CN105964267B - A kind of Cu-series catalyst for synthesizing methanol and preparation method thereof - Google Patents
A kind of Cu-series catalyst for synthesizing methanol and preparation method thereof Download PDFInfo
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- CN105964267B CN105964267B CN201610395342.7A CN201610395342A CN105964267B CN 105964267 B CN105964267 B CN 105964267B CN 201610395342 A CN201610395342 A CN 201610395342A CN 105964267 B CN105964267 B CN 105964267B
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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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
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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
- C07C29/156—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 iron group metals, platinum group metals 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
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- 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 present invention provides a kind of Cu-series catalyst for synthesizing methanol and preparation method thereof, this method includes mixing copper zinc mixed liquor with the first precipitating reagent aqueous solution cocurrent, and control pH is 7~8, stands aging, forms slurries A；Second precipitating reagent aqueous solution is added into soluble aluminum saline solution, control pH is 7~8, temperature is 40~50 DEG C, stands aging, obtains slurries B；Slurries A is mixed with slurries B, is filtered, solid phase is washed, it is dry, roast, forming processes, obtain Cu-series catalyst for synthesizing methanol.Above-mentioned preparation method step is simple, and controllability is strong, and raw material sources are extensive, is easy to industrialize, and the Cu-series catalyst for synthesizing methanol of high catalytic activity and thermal stability is can get using preparation method of the present invention, is suitable for containing CO, CO2、H2Synthesis gas produce methanol under low temperature, lower pressure, and the catalyst of the present invention using preceding without reduction, convenient for large-scale promotion and application.
Description
Technical field
The present invention relates to catalyst technical fields, and in particular to one kind is with Cu/ZnO/Al2O3Methanol as main component closes
At catalyst and preparation method thereof.
Background technology
Methanol is widely used in organic synthesis, medicine, agriculture as a kind of important basic chemical industry raw material and clean fuel
The numerous areas such as medicine, dyestuff, coating, plastics, synthetic rubber, synthetic fibers, automobile, national defence.Currently, plant-scale methanol life
Production is typically to be reacted under the conditions of existing for certain temperature, pressure and catalyst using synthesis gas as raw material.With society
Meeting rapid development of economy, the demand and production capacity of domestic and international methanol persistently increase, this just promotes high-performance methanol to synthesize
The development of catalyst becomes the research hotspot of methanol production.
There are many type of existing methanol synthesis catalyst, most commonly Cu-Zn-Al series catalysts.In the catalyst
In, copper is active component, and zinc is auxiliary agent, and synergistic effect between the two is the key factor that catalyst has high activity, specifically
For, the effect of ZnO is storage overflow hydrogen, promotes the reaction in Cu active sites, the dispersion degree and Cu-Zn active site densities of Cu are determined
The height of catalyst activity is determined；Aluminium oxide plays the role of providing holder for active material as carrier, when active material is equal
Even ground single layer be attached to the carrier surface of high dispersive i.e. effective rate of utilization maximum when, the activity of catalyst also just reaches highest.On
Activity of the Cu-series catalyst with the synthesis of good catalysis methanol under lower pressure and temperature is stated, and efficiency of carbon con version is high, production
Impurity content in object is low, thus is widely applied.But since the thermal discharge of methanol synthesis reaction is big, it be easy to cause copper system
The sintering of copper, leads to catalyst inactivation in catalyst, substantially reduces the service life of catalyst.
To solve deficiencies of the prior art, Chinese patent literature CN1176747C discloses a kind of copper system methanol
The preparation method of synthetic catalyst, this method, which reacts soluble aluminum salting liquid with ammonium hydroxide, is made alumina gel, then this is coagulated
Glue is mixed with copper, zinc reactive precursor, filters and collect filter cake, and filter cake is washed, dry, roasting, finished product catalyst.It is above-mentioned
Technology is by alumina support of the preparation with high specific surface area, although can improve methanol yield to a certain extent and urge
The thermal stability of agent, but according to the Evaluation of Thermal Stability result of catalyst from the point of view of, maximum value is only 0.90, is still remained
Larger room for improvement.Therefore, the thermal stability for how effectively improving Cu-series catalyst for synthesizing methanol extends its service life,
Have become a great problem of puzzlement those skilled in the art.
