CN103801302B - A kind of preparation method containing copper zinc catalyst - Google Patents
A kind of preparation method containing copper zinc catalyst Download PDFInfo
- Publication number
- CN103801302B CN103801302B CN201210443086.6A CN201210443086A CN103801302B CN 103801302 B CN103801302 B CN 103801302B CN 201210443086 A CN201210443086 A CN 201210443086A CN 103801302 B CN103801302 B CN 103801302B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- zinc
- copper
- accordance
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation method containing copper zinc catalyst.The method adopts carbonizatin method to prepare zinc compound precipitation and aluminum contained compound precipitation respectively, then by aging for two kinds of sediment mixing, add basic copper carbonate, then through washing, filtration, dry, roasting, compression molding, obtains Cu-contained catalyst simultaneously.The specific surface area of catalyst of the method gained is higher, and active particle is even, and raising active ingredient copper and co-catalyst zinc act synergistically, and improve the activity of Cu-contained catalyst and the service life of heat endurance and catalyst.This catalyst is suitable to catalst for synthesis of methanol.
Description
Technical field
The present invention relates to a kind of preparation method containing copper zinc catalyst, be specifically related to a kind of preparation method containing copper zinc catalyst for the synthesis of methyl alcohol with high activity, good thermal stability.
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.
CN1810357A adopts a traditional step coprecipitation to prepare 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.
CN101574649A 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.
CN1660490A 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.
CN101219382A discloses a kind of copper-based catalysts and preparation method of synthesizing methanol.By water-soluble for Cu, Zn, Al soluble-salt, by anhydrous Na
2cO
3wiring solution-forming soluble in water; By Na
2cO
3solution heats, and add the soluble salt solutions of Cu, Zn, pH=7.0 ~ 8.2 be terminal, aging must copper zinc mother liquor; At Al (NO
3)
3ammoniacal liquor, Na is added in solution
2cO
3solution, K
2cO
3solution or NH
4hCO
3solution, pH value terminal 8.0 ~ 11.0, aging aluminium emulsion; Join in Cu, Zn masterbatch by boehmite or aluminium emulsion, gained material washes with water without Na
+, filtration is drained, and dry, roasting, compression molding, pulverizes.
CN1329938A, CN101306369A, CN101327431A, CN101513615A adopt the preparation method of two steps and three step process catalst for synthesis of methanol, these methods change a traditional step and prepare catalyst for methanol process, preparation process is generally divided into two steps or three steps to prepare sediment, then by coprecipitate mixing, washing, dry, roasting, shaping obtained catalyst.
The catalst for synthesis of methanol method of above-mentioned patent Introduction is by adding new auxiliary agent (Li and surfactant), change the presoma of catalyst preparation process (step process changes two steps or three step process into) and change Al, carry out the structure of regulating catalyst, surface acidic-basic property, electronic property, to improve the activity of existing catalyst, selective or life-span, but improving catalst for synthesis of methanol key that the is active and life-span, to be that the specific area of increase catalyst and active ingredient copper and co-catalyst zinc distribute more even, act synergistically stronger, above patent does not all relate to.
Summary of the invention
For above-mentioned deficiency of the prior art, the invention provides a kind of preparation method containing copper zinc catalyst.The specific surface area of catalyst of the method gained is higher, and active particle is even, and raising active ingredient copper and co-catalyst zinc act synergistically, and improve the activity of Cu-contained catalyst and the service life of heat endurance and catalyst.This catalyst is as catalst for synthesis of methanol.
Catalyst granules prepared by the precipitation method is easy to uneven, the feed postition of active component is different and the composite oxide of metal grain size of formation can be made different, there is considerable influence to the specific area of catalyst, and coordinative role between active component dispersiveness, active metal component is also had a significant impact.Inventor is found by a large amount of experiments, catalst for synthesis of methanol is prepared by two step process processes, carbon dioxide and zinc solution, sodium metaaluminate co-precipitation is adopted to generate containing zinc coprecipitate slurries with containing aluminium coprecipitate slurries respectively, both sediment slurries are mixed, adds basic copper carbonate time aging and prepare catalst for synthesis of methanol.Adopt carbon dioxide to generate sediment with zinc solution and sodium metaaluminate co-precipitation respectively, increase the specific area of catalyst, add basic copper carbonate time aging, after aging, carry out roasting, the reunion easily occurring copper particle when precipitating can be prevented.After roasting simultaneously, CuO is dispersed on ZnO, CuO grain refinement, increases coordinative role between main metal component copper and promoter metal component zinc, improves the dispersiveness of active metal component copper, allow active metal in catalyst play one's part to the full, improve activity and the heat endurance of catalyst.
