation, obtains final product catalyst sample 5, is denoted as
13%GO/CuO-ZnO-ZrO2.The reducing condition of catalyst is：H2/N2=5/95,300 DEG C of temperature, pressure O.1MPa, air speed
2400h-1；Reaction condition：H2/CO2=3,250 DEG C of temperature, pressure 3.0MPa, W/F is 10gh/mol.The results are shown in Table 1.
Embodiment 6
Graphene oxide is prepared using improvement Hummers methods, the concentrated sulfuric 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
In being placed in 30 DEG C of waters bath with thermostatic control, continue to stir 1h, be subsequently adding 230mL deionized waters, while adding 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 it
Washed, in -18 DEG C of freezings, then using freeze drier after -56 DEG C of dryings, obtained graphite oxide sample.
200mL deionized water dissolvings are measured for solution A.0.80g GO are weighed, while pressing Cu/ZnO/ZrO2=4/3/3 matter
Amount ratio weighs 6.1gCu (NO3)2·3H2O、5.5gZn(NO3)2·6H2O、3.3gZrO(NO3)2·2H2O, both mix spend from
Sub- water dissolves be solution B, ultrasonic disperse 30min.7.1g anhydrous Nas CO are weighed by the solution of 1mol/L3, deionized water dissolving is
Solution C.Solution B is added dropwise simultaneously with solution C in solution A using peristaltic pump, and drop rate is 150mLh-1, mixing speed is
900r/min, reaction temperature is 70 DEG C of bath temperatures, controls pH=7, after completion of dropping, continues to stir 120min, then 30
DEG C aging 12h, filters, 60 DEG C of dried overnights, 350 DEG C of logical N2Roasting 5h, 20～40 mesh granulation, obtains final product catalyst sample 6, is denoted as
16%GO/CuO-ZnO-ZrO2.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 is 10gh/mol.The results are shown in Table 1.
The catalyst activity of table 1
Claims (3)
1. a kind of CO2The catalyst of preparing methanol by hydrogenation, it is characterised in that the catalyst contain Cu elements, Zn elements, Zr elements and
Graphene oxide GO, metallic element exists with simple substance or oxide form, and material quality is than GO: Cu-ZnO-ZrO2=0.04～
0.16: 1, wherein Cu/ZnO/ZrO2Mass ratio is 4/3/3.
2. a kind of CO according to claim 12The catalyst of preparing methanol by hydrogenation, it is characterised in that the catalyst is using such as
Prepared by lower section method, comprise the steps：
(1) catalyst composition metallic element is dissolved in deionized water in the form of nitrate, and copper source, zinc source and zirconium are weighed in proportion
Source, is configured to the aqueous solution that concentration is 1～3mol/L, and both are mixed, and ultrasonic disperse 30min is designated as B solution；Copper source is preferred
Copper nitrate, the preferred zinc nitrate in zinc source, the preferred zirconyl nitrate in zirconium source；
(2) carbonate deposition agent, the preferred Na of carbonate are prepared2CO3, deionized water dissolving, be configured to concentration be 1-3mol/L water
Solution, is designated as C solution；
(3) deionized water with B solution equal volume amounts is measured, solution A is labeled as；
(4) using co-precipitation method, by B solution and C solution, simultaneously constant speed is instilled in solution A, and bath temperature is 70 DEG C, control
Drop rate is 100-200mLh-1, pH is 7-8, and mixing speed is 900r/min；
(5) after completion of dropping, continue to stir 60-120min, in 20-40 DEG C of aging 8-26h；
(6) product Jing from filtering, washing, gained filter cake in 80-120 DEG C of dried overnight, 300-400 DEG C of roasting 5 hours, institute
Obtain powder sample and be designated as D；
(7) sample D is ground, compressing tablet is granulated to 20-40 mesh particles, obtains catalyst prod.
3. a kind of CO according to claim 12Preparing methanol by hydrogenation catalyst, it is characterised in that the catalyst is by as follows
Step application：
(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) it is H by the amount ratio of material2/CO2=1～3: 1, CO2+H2Gaseous mixture is passed through reactor, 200～300 DEG C of reaction temperature,
Pressure 12.0-4.0MPa, W/F are 5～20gh/mol.
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