Invention content
The technical problem to be solved in the present invention is to overcome the thermostabilization present in existing Cu-series catalyst for synthesizing methanol
Property poor, defect that service life is short, and then provide a kind of heat-resist, long lifespan and the high copper system methanol-fueled CLC of catalytic activity is urged
The preparation method of agent.
For this purpose, the present invention realizes that the technical solution of above-mentioned purpose is：
A kind of preparation method of Cu-series catalyst for synthesizing methanol, includes the following steps：
By soluble copper salt, soluble zinc salt formation copper-zinc mixed liquor soluble in water, by the copper-zinc mixed liquor and
One precipitating reagent aqueous solution cocurrent mixes, and reacts under constant stirring, and the pH value for controlling reaction system is 7~8, stands old
Change, obtains slurries A；
Second precipitating reagent aqueous solution is added into soluble aluminum saline solution, is reacted under stirring, and controls reaction
Temperature is 40~50 DEG C, the pH value of reaction system is 7~8, stands aging, obtains slurries B；
The slurries A is mixed with the slurries B, filters and collect solid phase, the solid phase is washed, dry, roasting and
Forming processes obtain Cu-series catalyst for synthesizing methanol；
Wherein, first precipitating reagent is sodium oxalate and/or potassium oxalate, and second precipitating reagent is ammonium carbonate and/or carbon
Sour hydrogen ammonium.
The molar ratio of the soluble copper salt and the soluble zinc salt is (1.5~2):1；
The molar concentration of copper ion is 0.26~0.3mol/L in the copper-zinc mixed liquor.
The amount of the substance of first precipitating reagent be the substance of the soluble copper salt and the soluble zinc salt amount it
1.02~1.04 times of sum；
The molar concentration of the first precipitating reagent aqueous solution is 0.46~0.5mol/L.
The soluble copper salt is copper nitrate；The soluble zinc salt is zinc nitrate；The aluminum soluble salt be aluminium chloride,
It is one or more in aluminum nitrate, aluminum sulfate.
The molar ratio of second precipitating reagent and the aluminum soluble salt is (3.02~3.04):1；
The molar ratio of the aluminum soluble salt and the soluble copper salt is 1:(1.5~2).
The molar concentration of the soluble aluminum saline solution is 0.3~0.35mol/L；
The molar concentration of the second precipitating reagent aqueous solution is 0.9~1.2mol/L.
The time of the aging is 0.5~1h.
The step of being washed to the solid phase be：By the solid phase dispersion in deionized water, heats and control temperature
Be 70~80 DEG C, stir it is lower carry out pulp processing, filtered after pulp, repeat above-mentioned washing step until sodium ion contains in solid phase
Amount is not more than 0.03wt%.
The temperature of the drying is 100~120 DEG C, the time is not less than 10h；
The roasting is carried out according to following calcination procedure in air atmosphere：200℃×1h、300℃×2h、450
℃×2h、550℃×4h；
In the forming process, graphite, compression molding are added into product of roasting.
One kind Cu-series catalyst for synthesizing methanol made from above-mentioned preparation method, in terms of the gross mass of catalyst, each component
Mass percentage be：
Cu >=40%, ZnO >=30%, Al2O3>=20%, Na2O<0.05%.