The preparation method of Cu-contained catalyst of the present invention, comprising:
(1), in the soluble salt solutions A of Zn, CO is passed into
2gas, reaction generates containing sediment slurries I;
(2), in sodium aluminate solution B, CO is passed into
2gas, generates containing sediment slurries II,
(3), by the sediment slurries II that contains containing sediment slurries I and step (2) gained of step (1) gained mix, under agitation aging, add basic copper carbonate time aging;
(4), the material that obtains of step (3) through washing, filter, dry, roasting, compression molding, obtains containing copper zinc catalyst.
Described in step (1), the soluble-salt of Zn can be nitrate and/or acetate.The concentration of the soluble salt solutions A of described Zn is 0.5 ~ 5.0mol/L, is preferably 1.0 ~ 3.0mol/L.Pass into the CO in the soluble salt solutions of Zn
2the total amount of gas and zinc salt mol ratio are 2 ~ 7, are preferably 3 ~ 5.
The concentration of the sodium aluminate solution B described in step (2) is 1.0 ~ 6.0mol/L, is preferably 2.0 ~ 4.0mol/L.Pass into CO in sodium aluminate solution
2in the total amount of gas with sodium metaaluminate with Al
2o
3the mol ratio of meter is 2 ~ 8, is preferably 3 ~ 6.
In step (3), aging temperature is 40 ~ 90 DEG C, is preferably 50 ~ 80 DEG C.Time aging, pH value controls is 7.0 ~ 12.0, is preferably 7.5 ~ 11.0.Ageing time is 0.5 ~ 5.0 hour, is preferably 1.0 ~ 3.0 hours.
Plastic process CO used described in step (1) and step (2)
2volumetric concentration 20v% ~ the 99v% of gas, is preferably 40v% ~ 95v%.
Plastic process described in step (1) and step (2), reaction temperature is 30 ~ 90 DEG C, is preferably 40 ~ 80 DEG C.During plastic, pH value controls is 6.0 ~ 11.0, is preferably 7.0 ~ 10.0.Gelation time is 0.2 ~ 4.0 hour, is preferably 0.5 ~ 3.0 hour.
In step (3) gained material, copper/zinc mol ratio is 0.1 ~ 10.0, and be preferably 0.2 ~ 5.0, (copper+zinc)/al mole ratio is 0.1 ~ 10.0, is preferably 3.0 ~ 8.0.
Step (4) described washing water purification temperature controls at 30 ~ 90 DEG C, is preferably 40 ~ 70 DEG C.Filter cake dehydrates under 50 ~ 150 DEG C of conditions, and baking temperature preferably 60 ~ 120 DEG C, 1 ~ 24 hour drying time, is preferably 2 ~ 16 hours drying time.300 ~ 360 DEG C of roastings 1 ~ 16 hour, be preferably 2 ~ 12 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%, being preferably CuO is 30% ~ 60%; ZnO is 20% ~ 40%; Al
2o
3be 6% ~ 30%.
Compared to method of the prior art, the catalyst of synthesizing methanol prepared by method of the present invention is adopted to have higher activity, the feature of Heat stability is good.
Detailed description of the invention
Further illustrate the solution of the present invention and effect below by embodiment, v% is volume fraction.
