CN103372438A - Preparation method of copper-containing catalyst - Google Patents
Preparation method of copper-containing catalyst Download PDFInfo
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- CN103372438A CN103372438A CN2012104426273A CN201210442627A CN103372438A CN 103372438 A CN103372438 A CN 103372438A CN 2012104426273 A CN2012104426273 A CN 2012104426273A CN 201210442627 A CN201210442627 A CN 201210442627A CN 103372438 A CN103372438 A CN 103372438A
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Abstract
The invention discloses a preparation method of a copper-containing catalyst. The method comprises the steps of adding a sodium metaaluminate solution to a zinc metal salt solution so that the pH value of a system is 9.0-11.0, then introducing CO2 gas into a reaction system to reduce the pH value by 0.3-2.8, repeating the steps to carry out gelling reaction, and adding basic copper carbonate during aging after gelling to prepare the copper-containing catalyst. The method has the beneficial effects of improving the physical and chemical properties of the catalyst, increasing the specific surface area of the catalyst, improving the synergism between the main active metal component copper and the cocatalyst metal component zinc, improving the dispersibility of an active phase, and improving the activity and stability of the catalyst. The catalyst is especially suitable to serve as a methanol synthesis catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of Cu-contained catalyst, be specifically related to a kind of preparation method of the Cu-contained catalyst for the synthesis of catalyst for methanol.
Background technology
Methyl alcohol is a kind of extremely important industrial chemicals, be widely used in organic synthesis, dyestuff, fuel, medicine, coating and national defense industry, its output is only second to synthetic ammonia and ethene, occupies the third place in the world, in recent years methyl alcohol demand and the production capacity sustainable growth along with industrial development.
Industrial methyl alcohol is general with containing H
2, CO, CO
2Synthesis gas under certain pressure, temperature and catalyst existence condition, produce.In generally adopting in the world at present, low-pressure vapor phase method synthesizing methanol, catalyst system therefor is essentially the mixed oxide of copper, zinc, aluminium.CuO, ZnO, Al in the catalst for synthesis of methanol
2O
3The effect of three components is variant, and CuO is main active component, ZnO and Al
2O
3Be auxiliary agent.Method for preparing catalyst is generally the mixing subcarbonate of using first coprecipitation (comprise and flow, instead add, just adding coprecipitation) to generate copper zinc, and then add aluminium hydroxide in the pulping process, the slurry that generates through washing, drying, roasting, compression molding.The research of at present catalyst preparation mainly concentrates on optimization and the improvement of preparation method and technique, improve catalyst activity by the ratio that changes catalytic component, the size of crystal grain, size and the pore-size distribution of specific area, improve the copper-based catalysts poor heat stability, selective hanging down and short problem of life-span.Method for preparing catalyst is different, and it is larger that the performance of gained catalyst can differ.
CN 1810357A adopts a traditional step coprecipitation to prepare a kind of catalst for synthesis of methanol.Nitrate mixed solution and NaCO with Cu, Zn, Al, Li
3Solution and stream are titrated in the deionized water of a small amount of high-speed stirred, keep simultaneously the pH of solution between 7 ~ 8, and is aging, suction filtration, washing, dries to get catalyst precarsor, and catalyst precarsor oven dry, roasting get finished product.The method is to adopt a typical step coprecipitation to prepare catalyst for methanol, has added LiNO in preparation process
3
CN 1329938A discloses a kind of preparation method of catalst for synthesis of methanol, and this catalyst is comprised of the oxide of copper, zinc, aluminium.Preparation process: a part is to make the coprecipitate that contains copper, zinc, aluminium compound with coprecipitation, and another part is to make the coprecipitate that contains copper, zinc compound with co-precipitation.The equal thermal decomposition of above-mentioned coprecipitate is the oxide of metal, and then with these two kinds of co-precipitation mixing, washing, dry, roasting, moulding makes catalyst.
CN 1660490A discloses a kind of preparation method of catalst for synthesis of methanol, its preparation process is: coprecipitation prepares adds a small amount of Surfactant OP in the methanol synthesis catalyst process, perhaps fractional precipitation prepares a small amount of Surfactant OP of interpolation in the methanol synthesis catalyst process, makes a kind of catalst for synthesis of methanol.
