CN103372438B - A kind of preparation method of Cu-contained catalyst - Google Patents
A kind of preparation method of Cu-contained catalyst Download PDFInfo
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- CN103372438B CN103372438B CN201210442627.3A CN201210442627A CN103372438B CN 103372438 B CN103372438 B CN 103372438B CN 201210442627 A CN201210442627 A CN 201210442627A CN 103372438 B CN103372438 B CN 103372438B
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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
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- 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 kind of preparation method of Cu-contained catalyst.The method in zinc metal salt solution, adds sodium aluminate solution make system pH be 9.0 ~ 11.0, then passes into CO
2make pH value reduce by 0.3 ~ 2.8 in gas to reaction system, repeat above-mentioned steps and carry out plastic reaction, add basic copper carbonate time aging after plastic to prepare Cu-contained catalyst.The method can improve the physico-chemical property of catalyst, increases the specific area of catalyst, increases coordinative role between main active metal component copper and promoter metal component zinc, improve the dispersiveness of active phase, improves activity and the stability of catalyst.This catalyst is suitable to catalst for synthesis of methanol especially.
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 third place in the world, methanol demands amount and the production capacity sustainable growth along with industrial development in recent years.
Industrial methyl alcohol is generally with containing H
2, CO, CO
2synthesis gas produce under certain pressure, temperature and catalyst existence condition.In generally adopting in the world at present, low-pressure vapor phase method synthesizing methanol, used catalyst is essentially the mixed oxide of copper, zinc, aluminium.CuO, ZnO, Al in catalst for synthesis of methanol
2o
3the effect of three components is variant, and CuO is main active component, ZnO and Al
2o
3for auxiliary agent.Method for preparing catalyst is generally the mixing subcarbonate first using coprecipitation to generate (comprise and flow, instead to add, just add coprecipitation) copper zinc, and then add aluminium hydroxide in pulping process, generate slurry through washing, drying, roasting, compression molding.The research of current catalyst preparing mainly concentrates on optimization and the improvement of preparation method and technique, catalyst activity is improved by changing the ratio of catalytic component, the size of crystal grain, the size of specific area and pore-size distribution, improve copper-based catalysts poor heat stability, the selective low problem short with the life-span.Method for preparing catalyst is different, and the performance of gained catalyst can differ larger.
CN 1810357A adopts a traditional step coprecipitation to prepare a kind of catalst for synthesis of methanol.By the nitrate mixed solution of Cu, Zn, Al, Li and NaCO
3solution stream is titrated in the deionized water of a small amount of high-speed stirred, keeps the pH of solution between 7 ~ 8 simultaneously, aging, suction filtration, washing, dries to obtain catalyst precarsor, and catalyst precarsor is dried, roasting obtains finished product.The method adopts a typical step coprecipitation to prepare catalyst for methanol, in preparation process, with the addition of LiNO
3.
CN 1329938A discloses a kind of preparation method of catalst for synthesis of methanol, and this catalyst is made up of the oxide of copper, zinc, aluminium.Preparation process a: part makes coprecipitate containing copper, zinc, aluminium compound by coprecipitation, another part makes coprecipitate containing copper, zinc compound with co-precipitation.The equal thermal decomposition of above-mentioned coprecipitate is the oxide of metal, then by these two kinds of co-precipitation mixing, washing, dry, roasting, and shaping obtained catalyst.
CN 1660490A discloses a kind of preparation method of catalst for synthesis of methanol, its preparation process is: coprecipitation is prepared in methanol synthesis catalyst process and added a small amount of Surfactant OP, or fractional precipitation is prepared in methanol synthesis catalyst process and is added a small amount of Surfactant OP, obtained a kind of catalst for synthesis of methanol.