Embodiment 1
In dissolving tank 1, add 500mL water, add 105gZn (NO
3)
26H
2o dissolves, and wiring solution-forming A, is elevated to 65 DEG C by solution A temperature, passes into the CO that concentration is 90v% in solution A
2, during plastic, the pH value of slurries controls to be 7.5 ± 0.2, and reaction time 0.5h generates containing sediment slurries I.In dissolving tank 2, add 500mL water, then add sodium metaaluminate 34 grams dissolving, wiring solution-forming B, is elevated to 65 DEG C by solution B temperature, passes into solution B the CO that concentration is 90v%
2, during plastic, the pH value of slurries controls to be 7.8 ± 0.2, and reaction time 0.5h generates containing sediment slurries II.Pass into CO in solution A
2the total amount of gas and the mol ratio of zinc salt are 3.5, pass into CO in solution B
2al in the total amount of gas and solution B
2o
3mol ratio is 4.0.By two kinds containing the mixing of sediment slurries, start aging when stirring, add basic copper carbonate (Cu
2(OH)
2cO
3) 132 grams, time aging, pH is 8.0 ± 0.2, and temperature is 70 DEG C, aging 1.5 hours, after material filtering, wash 3 times with water purification, filter cake is in 90 DEG C of dryings, 350 DEG C of roastings 6 hours after 8 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 51%; ZnO is 38%; Al
2o
3be 11%.The character of catalyst: specific area is 158m
2/ g, pore volume is 0.382cm
3/ g.
Embodiment 2
In dissolving tank 1, add 250mL water, add 87gZn (NO
3)
26H
2o dissolves, and wiring solution-forming A, is elevated to 60 DEG C by solution A temperature, passes into the CO that concentration is 95v% in solution A
2, during plastic, the pH value of slurries controls to be 7.8 ± 0.2, and reaction time 0.5h generates containing sediment slurries I.In dissolving tank 2, add 300mL water, then add sodium metaaluminate 48 grams dissolving, wiring solution-forming B, is elevated to 65 DEG C by solution B temperature, passes into solution B the CO that concentration is 95v%
2, during plastic, the pH value of slurries controls to be 7.8 ± 0.2, and reaction time 0.5h generates containing sediment slurries II.Pass into CO in solution A
2the total amount of gas and the mol ratio of zinc salt are 3.8, pass into CO in solution B
2al in the total amount of gas and solution B
2o
3mol ratio is 4.4.By two kinds containing the mixing of sediment slurries, start aging when stirring, add basic copper carbonate (Cu
2(OH)
2cO
3) 151 grams, time aging, pH is 8.5 ± 0.2, and temperature is 75 DEG C, aging 2 hours, after material filtering, wash 2 times with water purification, filter cake is in 120 DEG C of dryings, 330 DEG C of roastings 7 hours after 8 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 54%; ZnO is 33%; Al
2o
3be 13%.The character of catalyst: specific area is 147m
2/ g, pore volume is 0.371cm
3/ g.
Embodiment 3
In dissolving tank 1, add 400mL water, add 78gZn (NO
3)
26H
2o dissolves, and wiring solution-forming A, is elevated to 65 DEG C by solution A temperature, passes into the CO that concentration is 88v% in solution A
2, during plastic, the pH value of slurries controls to be 8.0 ± 0.2, and reaction time 0.5h generates containing sediment slurries I.In dissolving tank 2, add 400mL water, then add sodium metaaluminate 44 grams dissolving, wiring solution-forming B, is elevated to 55 DEG C by solution B temperature, passes into solution B the CO that concentration is 90v%
2, during plastic, the pH value of slurries controls to be 7.6 ± 0.2, and reaction time 0.5h generates containing sediment slurries II.Pass into CO in solution A
2the total amount of gas and the mol ratio of zinc salt are 2.8, pass into CO in solution B
2al in the total amount of gas and solution B
2o
3mol ratio is 3.5.By two kinds containing the mixing of sediment slurries, start aging when stirring, add basic copper carbonate (Cu
2(OH)
2cO
3) 162 grams, time aging, pH is 7.8 ± 0.2, and temperature is 72 DEG C, aging 2 hours, after material filtering, wash 3 times with water purification, filter cake is in 90 DEG C of dryings, 300 DEG C of roastings 8 hours after 8 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 32%; Al
2o
3be 12%.The character of catalyst: specific area is 141m
2/ g, pore volume is 0.357cm
3/ g.