The above-mentioned technical proposal of the present invention has the following advantages that：
1, the preparation method of Cu-series catalyst for synthesizing methanol of the present invention, by by copper-zinc mixed liquor and sodium oxalate
And/or the aqueous solution of potassium oxalate mixes in manner of cocurrent flow, and react under constant stirring, control pH value of reaction system is
7~8, aging is stood, the slurries A containing cupric oxalate and zinc oxalate is formed；The hybrid mode of above-mentioned cocurrent can be such that reaction solution is maintained at
Under one relatively steady state, the contact probability of copper ion, zinc ion and oxalate denominationby is impartial, is conducive to be formed simultaneously phase
The oxalate precipitation answered, it is normal so as to avoid the solubility product precipitated by two kinds when precipitating reagent (along adding) is added in copper-zinc mixed liquor
PH value is total when counting priority deposited phenomenon different and occurring, while also avoiding precipitating reagent copper-zinc mixed liquor (inverse to add) is added
Fluctuation of service is caused in variation；The abundant turbulence of certifiable slurries is stirred continuously in above-mentioned precipitation process simultaneously, is increased
Mass transfer rate makes each component uniformly mix, and avoids local over-concentration and causes the lattice defect precipitated and dislocation and contain impurity,
To advantageously form complete cupric oxalate, zinc oxalate crystal；Also, the pH value by controlling reaction system is 7~8, can be kept away
Exempt from the metal ions such as oxalate, copper, the zinc in the acid or hydrogen ion under alkaline condition, hydroxide ion and above-mentioned reaction system
In conjunction with weak electrolyte is formed, to be had an impact to precipitation；And the step of standing aging, can then be such that fine crystals constantly dissolve, then
It is deposited on coarse crystal, impurity constantly enters solution in the process, and crystal gradually grows up and tends towards stability, to form grass
Sour copper and zinc oxalate are uniformly dispersed each other and crystalline phase form is good, the mixed precipitation of free from admixture package.Some researches show that using alkali
Property sodium salt can lead to the sodium ion in slurries there are great amount of soluble as precipitating reagent, and the content of sodium ion is more, and methanol closes
It is poorer at the thermal stability of catalyst, when sodium oxide content in catalyst>The initial activity of catalyst is also affected when 0.5%；
And the present invention is not by wrapping up sodium ion substantially in copper zinc mixed precipitation made from the above method, so that the catalysis of the present invention
Agent has very high initial activity and thermal stability, it is ensured that the service life of catalyst is long.
Preparation method of the present invention initiatively using sodium oxalate and/or potassium oxalate as copper, the precipitating reagent of zinc, by
This obtained cupric oxalate and zinc oxalate can be separately converted to elemental copper and zinc oxide in subsequent roasting process, so on the one hand
Eliminate existing Cu-series catalyst for synthesizing methanol needed before use through reduction treatment with by copper oxide be reduced into catalytic activity at
Point-elemental copper, cause copper to be sintered because of heat release in reduction process to can avoid catalyst, is conducive to improve catalyst
Thermal stability；On the other hand, between small copper particle copper is improved since the presence of zinc oxide can effectively avoid the reunion of copper
Dispersion degree and utilization rate, while can also enhance the synergistic effect between copper, zinc, increase Cu-Zn active site densities, is urged so as to be promoted
The activity of agent catalysis methanol synthesis.
Preparation method of the present invention can be made by mixing the slurries A of copper zinc mixed precipitation with the slurries B of aluminum precipitation
Three kinds of cupric oxalate, zinc oxalate, aluminium hydroxide precipitations are evenly dispersed, then active constituent elemental copper, zinc oxide will after baking
Be homogeneously dispersed on alumina support, to effectively inhibit copper reunion, and make catalyst surface Cu/Zn ratios close to
Whole Cu/Zn ratios, thus can improve the thermal stability and catalytic activity of catalyst.The present invention, which limits, uses ammonium carbonate and/or carbon
On the one hand precipitating reagent of the sour hydrogen ammonium as aluminium can avoid using ammonium hydroxide commonly used in the prior art, thus overcome ammonium hydroxide because of alkali
Property relatively strong and volatility it is big and caused by line equipment etching problem；On the other hand it can avoid introducing impurity into catalyst,
This is because the ammonium salt generated while aluminum hydroxide precipitation formation is decomposed into gas effusion in subsequent roasting process,
Thus it can make the preparation method of the present invention that there is good operability and controllability, be convenient for large-scale promotion application.
2, the preparation method of Cu-series catalyst for synthesizing methanol of the present invention, by limit copper-zinc mixed liquor in copper from
Molar concentration, molar concentration, the solubility of the molar ratio of soluble copper salt and soluble zinc salt, the first precipitating reagent aqueous solution of son
The molar concentration of the molar concentration of aluminum saline solution, the second precipitating reagent aqueous solution, the concentration for thus controlling each solution were unlikely to
Greatly, it to achieve the purpose that slow crystallization, not only contributes to obtain short grained sediment, makes carrier that there is ratio table as big as possible
Area improves the dispersion degree and utilization rate of active component；It can also prevent from wrapping up impurity in crystal, further ensure catalyst
High activity and thermal stability.