CN 101574649A discloses a kind of preparation method of catalst for synthesis of methanol, step is reacted by the mixed aqueous solution of the aqueous solution of aluminum soluble salt and alkali metal hydroxide-carbonate, generate a kind of transparent meta-aluminate aqueous solution, then it is carried out coprecipitation reaction with containing the copper of water-soluble high-molecular compound, the transparent aqueous solution of zinc salt, generate the mixing co-precipitation of a kind of copper, zinc, aluminium, then through washing, drying, granulation process, roasting, beat that sheet is shaping can obtain 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), changing the presoma of catalyst preparation process (step process changes two steps or three step process into) and change Al, come the structure of regulating catalyst, surface acidic-basic property, electronic property, to improve the activity of existing catalyst, selective or life-span.But improve catalst for synthesis of methanol key that the is active and life-span be to increase the specific area of catalyst and active ingredient copper and co-catalyst zinc distribute more evenly, above patent does not all relate to.
Summary of the invention
For above-mentioned deficiency of the prior art, the invention provides the preparation method of simple, the easy-operating synthesis Cu-contained catalyst of a kind of technique.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 improves 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 has considerable influence to the specific area of catalyst, and the feed postition of active component also has a significant impact coordinative role between active component dispersiveness, active metal component.Inventor is found by a large amount of experiments, in zinc metal salt solution, first adds sodium metaaluminate, and then passes into CO
2gas, so repeated multiple timesly carry out plastic reaction, and when aging, add basic copper carbonate prepare Cu-contained catalyst, the physico-chemical property of catalyst can be improved, increase the specific area of catalyst, increase coordinative role between main metal component copper and promoter metal component zinc, improve the dispersiveness of active metal component copper, allow active metal in catalyst play one's part to the full, improve activity and the stability of catalyst.
The preparation method of Cu-contained catalyst of the present invention, comprises the following steps:
(1), by the soluble-salt of Zn wiring solution-forming A soluble in water is mixed, preparation sodium aluminate solution B;
(2), add in solution A by part solution B, system pH is 9.0 ~ 11.0, then passes into CO
2pH value is made to reduce by 0.3 ~ 2.8 in gas to reaction system;
(3), repeat step (2) process 1 ~ 6 time, during cemented into bundles, the pH value of reaction system is 8.0 ~ 10.0;
(4), by aging for the reacting slurry of step (3) gained, time aging, basic copper carbonate is added;
(5), the material that obtains of step (4) through washing, filter, dry, roasting, compression molding, obtains Cu-contained catalyst.
Described in step (1), the soluble-salt of Zn can be nitrate and/or acetate, zinc (Zn in solution A
2+) concentration is 0.5 ~ 5.0mol/L, be preferably 1.0 ~ 3.0mol/L, in solution B, sodium metaaluminate concentration is 1.0 ~ 6.0mol/L, is preferably 2.0 ~ 4.0mol/L.
Gelation Conditions described in step (2) and step (3): reaction temperature is 20 ~ 90 DEG C, is preferably 40 ~ 80 DEG C.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 the alkaline solution B containing aluminium at every turn added in step (2) and step (3) can be equal, also can be unequal, and preferably each addition is equal.
Aging temperature 50 ~ 100 DEG C after step (4) plastic, is preferably 60 ~ 90 DEG C, and it is 6.0 ~ 11.0 that aging pH value controls, and be preferably 7.0 ~ 10.0, ageing time is 05 ~ 5.0 hour, is preferably 1.0 ~ 3.0 hours.
In Cu-contained catalyst of the present invention, copper/zinc mol ratio is 0.1 ~ 10, and be preferably 0.2 ~ 5, (copper+zinc)/al mole ratio is 0.1 ~ 10, is preferably 3 ~ 8.
Step (5) described washing spends deionized water, and wash temperature controls at 30 ~ 90 DEG C, is preferably 40 ~ 70 DEG C.Filter cake is dry under 50 ~ 150 DEG C of conditions, and baking temperature preferably 60 ~ 120 DEG C, 0.5 ~ 24 hour drying time, is preferably 1 ~ 16 hour drying time.300 ~ 360 DEG C of roastings 1 ~ 16 hour, be preferably 2 ~ 10 hours.