CN 101574649A discloses a kind of preparation method of catalst for synthesis of methanol, step is the mixed aqueous solution reaction with the aqueous solution of aluminum soluble salt and alkali metal hydroxide-carbonate, generate a kind of transparent meta-aluminate aqueous solution, then with its with contain the copper of water-soluble high-molecular compound, the transparent aqueous solution of zinc salt carries out coprecipitation reaction, generate the mixing co-precipitation of a kind of copper, zinc, aluminium, then through washing, drying, granulation processing, roasting, play the sheet moulding and can make a kind of highly active catalst for synthesis of methanol.
The catalst for synthesis of methanol method of above-mentioned patent Introduction is by adding new auxiliary agent (Li and surfactant), change catalyst preparation process the presoma of (step process changes two step or three step process into) and change Al, come structure, surface acid alkalescence, the electronic property of regulating catalyst, with the activity of improving existing catalyst, selective or life-span.Be to increase the more even of the specific area of catalyst and active ingredient copper and the distribution of co-catalyst zinc but improve catalst for synthesis of methanol the key active and life-span, above patent does not all relate to.
Summary of the invention
For above-mentioned deficiency of the prior art, the invention provides that a kind of technique is simple, the preparation method of easy-operating synthetic Cu-contained catalyst.The catalyst of the method gained is particularly suitable as catalst for synthesis of methanol, and the specific area of this catalyst is higher, and it is more even that active ingredient copper and co-catalyst zinc distribute, and improved the activity of Cu-contained catalyst and the service life of heat endurance and catalyst.
Different aluminium sources is different with the composite oxide of metal grain size that precipitating reagent obtains, and then the specific area of catalyst is had considerable influence, and the adding mode of active component also has a significant impact coordinative role between active component dispersiveness, the active metal component.The inventor finds by a large amount of experiments, in the zinc metal salt solution, adds first sodium metaaluminate, and then pass into CO
2Gas, so repeated multiple timesly become the glue reaction, and the adding basic copper carbonate prepares Cu-contained catalyst when aging, can improve the physico-chemical property of catalyst, increase the specific area of catalyst, increase coordinative role between main metal component copper and the promoter metal component zinc, improve the dispersiveness of active metal component copper, allow reactive metal plays one's part to the full in the catalyst, improve the active and stable of catalyst.
The preparation method of Cu-contained catalyst of the present invention may further comprise the steps:
(1), the soluble-salt with Zn mixes wiring solution-forming A soluble in water, preparation sodium aluminate solution B;
(2), the part solution B is added in the solution A, system pH is 9.0～11.0, then passes into CO
2Gas makes the pH value reduce by 0.3 ~ 2.8 to reaction system;
(3), repeating step (2) process 1～6 time, the pH value of reaction system is 8.0～10.0 during cemented into bundles;
(4), the reacting slurry with step (3) gained wears out adding basic copper carbonate when aging;
(5), the material that obtains of step (4) through washing, filter, dry, roasting, compression molding obtains Cu-contained catalyst.
The soluble-salt of Zn can be nitrate and/or acetate described in the step (1), zinc (Zn in the solution A
2+) concentration is 0.5～5.0mol/L, is preferably 1.0～3.0mol/L, sodium metaaluminate concentration is 1.0～6.0mol/L in the solution B, is preferably 2.0～4.0mol/L.
Step (2) becomes the adhesive tape part with described in the step (3): reaction temperature is 20～90 ℃, is preferably 40～80 ℃.Each gelation time is 5 ~ 35 minutes, is preferably 10 ~ 25 minutes.Described CO
2Gas concentration is 20v%～99v%, is preferably 40v%～95v%.
In the inventive method, the amount of each alkaline solution B that contains aluminium that adds can equate in step (2) and the step (3), also can be unequal, and preferably each addition equates.