3, the preparation method of Cu-series catalyst for synthesizing methanol of the present invention, by using deionized water at 70~80 DEG C
Under to solid phase carry out pulp processing, until solid phase in sodium ion content be not more than 0.03wt%, thus can remove can in solid phase
The sodium ion that can be wrapped up, to ensure that catalyst has as high as possible catalytic activity and thermal stability.
Preparation method of the present invention is using 200 DEG C × 1h, 300 DEG C × 2h, 450 DEG C × 2h, the program of 550 DEG C × 4h
Roasting precipitation, to ensure that cupric oxalate, zinc oxalate and aluminum hydroxide precipitation can fully be pyrolyzed as copper, zinc oxide and aluminium oxide；To
Graphite is added in product of roasting to serve as molding adhesive, catalytic inner can be made to form certain hole by this forming process
Gap structure further increases its catalytic activity to be conducive to increase the specific surface area of catalyst.
4, in Cu-series catalyst for synthesizing methanol of the present invention, Cu >=40%, ZnO >=30%, Al2O3>=20%, Na2O
<0.05%, copper-zinc synergistic effect and low sodium content make the initial activity of catalyst of the present invention be not less than 1.68gmL-1·h-1,
The value of thermal stability is up to 0.97, this shows using Cu-series catalyst for synthesizing methanol tool made from preparation method of the present invention
There are the activity and thermal stability of quite high catalysis methanol synthesis.
Specific implementation mode
Cu-series catalyst for synthesizing methanol provided by the present invention and preparation method thereof is carried out with reference to specific embodiment
It is described in detail.
Embodiment 1
The preparation method of Cu-series catalyst for synthesizing methanol described in the present embodiment includes the following steps：
Prepare the aqueous solution 2L containing 126g sodium oxalates；By 136g Cu (NO3)2·3H2O and 110gZn (NO3)2·6H2O
It is dissolved in formation copper-zinc mixed liquor in 2L water；Above-mentioned two solution cocurrent is added in reaction kettle under constant stirring, control reaction
The pH value of system is 7~8, stands aging 1h after the completion of charging, obtains slurries A；
Prepare the NH containing 88g4HCO3Aqueous solution 1L is for use；By 139g Al (NO3)3·9H2O is dissolved in 1L water；By carbonic acid
Hydrogen aqueous ammonium is added slowly in aluminum nitrate aqueous solution, is reacted under stirring, and the pH value for controlling reaction system is 7~8,
Temperature 50 C persistently stirs 30min, stands aging 1h after the completion of charging, obtain slurries B；
Slurries A and slurries B are sufficiently mixed, filtered after stirring 20min, solid phase is collected, by solid phase dispersion in 2L deionizations
In water, be heated to 70 DEG C, stir it is lower carry out pulp processing, filtered after 1h, repeat pulp 4 times until in solid phase sodium ion content
No more than 0.03wt%；
Material dry 10h at 110 DEG C, then roasts according to following procedure in air atmosphere after filtering：200℃×
1h, 300 DEG C × 2h, 450 DEG C × 2h, 550 DEG C × 4h, into product of roasting addition account for the graphite of product of roasting quality 3%, tabletting
Molding, obtains Cu-series catalyst for synthesizing methanol, is denoted as catalyst 1#.
In terms of the gross mass of catalyst 1#, the mass percentage of each component is：Cu 42.3%, ZnO35.4%, Al2O3
22.27%, Na2O 0.03%.
Embodiment 2
The preparation method of Cu-series catalyst for synthesizing methanol described in the present embodiment includes the following steps：
Prepare the aqueous solution 2L containing 127g sodium oxalates；By 140g Cu (NO3)2·3H2O and 101g Zn (NO3)2·6H2O
It is dissolved in formation copper-zinc mixed liquor in 2L water；Above-mentioned two solution cocurrent is added in reaction kettle under constant stirring, control reaction
The pH value of system is 7~8, stands aging 0.5h after the completion of charging, obtains slurries A；
Prepare the NH containing 81g4HCO3Aqueous solution 1L is for use；By 128g Al (NO3)3·9H2O is dissolved in 1L water；By carbonic acid
Hydrogen aqueous ammonium is added slowly in aluminum nitrate aqueous solution, is reacted under stirring, and the pH value for controlling reaction system is 7~8,
Temperature 50 C persistently stirs 30min, stands aging 1h after the completion of charging, obtain slurries B；
Slurries A and slurries B are sufficiently mixed, filtered after stirring 30min, solid phase is collected, by solid phase dispersion in 2L deionizations
In water, be heated to 75 DEG C, stir it is lower carry out pulp processing, filtered after 1h, repeat pulp 4 times until in solid phase sodium ion content
No more than 0.03wt%；
Material dry 15h at 100 DEG C, then roasts according to following procedure in air atmosphere after filtering：200℃×
1h, 300 DEG C × 2h, 450 DEG C × 2h, 550 DEG C × 4h, into product of roasting addition account for the graphite of product of roasting quality 3%, tabletting
Molding, obtains Cu-series catalyst for synthesizing methanol, is denoted as catalyst 2#.
In terms of the gross mass of catalyst 2#, the mass percentage of each component is：Cu 45.3%, ZnO34.66%,
Al2O320%, Na2O 0.04%.
Embodiment 3
The preparation method of Cu-series catalyst for synthesizing methanol described in the present embodiment includes the following steps：
Prepare the aqueous solution 2L containing 126g sodium oxalates；By 144g Cu (NO3)2·3H2O and 89gZn (NO3)2·6H2O is molten
Copper-zinc mixed liquor is formed in 2L water；Above-mentioned two solution cocurrent is added in reaction kettle under constant stirring, controls reactant
The pH value of system is 7~8, stands aging 1h after the completion of charging, obtains slurries A；
Prepare the NH containing 72g4HCO3Aqueous solution 1L is for use；By 113g Al (NO3)3·9H2O is dissolved in 1L water；By carbonic acid
Hydrogen aqueous ammonium is added slowly in aluminum nitrate aqueous solution, is reacted under stirring, and the pH value for controlling reaction system is 7~8,
Temperature 50 C continues to stir 30min, stands aging 0.5h after the completion of charging, obtain slurries B；
Slurries A and slurries B are sufficiently mixed, filtered after stirring 30min, solid phase is collected, by solid phase dispersion in 2L deionizations
In water, be heated to 80 DEG C, stir it is lower carry out pulp processing, filtered after 1h, repeat pulp 3 times until in solid phase sodium ion content
No more than 0.03wt%；
Material dry 12h at 120 DEG C, then roasts according to following procedure in air atmosphere after filtering：200℃×
1h, 300 DEG C × 2h, 450 DEG C × 2h, 550 DEG C × 4h, into product of roasting addition account for the graphite of product of roasting quality 3%, tabletting
Molding, obtains Cu-series catalyst for synthesizing methanol, is denoted as catalyst 3#.
In terms of the gross mass of catalyst 3#, the mass percentage of each component is：Cu 41.26%, ZnO31.2%, Al2O3
27.5%, Na2O 0.04%.
Embodiment 4
The preparation method of Cu-series catalyst for synthesizing methanol described in the present embodiment includes the following steps：
Prepare the aqueous solution 2L containing 126g sodium oxalates；By 144g Cu (NO3)2·3H2O and 118g Zn (NO3)2·6H2O
It is dissolved in formation copper-zinc mixed liquor in 2L water；Above-mentioned two solution cocurrent is added in reaction kettle under constant stirring, control reaction
The pH value of system is 7~7.5, stands aging 1h after the completion of charging, obtains slurries A；
Prepare the NH containing 96g4HCO3Aqueous solution 1L is for use；By 150g Al (NO3)3·9H2O is dissolved in 1L water；By carbonic acid
Hydrogen aqueous ammonium is added slowly in aluminum nitrate aqueous solution, is reacted under stirring, and control reaction system pH value be 7.5~
8,40 DEG C of temperature continue to stir 30min, stand aging 0.5h after the completion of charging, obtain slurries B；
Slurries A and slurries B are sufficiently mixed, filtered after stirring 30min, solid phase is collected, by solid phase dispersion in 2L deionizations
In water, be heated to 80 DEG C, stir it is lower carry out pulp processing, filtered after 1h, repeat pulp 3 times until in solid phase sodium ion content
No more than 0.03wt%；
Material dry 12h at 120 DEG C, then roasts according to following procedure in air atmosphere after filtering：200℃×
1h, 300 DEG C × 2h, 450 DEG C × 2h, 550 DEG C × 4h, into product of roasting addition account for the graphite of product of roasting quality 3%, tabletting
Molding, obtains Cu-series catalyst for synthesizing methanol, is denoted as catalyst 4#.
In terms of the gross mass of catalyst 4#, the mass percentage of each component is：Cu 40%, ZnO31.26%, Al2O3
28.7%, Na2O 0.04%.
Embodiment 5
The preparation method of Cu-series catalyst for synthesizing methanol described in the present embodiment includes the following steps：
Prepare the aqueous solution 2L containing 126g sodium oxalates；By 136g Cu (NO3)2·3H2O and 83g Zn (NO3)2·6H2O
It is dissolved in formation copper-zinc mixed liquor in 2L water；Above-mentioned two solution cocurrent is added in reaction kettle under constant stirring, control reaction
The pH value of system is 7.5~8, stands aging 1h after the completion of charging, obtains slurries A；
Prepare (the NH containing 93g4)2CO3Aqueous solution 1L is for use；By 120g Al (NO3)3·9H2O is dissolved in 1L water；By carbon
Sour hydrogen aqueous ammonium is added slowly in aluminum nitrate aqueous solution, is reacted under stirring, and control reaction system pH value be 7~
7.5, temperature 45 C continues to stir 30min, stands aging 0.5h after the completion of charging, obtain slurries B；
Slurries A and slurries B are sufficiently mixed, filtered after stirring 30min, solid phase is collected, by solid phase dispersion in 2L deionizations
In water, be heated to 80 DEG C, stir it is lower carry out pulp processing, filtered after 1h, repeat pulp 3 times until in solid phase sodium ion content
No more than 0.03wt%；
Material dry 12h at 120 DEG C, then roasts according to following procedure in air atmosphere after filtering：200℃×
1h, 300 DEG C × 2h, 450 DEG C × 2h, 550 DEG C × 4h, into product of roasting addition account for the graphite of product of roasting quality 3%, tabletting
Molding, obtains Cu-series catalyst for synthesizing methanol, is denoted as catalyst 5#.
In terms of the gross mass of catalyst 5#, the mass percentage of each component is：Cu 41.46%, ZnO30%, Al2O3
28.5%, Na2O 0.04%.
Comparative example 1
The preparation method of Cu-series catalyst for synthesizing methanol 6# is with embodiment 3 in this comparative example, only difference is that, it adopts
102g sodium carbonate is used to replace sodium oxalate as the first precipitating reagent.
Comparative example 2
The preparation method of Cu-series catalyst for synthesizing methanol 7# is with embodiment 3 in this comparative example, only difference is that, slurry
The forming process of liquid A is as follows：
Under constant stirring, copper-zinc mixed liquor is slowly added into sodium oxalate water solution, controls the pH value of reaction system
It is 7~8, aging 1h is stood after the completion of charging, obtains slurries A.
Comparative example 3
The preparation method of Cu-series catalyst for synthesizing methanol 8# is with embodiment 3 in this comparative example, only difference is that, slurry
The forming process of liquid A is as follows：
Under constant stirring, sodium oxalate water solution is slowly added into copper-zinc mixed liquor, controls the pH value of reaction system
It is 7~8, aging 1h is stood after the completion of charging, obtains slurries A.
Experimental example
The catalytic activity and thermal stability of above-mentioned Cu-series catalyst for synthesizing methanol 1#~8# are tested, specific method is such as
Under：
Evaluating apparatus：Continuous flow reactor of fixed bed, dress dosage 2mL.
Methanol-fueled CLC condition：System pressure 5MPa, 230 DEG C of reaction temperature, air speed 10000h-1。
Synthesis gas：CO 13~15v%, CO24~6v%, H255~65v%, N2Balance.
Initial activity evaluation method：
Catalyst packing finishes, and examines air-tightness.230 DEG C are warming up to, synthesis gas is passed through, by reactor pressure gradually by normal
Pressure is promoted to reaction pressure 5MPa, then adjusts flow and air speed is promoted to 10000h-1, start timing after above, first
Stablize 2h, release the waste liquid in condenser, hereafter collects sample every 3h graduated cylinders, calculate space-time yield E, twice in succession result
When identical, which is initial activity, and the results are shown in Table 1.
In addition, also needing reduction treatment before carrying out above-mentioned activity rating for catalyst 6#~8#：Open reduction
Gas (H25%, N2Balance), according to air speed 1000h-1It adjusts flow and then heats to 230 DEG C, restore 3h in 230 DEG C of constant temperature, also
After original, keeps 230 DEG C of temperature constant, switch to synthesis gas.
Evaluation of Thermal Stability method：
System pressure is down to normal pressure, temperature is gradually increased to 350 DEG C, maintains 10h under synthesis gas atmosphere, temperature is dropped back to
To 230 DEG C, system pressure is adjusted to 5MPa, air speed 10000h-1, heat-resisting rear activity rating is carried out, evaluation procedure is evaluated with initial activity,
The thermal stability for characterizing sample with the ratio of initial activity with heat-resisting rear activity, the results are shown in Table 1.
The activity of catalyst is weighed with space-time yield E, i.e., the methanol quality of output in the per volume of catalyst unit interval
(being calculated with water content 10% in the methanol solution of releasing)：
E=(V × 0.9 × 0.8)/(2 × 3) g/ (mLh)
In above formula：V, the methanol solution volume being collected into, mL；0.9, methanol content when water content is 10% in methanol solution
It is 90%；0.8, methanol density, g/mL；2, loaded catalyst, mL；3, take a methanol solution sample, h per 3h.
The catalytic activity and thermal stability of 1 Cu-series catalyst for synthesizing methanol 1#~8# of table
As it can be seen from table 1 compared with catalyst 6#~8#, catalyst 1#~5# has higher initial activity, through high temperature
Activity reduces little after processing, and heat resistance is good, and thus explanation is conducive to obtain high using preparation method of the present invention
The Cu-series catalyst for synthesizing methanol of catalytic activity and thermal stability, and reproducible, the performance stabilization of five groups of laboratory samples.This
The invention Cu-series catalyst for synthesizing methanol can be suitably used for containing CO, CO2、H2Synthesis gas produce first under low temperature, lower pressure
The preparation process of alcohol, catalyst is simple, and controllability is strong, and raw material sources are extensive, is easy to industrialize, and catalyst produced by the present invention
It is being not necessarily to reduction, its large-scale promotion of being more convenient for and application using preceding.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of preparation method of Cu-series catalyst for synthesizing methanol, which is characterized in that include the following steps：
By soluble copper salt, soluble zinc salt formation copper-zinc mixed liquor soluble in water, the copper-zinc mixed liquor is sunk with first
Agent aqueous solution cocurrent in shallow lake mixes, and reacts under constant stirring, and the pH value for controlling reaction system is 7 ~ 8, stands aging, obtains
Slurries A；
Second precipitating reagent aqueous solution is added into soluble aluminum saline solution, is reacted under stirring, and controlling reaction temperature
PH value for 40 ~ 50 DEG C, reaction system is 7 ~ 8, stands aging, obtains slurries B；
The slurries A is mixed with the slurries B, filters and collect solid phase, the solid phase is washed, dry, roasting and molding
Processing, obtains Cu-series catalyst for synthesizing methanol；
Wherein, first precipitating reagent is sodium oxalate and/or potassium oxalate, and second precipitating reagent is ammonium carbonate and/or bicarbonate
Ammonium；
The molar ratio of the soluble copper salt and the soluble zinc salt is (1.5 ~ 2):1；
The roasting is carried out according to following calcination procedure in air atmosphere：200℃×1h、300℃×2h、450℃×
2h、550℃×4h。
2. the preparation method of Cu-series catalyst for synthesizing methanol according to claim 1, which is characterized in that in the copper-zinc
The molar concentration of copper ion is 0.26 ~ 0.3mol/L in mixed liquor.