Embodiment 4
In dissolving tank 1, add 500mL water, add 98gZn (NO
3)
26H
2o dissolves, and wiring solution-forming A, is elevated to 70 DEG C by solution A temperature, passes into the CO that concentration is 95v% in solution A
2, during plastic, the pH value of slurries controls to be 8.2 ± 0.2, and reaction time 0.5h generates containing sediment slurries I.In dissolving tank 2, add 500mL water, then add sodium metaaluminate 52 grams dissolving, wiring solution-forming B, is elevated to 75 DEG C by solution B temperature, passes into solution B the CO that concentration is 95v%
2, during plastic, the pH value of slurries controls to be 7.6 ± 0.2, and reaction time 0.5h generates containing sediment slurries II.Pass into CO in solution A
2the total amount of gas and the mol ratio of zinc salt are 3.8, pass into CO in solution B
2al in the total amount of gas and solution B
2o
3mol ratio is 3.0.By two kinds containing the mixing of sediment slurries, start aging when stirring, add basic copper carbonate (Cu
2(OH)
2cO
3) 125 grams, time aging, pH is 8.2 ± 0.2, and temperature is 80 DEG C, aging 3 hours, after material filtering, wash 3 times with water purification, filter cake is in 90 DEG C of dryings, 350 DEG C of roastings 4 hours after 8 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 50%; ZnO is 36%; Al
2o
3be 14%.The character of catalyst: specific area is 185m
2/ g, pore volume is 0.399cm
3/ g.
Comparative example 1
Method for preparing catalyst disclosed in CN101219382A, preparation forms identical reference agent E with the catalyst of embodiment 1.
(1). get 188gCu (NO
3)
2, 105gZn (NO
3)
2be dissolved in 800mL deionized water, be uniformly mixed.
(2). get 0.5molL
-1na (CO
3)
2solution 220mL is placed in 500mL beaker, is heated to 65 DEG C, under agitation the mixed liquor of step (1) gained is added to Na (CO with the speed of 25mL/min
3)
2in solution, the pH=8.2 both controlling after reinforced, Cu, Zn masterbatch is aging 1h at 82 DEG C;
(3). get Al (NO
3)
39H
2o72g is dissolved in 400mL deionized water, and 4mL ammoniacal liquor is added to Al (NO
3)
3aging 1h is stirred in solution;
(4). joined by the emulsion of aging aluminium in aging Cu, Zn masterbatch, stir after 40min, gained material spends deionized water to without Na
+;
(5). filter and drain, filter cake dries 2h at 110 DEG C, pulverizes, at Muffle furnace roasting 3h at 350 DEG C;
(6). finally (5) gained mixed oxide compressing tablet, pulverize for 16-40 order is for subsequent use.Gained catalyst sample E.
The composition of catalyst E, in mass fraction, as follows: CuO is 51%; ZnO is 38%; Al
2o
3be 11%.。The character of catalyst: specific area is 93m
2/ g, pore volume is 0.125cm
3/ g.
Comparative example 2
By method for preparing catalyst disclosed in CN101574649A, preparation forms identical reference agent F with the catalyst of embodiment 1.
Take Al (NO
3)
39H
2o72g, adds deionized water 200ml stirring and dissolving, takes NaOH40g, NaCO
350g is molten with 500ml deionized water altogether.Under the condition of 20 DEG C ~ 50 DEG C, by NaOH-NaCO
350g solution slowly adds Al (NO
3)
3, control terminal PH>=12, obtain a kind of water white sodium aluminate solution, for subsequent use.
Take Cu (NO
3)
23H
2o188g, Zn (NO
3)
26H
2o105g is dissolved in 250ml deionized water; Take 1g polyvinyl alcohol, be dissolved in 250ml deionized water.Then by these two kinds of solution mixing, a kind of blue-tinted transparent solution is made.
Solution containing sodium metaaluminate and copper nitrate-zinc nitrate is flowed reaction under the condition of 40 DEG C ~ 90 DEG C, and to control ph value of reaction be 6.5 ~ 8.5.React complete continuation and stir 60 minutes at the reaction temperatures, material is through washing, then in an oven in 100 DEG C ~ 150 DEG C dryings 4 hours, roasting 4 hours at 350 DEG C in Muffle furnace, cold go after add the deflocculated graphite of 2% and the deionized water of 3%, sheet is beaten shaping, gained catalyst sample F after being mixed.