Cu-contained catalyst of the present invention, with the weight of catalyst for benchmark, the composition of catalyst comprises, in mass fraction: CuO is 20% ~ 75%, ZnO is 15% ~ 50%, Al
2o
3be 5% ~ 30%; Preferably CuO is 30% ~ 60%, ZnO is 20% ~ 40%, Al
2o
3be 6% ~ 30%.
Compared to method of the prior art, adopt Cu-contained catalyst prepared by method of the present invention to have higher activity, the feature of Heat stability is good, this catalyst is suitable to catalst for synthesis of methanol especially.
Detailed description of the invention
The solution of the present invention and effect is further illustrated below by embodiment.In the present invention, wt% is mass fraction.
In the present invention, specific area and pore volume adopt low temperature liquid nitrogen determination of adsorption method.
Embodiment 1
In dissolving tank 1, add 500mL water, add 79gZn (NO
3)
26H
2o dissolves, and preparating acid sex work solution A, adds 500mL water in dissolving tank 2, then adds sodium metaaluminate 48 grams dissolving, prepares alkaline working solution B.In retort, add solution A, temperature rises to 70 DEG C.When stirring, 150ml solution B being added and plastic in solution A retort is housed, the pH value controlling slurries in retort is 10.5, then passes into CO
2gas, concentration is 80v%, and gelling temperature controls at 70 DEG C, and in retort, the pH value of slurries is 9.0, repeats aforesaid operations process 3 times, and controlling reacting slurry pH value during cemented into bundles is 9.5.Start aging when stirring, add basic copper carbonate (Cu
2(OH)
2cO
3) 164 grams, time aging, pH is 9.5, and temperature is 75 DEG C, aging 2 hours, after material filtering, wash 4 times with water, filter cake is in 100 DEG C of dryings, 360 DEG C of roastings 4 hours after 6 hours, and the material after roasting adds appropriate graphite and hydraulic pressure is in blocks, and 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 is 0.402cm
3/ g.
Embodiment 2
In dissolving tank 1, add 500mL water, add 83gZn (NO
3)
26H
2o dissolves, and preparating acid sex work solution A, adds 400mL water in dissolving tank 2, then adds sodium metaaluminate 44 grams dissolving, prepares alkaline working solution B.In retort, add solution A, temperature rises to 65 DEG C.When stirring, 100ml solution B being added and plastic in solution A retort is housed, the pH value controlling slurries in retort is 11.0, then passes into CO
2gas, concentration is 85v%, gelling temperature 65 DEG C, and in retort, the pH value of slurries is 8.4, repeats aforesaid operations process 3 times, and controlling reacting slurry pH value during cemented into bundles is 8.6.Start aging when stirring, add basic copper carbonate (Cu
2(OH)
2cO
3) 153 grams, time aging, pH is 8.6, and temperature is 75 DEG C, aging 2.5 hours, after material filtering, wash 3 times with water, filter cake is in 120 DEG C of dryings, 340 DEG C of roastings 5 hours after 5 hours, and the material after roasting adds appropriate graphite and hydraulic pressure is in blocks, and 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 is 0.389cm
3/ g.
Embodiment 3
In dissolving tank 1, add 500mL water, add 99gZn (NO
3)
26H
2o dissolves, and preparating acid sex work solution A, adds 360mL water in dissolving tank 2, then adds sodium metaaluminate 36 grams dissolving, prepares alkaline working solution B.In retort, add solution A, temperature rises to 75 DEG C.When stirring, 120ml solution B being added and plastic in solution A retort is housed, the pH value controlling slurries in retort is 10, then passes into CO
2gas, concentration is 92v%, gelling temperature 75 DEG C, and in retort, the pH value of slurries is 9.5, repeats aforesaid operations process 2 times, and controlling reacting slurry pH value during cemented into bundles is 9.0.Start aging when stirring, add basic copper carbonate (Cu
2(OH)
2cO
3) 174 grams, time aging, pH is 9.2, and temperature is 80 DEG C, aging 3 hours, after material filtering, wash 4 times with water, filter cake is in 80 DEG C of dryings, 330 DEG C of roastings 6 hours after 10 hours, and the material after roasting adds appropriate graphite and hydraulic pressure is in blocks, and 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 is 0.411cm
3/ g.