Aging temperature is 50～100 ℃ behind step (4) the one-tenth glue, is preferably 60～90 ℃, and aging pH value is controlled to be 6.0 ~ 11.0, is preferably 7.0 ~ 10.0, and ageing time is 05 ~ 5.0 hour, is preferably 1.0 ~ 3.0 hours.
In the Cu-contained catalyst of the present invention, copper/zinc mol ratio is 0.1～10, is preferably 0.2～5, and (copper+zinc)/al mole ratio is 0.1～10, is preferably 3～8.
The described washing of step (5) is washed with deionized water, and wash temperature is controlled at 30～90 ℃, is preferably 40～70 ℃.Filter cake is dry under 50 ~ 150 ℃ of conditions, and preferably 60 ~ 120 ℃ of baking temperatures, are preferably 1 ~ 16 hour drying time at 0.5 ~ 24 hour drying time.300～360 ℃ of roastings 1 ~ 16 hour, be preferably 2 ~ 10 hours.
Cu-contained catalyst of the present invention, take the weight of catalyst as benchmark, the composition of catalyst comprises, is 15%～50%, Al take mass fraction: CuO as 20%～75%, ZnO
2O
3Be 5%～30%; Being preferably CuO is that 30%～60%, ZnO is 20%～40%, Al
2O
3Be 6%～30%.
Than method of the prior art, adopt the prepared Cu-contained catalyst of method of the present invention to have higher activity, the characteristics of Heat stability is good, this catalyst is suitable to catalst for synthesis of methanol especially.
The specific embodiment
Further specify the solution of the present invention and effect below by embodiment.Among the present invention, wt% is mass fraction.
Among the present invention, specific area and pore volume are to adopt the low temperature liquid nitrogen determination of adsorption method.
Embodiment 1
To dissolving tank 1 interior adding 500mL water, add 79gZn (NO
3)
26H
2The O dissolving, preparating acid sex work solution A to dissolving tank 2 interior adding 500mL water, then adds sodium metaaluminate 48 gram dissolvings, prepares alkaline working solution B.Add solution A in retort, temperature rises to 70 ℃.In situation about stirring, the 150ml solution B added to be equipped with in the solution A retort become glue, the pH value of slurries is 10.5 in the control retort, then passes into CO
2Gas, concentration are 80v%, become the glue temperature to be controlled at 70 ℃, and the pH value of slurries is 9.0 in the retort, repeats aforesaid operations process 3 times, and control reacting slurry pH value is 9.5 during cemented into bundles.Begin to wear out in the situation about stirring, add basic copper carbonate (Cu
2(OH)
2CO
3) 164 grams, pH is 9.5 when aging, temperature is 75 ℃, aging 2 hours, behind material filtering, wash with water 4 times, filter cake is in the 360 ℃ of roastings 4 hours after 6 hours of 100 ℃ of dryings, the material after the roasting add an amount of graphite and hydraulic pressure in blocks, compressing tablet obtains final catalyst A.
The composition of catalyst A, in mass fraction, as follows: CuO is 54%; ZnO is 32%; Al
2O
3Be 14%.The character of catalyst: specific area is 171m
2/ g, pore volume are 0.402cm
3/ g.
Embodiment 2
To dissolving tank 1 interior adding 500mL water, add 83gZn (NO
3)
26H
2The O dissolving, preparating acid sex work solution A to dissolving tank 2 interior adding 400mL water, then adds sodium metaaluminate 44 gram dissolvings, prepares alkaline working solution B.Add solution A in retort, temperature rises to 65 ℃.In situation about stirring, the 100ml solution B added to be equipped with in the solution A retort become glue, the pH value of slurries is 11.0 in the control retort, then passes into CO
2Gas, concentration are 85v%, become 65 ℃ of glue temperature, and the pH value of slurries is 8.4 in the retort, repeat aforesaid operations process 3 times, and control reacting slurry pH value is 8.6 during cemented into bundles.Begin to wear out in the situation about stirring, add basic copper carbonate (Cu
2(OH)
2CO
3) 153 grams, pH is 8.6 when aging, temperature is 75 ℃, aging 2.5 hours, behind material filtering, wash with water 3 times, filter cake is in the 340 ℃ of roastings 5 hours after 5 hours of 120 ℃ of dryings, the material after the roasting add an amount of graphite and hydraulic pressure in blocks, compressing tablet obtains final catalyst B.
The composition of catalyst B, in mass fraction, as follows: CuO is 53%; ZnO is 34%; Al
2O
3Be 13%.The character of catalyst: specific area is 154m
2/ g, pore volume are 0.389cm
3/ g.
Embodiment 3
To dissolving tank 1 interior adding 500mL water, add 99gZn (NO
3)
26H
2The O dissolving, preparating acid sex work solution A to dissolving tank 2 interior adding 360mL water, then adds sodium metaaluminate 36 gram dissolvings, prepares alkaline working solution B.Add solution A in retort, temperature rises to 75 ℃.In situation about stirring, the 120ml solution B added to be equipped with in the solution A retort become glue, the pH value of slurries is 10 in the control retort, then passes into CO
2Gas, concentration are 92v%, become 75 ℃ of glue temperature, and the pH value of slurries is 9.5 in the retort, repeat aforesaid operations process 2 times, and control reacting slurry pH value is 9.0 during cemented into bundles.Begin to wear out in the situation about stirring, add basic copper carbonate (Cu
2(OH)
2CO
3) 174 grams, pH is 9.2 when aging, temperature is 80 ℃, aging 3 hours, behind material filtering, wash with water 4 times, filter cake is in the 330 ℃ of roastings 6 hours after 10 hours of 80 ℃ of dryings, the material after the roasting add an amount of graphite and hydraulic pressure in blocks, compressing tablet obtains final catalyst C.
The composition of catalyst C, in mass fraction, as follows: CuO is 56%; ZnO is 36%; Al
2O
3Be 8%.The character of catalyst: specific area is 184m
2/ g, pore volume are 0.411cm
3/ g.
Embodiment 4
To dissolving tank 1 interior adding 500mL water, add 95gZn (NO
3)
26H
2The O dissolving, preparating acid sex work solution A to dissolving tank 2 interior adding 520mL water, then adds sodium metaaluminate 32 gram dissolvings, prepares alkaline working solution B.Add solution A in retort, temperature rises to 78 ℃.In situation about stirring, the 130ml solution B added to be equipped with in the solution A retort become glue, the pH value of slurries is 10.2 in the control retort, then passes into CO
2Gas, concentration are 95v%, become 78 ℃ of glue temperature, and the pH value of slurries is 9.5 in the retort, repeat aforesaid operations process 2 times, and control reacting slurry pH value is 9.5 during cemented into bundles.Begin to wear out in the situation about stirring, add basic copper carbonate (Cu
2(OH)
2CO
3) 184 grams, pH is 9.5 when aging, temperature is 80 ℃, aging 2 hours, behind material filtering, wash with water 3 times, filter cake is in the 350 ℃ of roastings 5 hours after 12 hours of 70 ℃ of dryings, the material after the roasting add an amount of graphite and hydraulic pressure in blocks, compressing tablet obtains final catalyst D.
The composition of catalyst D, in mass fraction, as follows: CuO is 58%; ZnO is 35%; Al
2O
3Be 7%.The character of catalyst: specific area is 197m
2/ g, pore volume are 0.422cm
3/ g.
Comparative Examples 1
Press the disclosed method for preparing catalyst of CN 101574649A, preparation forms identical reference agent E with the catalyst of embodiment 2.
Take by weighing Al (NO
3)
39H
2O69g adds deionized water 200ml stirring and dissolving, takes by weighing NaOH40g, NaCO
350g is total in molten and the 500ml deionized water.Under 35 ℃ condition, with NaOH-NaCO
350g solution slowly adds Al (NO
3)
3, control terminal point pH 〉=12 obtain water white sodium aluminate solution, and are for subsequent use.
Take by weighing Cu (NO
3)
23H
2O195g, Zn (NO
3)
26H
2O83g is dissolved in the 250ml deionized water; Take by weighing the 1g polyvinyl alcohol, be dissolved in the 250ml deionized water.Then these two kinds of solution are mixed, make blue clear solution.
To contain solution also stream reaction under 70 ℃ condition of sodium metaaluminate and copper nitrate-zinc nitrate, the control pH value in reaction is 7.8 ± 0.2.React complete continuation and stirred 60 minutes under reaction temperature, material is through washing, then in baking oven in 110 ℃ of dryings 4 hours, 350 ℃ of lower roastings are 4 hours in Muffle furnace, the cold deflocculated graphite of rear adding 2wt% and the deionized water of 3wt% of going played sheet moulding, gained catalyst sample E after being mixed.
The composition of catalyst E, in mass fraction, CuO is 53%; ZnO is 34%; Al
2O
3Be 13%.The character of catalyst: specific area is 78m
2/ g, pore volume are 0.127cm
3/ g.
Comparative Examples 2
Comparative Examples 2 adopts the catalst for synthesis of methanol of traditional handicraft preparation, and preparation forms identical reference agent F with the catalyst of embodiment 2.
Take by weighing Cu (NO
3)
23H
2O195g, Zn (NO
3)
26H
2O83g is dissolved in wiring solution-forming A in the 850mL deionized water, is heated to 70 ℃; Take by weighing 106 gram Na
2CO
3Be dissolved in wiring solution-forming B in the 1000ml deionized water, be heated to 70 ℃; Under the condition that stirs, solution A and solution B and stream added be equipped with in the retort of 500ml deionized water, gelation time is 1 hour, the control endpoint pH is 7.8, continues to stir 30min precipitation color and becomes blue-green by blueness, keeps 80 ℃ of precipitation temperatures; Static 3 hours, add 20gAl (OH) in the slip that makes
3, then after filtration, wash to Na
+Content≤0.035wt%, the filter cake that obtains is 100～120 ℃ of oven dry, again 320 ℃ of roastings 4 hours, the material after the roasting add an amount of graphite and hydraulic pressure in blocks, obtain catalyst F.
The composition of catalyst F, in mass fraction, CuO is 53%; ZnO is 34%; Al
2O
3Be 13%.The character of catalyst: specific area is 65m
2/ g, pore volume are 0.103cm
3/ g.
Embodiment 5
Catalst for synthesis of methanol is pulverized the order for 16-40, adopt before use low-concentration hydrogen (H
2/ N
2=3/97(volume ratio)) hydrogen nitrogen mixed gas reduction 16～20h, the highest reduction temperature is 235 ℃.Carry out the activity rating of catalyst at miniature fixed-bed reactor.Loaded catalyst is 5ml, and unstripped gas consists of CO/H
2/ CO
2/ N
2=12/70/3/15(volume ratio), reaction pressure is 5.0MPa, and air speed is 10000h
-1, reaction temperature is 250 ℃, measures CO and CO
2Conversion ratio be the catalyst initial activity.Then with catalyst in synthetic atmosphere with 450 ℃ of heat treatment 5h, drop to again 250 ℃ and measure CO and CO
2Conversion ratio be active after the heat treatment, i.e. heat resistance.Product gas chromatograph analysis, the space-time yield gmL of methanol
-1H
-1Namely every milliliter of grams of producing methyl alcohol per hour the results are shown in Table 1.Find out that from result of the test methanol synthesis catalyst of the present invention has the selective of high activity, heat resistance and excellence.
The evaluation of table 1 catalyst activity and heat resistance experimental result
| Catalyst | Initial activity, % | Initial activity, % | Heat-resisting rear activity, % | Heat-resisting rear activity, % | The methyl alcohol space-time yield, (gmL -1·h -1） | Methyl alcohol is selective, % |
| ? | CO | CO 2 | CO | CO 2 | ? | ? |
| A | 95.63 | 83.26 | 85.96 | 77.02 | 3.21 | 95.36 |
| B | 94.61 | 83.12 | 86.98 | 76.85 | 3.12 | 95.86 |
| C | 94.96 | 83.32 | 84.01 | 75.96 | 3.08 | 97.01 |
| D | 94.41 | 84.56 | 87.96 | 78.45 | 3.18 | 94.85 |
| E | 80.36 | 73.45 | 68.21 | 60.54 | 1.98 | 84.65 |
| F | 82.89 | 75.59 | 65.19 | 57.74 | 1.87 | 82.39 |
Claims (9)
1. the preparation method of a Cu-contained catalyst comprises:
(1), with the soluble-salt of Zn wiring solution-forming A soluble in water, preparation sodium aluminate solution B;
(2), the part solution B is added in the solution A, system pH is 9.0～11.0, then passes into CO
2Gas makes the pH value reduce by 0.3 ~ 2.8 to reaction system;
(3), repeating step (2) process 1～6 time, the pH value of reaction system is 8.0～10.0 during cemented into bundles;
(4), the reacting slurry with step (3) gained wears out adding basic copper carbonate when aging;
(5), the material that obtains of step (4) through washing, filter, dry, roasting, compression molding obtains Cu-contained catalyst.
2. in accordance with the method for claim 1, it is characterized in that the Zn soluble-salt described in the step (1) is nitrate and/or acetate, zinc concentration is 0.5～5.0mol/L in the solution A; Sodium metaaluminate concentration is 1.0～6.0mol/L in the solution B.
3. in accordance with the method for claim 1, it is characterized in that zinc concentration is 1.0～3.0mol/L in step (1) solution A; Sodium metaaluminate concentration is 2.0～4.0mol/L in the solution B.
4. in accordance with the method for claim 1, it is characterized in that in the described Cu-contained catalyst that copper/zinc atom mol ratio is 0.1～10.0, (copper+zinc)/aluminium atomic molar ratio is 0.1～10.0.
5. in accordance with the method for claim 1, it is characterized in that in the described Cu-contained catalyst that copper/zinc atom mol ratio is 0.2～5.0, (copper+zinc)/aluminium atomic molar ratio is 3.0～8.0.
6. in accordance with the method for claim 1, it is characterized in that step (2) and step (3) are described becomes the adhesive tape part: reaction temperature is 20～90 ℃, and each gelation time is 5 ~ 35 minutes, described CO
2Gas concentration is 20v%～99v%.
7. in accordance with the method for claim 1, it is characterized in that described in the step (4) becoming that aging temperature is 50～100 ℃ behind the glue, aging pH value is controlled to be 6.0 ~ 10.0, and ageing time is 0.5 ~ 5.0 hour.
8. the temperature that in accordance with the method for claim 1, it is characterized in that the described washing of step (5) is controlled at 30～90 ℃; Filter cake is dry under 50 ~ 150 ℃ of conditions, and 0.5 ~ 24.0 hour drying time was 300～360 ℃ of roastings 1 ~ 16 hour.
9. according to the arbitrary described method of claim 1 ~ 8, it is characterized in that described Cu-contained catalyst, take the weight of catalyst as benchmark, the composition of catalyst comprises, is 15%～50%, Al take mass fraction: CuO as 20%～75%, ZnO
2O
3Be 5%～30%.
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|---|---|---|---|---|
| CN107774263A (en) * | 2016-08-31 | 2018-03-09 | 中国石油化工股份有限公司 | A kind of preparation method of catalst for synthesis of methanol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101298052A (en) * | 2008-06-20 | 2008-11-05 | 华东理工大学 | Copper zinc catalyst and precursor, preparation and use thereof |
| CN101574649A (en) * | 2009-05-25 | 2009-11-11 | 来安县迅能催化剂有限公司 | Methanol catalyst preparation method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101298052A (en) * | 2008-06-20 | 2008-11-05 | 华东理工大学 | Copper zinc catalyst and precursor, preparation and use thereof |
| CN101574649A (en) * | 2009-05-25 | 2009-11-11 | 来安县迅能催化剂有限公司 | Methanol catalyst preparation method |
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|---|---|---|---|---|
| CN107774263A (en) * | 2016-08-31 | 2018-03-09 | 中国石油化工股份有限公司 | A kind of preparation method of catalst for synthesis of methanol |
| CN107774263B (en) * | 2016-08-31 | 2019-11-15 | 中国石油化工股份有限公司 | A kind of preparation method of catalst for synthesis of methanol |
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