The composition of catalyst F, in mass fraction, as follows: CuO is 51%; ZnO is 38%; Al
2o
3be 11%.The character of catalyst: specific area is 103m
2/ g, pore volume is 0.129cm
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) 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 milliliter number 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 selective (%) |
| CO | CO 2 | CO | CO 2 | |||
| A | 97.78 | 86.18 | 87.91 | 78.31 | 3.41 | 97.54 |
| B | 96.26 | 86.37 | 88.51 | 79.23 | 3.32 | 96.95 |
| C | 96.69 | 87.29 | 87.47 | 77.28 | 3.47 | 96.18 |
| D | 95.98 | 86.17 | 86.43 | 79.54 | 3.25 | 97.01 |
| E | 75.86 | 68.45 | 69.21 | 59.12 | 1.91 | 82.24 |
| F | 74.74 | 71.59 | 65.49 | 57.34 | 1.85 | 79.31 |
Claims (11)
1., containing a preparation method for copper zinc catalyst, comprising:
(1), in the soluble salt solutions A of Zn, CO is passed into
2gas, reaction generates containing sediment slurries I;
(2), in sodium aluminate solution B, CO is passed into
2gas, generates containing sediment slurry II;
(3), by the sediment slurries II that contains containing sediment slurries I and step (2) gained of step (1) gained mix, under agitation aging, add basic copper carbonate time aging;
(4), the material that obtains of step (3) through washing, filter, dry, roasting, compression molding, obtains containing copper zinc catalyst;
Wherein, the plastic process in step (1) and step (2), reaction temperature is 30 ~ 90 DEG C, and during plastic, pH value controls is 6.0 ~ 11.0, and gelation time is 0.2 ~ 4.0 hour;
In step (3), aging temperature is 40 ~ 90 DEG C, and time aging, pH value controls is 7.0 ~ 12.0, and ageing time is 0.5 ~ 5.0 hour;
In step (3) gained material, copper/zinc mol ratio is 0.1 ~ 10.0, and (copper+zinc)/al mole ratio is 0.1 ~ 10.0.
2. in accordance with the method for claim 1, it is characterized in that the soluble-salt of Zn described in step (1) is nitrate and/or acetate; The concentration of the soluble salt solutions A of described Zn is 0.5 ~ 5.0mol/L; The concentration of the sodium aluminate solution B described in step (2) is 1.0 ~ 6.0mol/L.
3. in accordance with the method for claim 1, it is characterized in that the concentration of the soluble-salt of Zn in step (1) solution A is 1.0 ~ 3.0mol/L, in solution B, sodium metaaluminate concentration is 2.0 ~ 4.0mol/L.
4. in accordance with the method for claim 1, it is characterized in that, in step (1), passing into the CO in the soluble salt solutions of Zn
2the total amount of gas and zinc salt mol ratio are 2 ~ 7.
5. in accordance with the method for claim 1, it is characterized in that, in step (2), passing into CO in sodium aluminate solution
2the total amount of gas and sodium metaaluminate are with Al
2o
3the mol ratio of meter is 2 ~ 8.
6. in accordance with the method for claim 1, it is characterized in that, in step (3), aging temperature is 50 ~ 80 DEG C; Time aging, pH value controls is 7.5 ~ 11.0, and ageing time is 1.0 ~ 3.0 hours.
7. in accordance with the method for claim 1, it is characterized in that the plastic process CO used in step (1) and step (2)
2volumetric concentration 20v% ~ the 99v% of gas.
8. in accordance with the method for claim 1, it is characterized in that the plastic process in step (1) and step (2), reaction temperature is 40 ~ 80 DEG C, and during plastic, pH value controls is 7.0 ~ 10.0, and gelation time is 0.5 ~ 3.0 hour.
9. in accordance with the method for claim 1, it is characterized in that, in step (3) gained material, copper/zinc mol ratio is 0.2 ~ 5.0, (copper+zinc)/al mole ratio is 3.0 ~ 8.0.
10. in accordance with the method for claim 1, it is characterized in that step (4) described drying is 50 ~ 150 DEG C of dryings 1 ~ 24 hour, described roasting is 300 ~ 360 DEG C of roastings 1 ~ 16 hour.