Embodiment 4
In dissolving tank 1, add 500mL water, add 95gZn (NO
3)
26H
2o dissolves, and preparating acid sex work solution A, adds 520mL water in dissolving tank 2, then adds sodium metaaluminate 32 grams dissolving, prepares alkaline working solution B.In retort, add solution A, temperature rises to 78 DEG C.When stirring, 130ml solution B being added and plastic in solution A retort is housed, the pH value controlling slurries in retort is 10.2, then passes into CO
2gas, concentration is 95v%, gelling temperature 78 DEG C, and in retort, the pH value of slurries is 9.5, repeats aforesaid operations process 2 times, and controlling reacting slurry pH value during cemented into bundles is 9.5.Start aging when stirring, add basic copper carbonate (Cu
2(OH)
2cO
3) 184 grams, time aging, pH is 9.5, and temperature is 80 DEG C, aging 2 hours, after material filtering, wash 3 times with water, filter cake is in 70 DEG C of dryings, 350 DEG C of roastings 5 hours after 12 hours, and the material after roasting adds appropriate graphite and hydraulic pressure is in blocks, and 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 is 0.422cm
3/ g.
Comparative example 1
By method for preparing catalyst disclosed in CN 101574649A, preparation forms identical reference agent E with the catalyst of embodiment 2.
Take Al (NO
3)
39H
2o69g, adds deionized water 200ml stirring and dissolving, takes NaOH40g, NaCO
350g is molten with 500ml deionized water altogether.Under the condition of 35 DEG C, by NaOH-NaCO
350g solution slowly adds Al (NO
3)
3, control terminal pH>=12, obtain water white sodium aluminate solution, for subsequent use.
Take Cu (NO
3)
23H
2o195g, Zn (NO
3)
26H
2o83g is dissolved in 250ml deionized water; Take 1g polyvinyl alcohol, be dissolved in 250ml deionized water.Then by these two kinds of solution mixing, blue-tinted transparent solution is made.
Solution containing sodium metaaluminate and copper nitrate-zinc nitrate is flowed reaction under the condition of 70 DEG C, and to control pH value in reaction be 7.8 ± 0.2.React complete continuation and stir 60 minutes at the reaction temperatures, material passes through washing, then in an oven in 110 DEG C of dryings 4 hours, roasting 4 hours at 350 DEG C in Muffle furnace, cold go after add the deflocculated graphite of 2wt% and the deionized water of 3wt%, beat sheet after being mixed shaping, gained catalyst sample E.
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 is 0.127cm
3/ g.
Comparative example 2
The catalst for synthesis of methanol that comparative example 2 adopts traditional handicraft to prepare, preparation forms identical reference agent F with the catalyst of embodiment 2.
Take Cu (NO
3)
23H
2o195g, Zn (NO
3)
26H
2o83g is dissolved in wiring solution-forming A in 850mL deionized water, is heated to 70 DEG C; Take 106 grams of Na
2cO
3be dissolved in wiring solution-forming B in 1000ml deionized water, be heated to 70 DEG C; Under the condition stirred, by solution A and solution B and stream adds in the retort that 500ml deionized water is housed, gelation time is 1 hour, and controlling endpoint pH is 7.8, continues to stir 30min and precipitates color and become blue-green from blueness, keep precipitation temperature 80 DEG C; Static 3 hours, in obtained slip, add 20gAl (OH)
3, then after filtration, wash to Na
+content≤0.035wt%, the filter cake obtained is 100 ~ 120 DEG C of oven dry, then 320 DEG C of roastings 4 hours, the material after roasting adds appropriate graphite and hydraulic pressure is in blocks, obtains 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 is 0.103cm
3/ g.
Embodiment 5
Catalst for synthesis of methanol is pulverized for 16-40 order, adopt low-concentration hydrogen (H before use
2/ N
2=3/97(volume ratio)) hydrogen nitrogen mixed gas reduction 16 ~ 20h, the highest reduction temperature is 235 DEG C.Miniature fixed-bed reactor carries out the activity rating of catalyst.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 DEG C, measures CO and CO
2conversion ratio be catalyst initial activity.Then catalyst is being synthesized by 450 DEG C of heat treatment 5h in atmosphere, then dropping to 250 DEG C of mensuration CO and CO
2conversion ratio be active after heat treatment, i.e. heat resistance.Product chromatographic, the space-time yield gmL of methanol
-1h
-1namely the grams of every milliliter of product methyl alcohol per hour, the results are shown in Table 1.Find out 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, % | 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 (6)
1. a preparation method for Cu-contained catalyst, comprising:
(1), by wiring solution-forming A soluble in water for the soluble-salt of Zn, preparation sodium aluminate solution B;
(2), add in solution A by part solution B, system pH is 9.0 ~ 11.0, then passes into CO
2pH value is made to reduce by 0.3 ~ 2.8 in gas to reaction system;
(3), repeat step (2) process 1 ~ 6 time, during cemented into bundles, the pH value of reaction system is 8.0 ~ 10.0;
(4), by aging for the reacting slurry of step (3) gained, time aging, basic copper carbonate is added;
(5), the material that obtains of step (4) through washing, filter, dry, roasting, compression molding, obtains Cu-contained catalyst;
Zn soluble-salt described in step (1) is nitrate and/or acetate, and in solution A, zinc concentration is 0.5 ~ 5.0mol/L; In solution B, sodium metaaluminate concentration is 1.0 ~ 6.0mol/L;
Step (2) and step (3) described Gelation Conditions: reaction temperature is 20 ~ 90 DEG C, each gelation time is 5 ~ 35 minutes, described CO
2gas concentration is 20v% ~ 99v%;
After plastic described in step (4), aging temperature is 50 ~ 100 DEG C, and it is 6.0 ~ 10.0 that aging pH value controls, and ageing time is 0.5 ~ 5.0 hour.
2. in accordance with the method for claim 1, it is characterized in that in step (1) solution A, zinc concentration is 1.0 ~ 3.0mol/L; In solution B, sodium metaaluminate concentration is 2.0 ~ 4.0mol/L.
3. in accordance with the method for claim 1, it is characterized in that in described Cu-contained catalyst, copper/zinc atom mol ratio is 0.1 ~ 10.0, and (copper+zinc)/aluminium atomic molar ratio is 0.1 ~ 10.0.
4. in accordance with the method for claim 1, it is characterized in that in described Cu-contained catalyst, copper/zinc atom mol ratio is 0.2 ~ 5.0, and (copper+zinc)/aluminium atomic molar ratio is 3.0 ~ 8.0.
5. in accordance with the method for claim 1, it is characterized in that the temperature of step (5) described washing controls at 30 ~ 90 DEG C; Filter cake is dry under 50 ~ 150 DEG C of conditions, and 0.5 ~ 24.0 hour drying time, 300 ~ 360 DEG C of roastings 1 ~ 16 hour.
6., according to the arbitrary described method of claim 1 ~ 5, it is characterized in that described Cu-contained catalyst, with the weight of catalyst for benchmark, the composition of catalyst comprises, in mass fraction: CuO is 20% ~ 75%, ZnO is 15% ~ 50%, Al
2o
3be 5% ~ 30%.
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|---|---|---|---|---|
| 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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| 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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