3. the preparation method of Cu-series catalyst for synthesizing methanol according to claim 1 or 2, which is characterized in that described first
The amount of the substance of precipitating reagent is 1.02 ~ 1.04 times of the sum of the soluble copper salt and the amount of substance of the soluble zinc salt；
The molar concentration of the first precipitating reagent aqueous solution is 0.46 ~ 0.5mol/L.
4. the preparation method of Cu-series catalyst for synthesizing methanol according to claim 1, which is characterized in that the soluble copper
Salt is copper nitrate；The soluble zinc salt is zinc nitrate；The aluminum soluble salt is one in aluminium chloride, aluminum nitrate, aluminum sulfate
Kind is a variety of.
5. the preparation method of Cu-series catalyst for synthesizing methanol according to claim 1, which is characterized in that second precipitation
The molar ratio of agent and the aluminum soluble salt is (3.02 ~ 3.04):1；
The molar ratio of the aluminum soluble salt and the soluble copper salt is 1:(1.5~2).
6. the preparation method of Cu-series catalyst for synthesizing methanol according to claim 1, which is characterized in that the soluble aluminum
The molar concentration of saline solution is 0.3 ~ 0.35mol/L；
The molar concentration of the second precipitating reagent aqueous solution is 0.9 ~ 1.2mol/L.
7. the preparation method of Cu-series catalyst for synthesizing methanol according to claim 1, which is characterized in that the aging when
Between be 0.5 ~ 1h.
8. the preparation method of Cu-series catalyst for synthesizing methanol according to claim 1, which is characterized in that the solid phase into
Row washing the step of be：By the solid phase dispersion in deionized water, heats and controlled at 70 ~ 80 DEG C, stir lower carry out
Pulp processing, is filtered after pulp, repeats above-mentioned washing step until the content of sodium ion is not more than 0.03wt% in solid phase.
9. the preparation method of Cu-series catalyst for synthesizing methanol according to claim 1, which is characterized in that the temperature of the drying
Degree is 100 ~ 120 DEG C, the time is not less than 10h；
In the forming process, graphite, compression molding are added into product of roasting.
10. a kind of Cu-series catalyst for synthesizing methanol, feature made from claim 1-9 any one of them preparation methods exist
In in terms of the gross mass of catalyst, the mass percentage of each component is：
Cu >=40%, ZnO >=30%, Al2O3>=20%, Na2O ＜ 0.05%.
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| CN101306369A (en) * | 2008-07-11 | 2008-11-19 | 西南化工研究设计院 | Catalyst for synthesizing methanol and preparing process thereof |
| CN101733109A (en) * | 2008-11-06 | 2010-06-16 | 南化集团研究院 | Preparation method of copper-based catalyst |
| CN102451695A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工集团公司 | Preparation method of copper base catalyst for methanol synthesis |
| CN104383928A (en) * | 2014-11-18 | 2015-03-04 | 大连瑞克科技有限公司 | Preparing method of high-performance catalyst for hydrogenation of carbon dioxide for synthesizing methyl alcohol |
| CN104888788A (en) * | 2015-05-07 | 2015-09-09 | 山西大同大学 | Copper-based catalyst for catalyzing methanol synthesis through hydrogenation reaction of carbon dioxide, method fore preparing catalyst and application of catalyst |
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| CN101306369A (en) * | 2008-07-11 | 2008-11-19 | 西南化工研究设计院 | Catalyst for synthesizing methanol and preparing process thereof |
| CN101733109A (en) * | 2008-11-06 | 2010-06-16 | 南化集团研究院 | Preparation method of copper-based catalyst |
| CN102451695A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工集团公司 | Preparation method of copper base catalyst for methanol synthesis |
| CN104383928A (en) * | 2014-11-18 | 2015-03-04 | 大连瑞克科技有限公司 | Preparing method of high-performance catalyst for hydrogenation of carbon dioxide for synthesizing methyl alcohol |
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