11. in accordance with the method for claim 1, and it is characterized in that described containing copper zinc 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%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210443086.6A CN103801302B (en) | 2012-11-08 | 2012-11-08 | A kind of preparation method containing copper zinc catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210443086.6A CN103801302B (en) | 2012-11-08 | 2012-11-08 | A kind of preparation method containing copper zinc catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103801302A CN103801302A (en) | 2014-05-21 |
| CN103801302B true CN103801302B (en) | 2016-03-30 |
Family
ID=50698975
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210443086.6A Active CN103801302B (en) | 2012-11-08 | 2012-11-08 | A kind of preparation method containing copper zinc catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103801302B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109289854B (en) * | 2018-11-01 | 2020-10-27 | 西南化工研究设计院有限公司 | High-stability high-strength methanol synthesis catalyst and preparation method thereof |
| CN112023962B (en) * | 2019-06-03 | 2023-10-03 | 国家能源投资集团有限责任公司 | Catalyst for methanol synthesis, preparation method thereof and method for synthesizing methanol |
| CN115555028B (en) * | 2022-09-30 | 2023-09-05 | 四川蜀泰化工科技有限公司 | Methanol synthesis catalyst and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1398787A (en) * | 2002-05-31 | 2003-02-26 | 中国石油化工集团公司 | Prepn of gamma-alumina |
| CN101574649A (en) * | 2009-05-25 | 2009-11-11 | 来安县迅能催化剂有限公司 | Methanol catalyst preparation method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005020630A1 (en) * | 2005-05-03 | 2006-11-23 | Süd-Chemie AG | Preparation of Cu / Zn / Al catalysts via the formate route |
-
2012
- 2012-11-08 CN CN201210443086.6A patent/CN103801302B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1398787A (en) * | 2002-05-31 | 2003-02-26 | 中国石油化工集团公司 | Prepn of gamma-alumina |
| CN101574649A (en) * | 2009-05-25 | 2009-11-11 | 来安县迅能催化剂有限公司 | Methanol catalyst preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103801302A (en) | 2014-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105126845B (en) | Catalyst and preparation method for preparing ethanol by oxalate hydrogenation | |
| CN102407122B (en) | Preparation method of octylene aldehyde gas phase hydrogenation catalyst for octanol production | |
| CN103372441B (en) | Preparation method of methanol synthesis catalyst | |
| CN104624196B (en) | A kind of high-specific surface area fischer-tropsch synthetic catalyst and preparation method and application | |
| CN103372437B (en) | The preparation method of copper-zinc system catalyst | |
| CN103372439B (en) | The preparation method of catalst for synthesis of methanol | |
| CN105214672B (en) | A kind of preparation method for the catalyst for methanol that maximizes | |
| CN106238051A (en) | Catalyst for ethyl acetate preparation of ethanol by hydrogenating and its preparation method and application | |
| CN103372440B (en) | Preparation method of methanol synthesis catalyst | |
| CN103801302B (en) | A kind of preparation method containing copper zinc catalyst | |
| CN103372445B (en) | Preparation method of copper-zinc series catalyst | |
| CN103801301B (en) | A kind of preparation method of Cu-contained catalyst | |
| CN103551154B (en) | Preparation methods and catalysis method of dimethyl maleate hydrogenation catalyst | |
| CN106622256B (en) | A kind of preparation method of high concentration CO methanation catalyst | |
| CN103372444B (en) | A kind of preparation method of copper-based catalysts | |
| CN116060084A (en) | Alumina-supported copper-rare earth metal oxide catalyst and preparation method thereof | |
| CN112221509B (en) | Preparation method of high-stability methanol synthesis catalyst | |
| CN105964267B (en) | A kind of Cu-series catalyst for synthesizing methanol and preparation method thereof | |
| CN102950001A (en) | High-temperature-resistant methanol catalyst and preparation method thereof | |
| CN103372443B (en) | Preparation method of copper-based catalyst | |
| CN103372438B (en) | A kind of preparation method of Cu-contained catalyst | |
| CN103372442B (en) | Preparation method of copper-containing catalyst | |
| CN104353464B (en) | A kind of preparation method of high activity methanol catalyst | |
| CN106423202A (en) | Preparation method of rhodium-ruthenium composite catalyst for preparing ethyl alcohol through acetic acid hydrogenation | |
| CN107583650A (en) | A kind of copper-based carbon-oxide high-temperature conversion catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |