CN106540700A - A kind of preparation method of High-temperature-resmethanol methanol catalyst - Google Patents
A kind of preparation method of High-temperature-resmethanol methanol catalyst Download PDFInfo
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- CN106540700A CN106540700A CN201510587978.7A CN201510587978A CN106540700A CN 106540700 A CN106540700 A CN 106540700A CN 201510587978 A CN201510587978 A CN 201510587978A CN 106540700 A CN106540700 A CN 106540700A
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Abstract
The invention belongs to catalyst and its preparing technical field, are related to a kind of preparation method of high temperature resistant catalst for synthesis of methanol, serve as interval body with rich aluminium profiles spinelle and take rugged catalyst, prevent the aggregation of active component Cu high temperature sintering and catalyst body phase from subsiding.Catalyst preparation is initially with parent precipitant and carrier precipitation agent difference precipitate C u, Zn mixed nitrate mother solution and Al and metal M（M is the one kind in Zn, Mg, Mn, Ca, and its M/Al mol ratio is 1:2~1:8）Mixed solution, parent precipitate and carrier precipitation thing are obtained Jing after aging washing；Rich aluminium profiles spinelle is mixed with above-mentioned parent precipitate, carrier precipitation thing beating according to a certain ratio subsequently, subsequent sucking filtration, drying, roasting obtain a kind of high temperature resistant catalst for synthesis of methanol.
Description
Technical field
The invention belongs to catalst for synthesis of methanol preparing technical field, and in particular to a kind of preparation method of catalst for synthesis of methanol carrier.
Background technology
Methanol is important basic chemical industry product, and current domestic production capacity has exceeded 5,000,000 ten thousand tons.Last century the mid-1960s are developed into by Material synthesis methanol technics of synthesis gas in the world, has started to adopt low temperature（Less than 300 DEG C）Low pressure（5.0MPa）Copper-based catalysts.The catalyst main component is CuO/ZnO/Al2O3, the appearance that main representative unit has ICI companies of Britain and Lurgi companies of Germany, the catalyst realizes the booming of methanol industry.In recent decades in the industry in order to more effectively reduce unit methanol production cost, Lurgi companies took the lead in proposing big methanol in 1997（Megamethanol）Concept, methanol synthesizer maximizes becomes the direction of methanol industry development.The Enlargement Tendency not only to it is advanced efficiently, the reactor of reasonable energy utilization put forward higher requirement, and to supporting catalyst it is also proposed that harsher requirement, thus developing resistant to elevated temperatures catalst for synthesis of methanol becomes one of emphasis direction of research and development.
The heat-resistant activity of catalyst in order to adapt to the use condition of big methanol device, is further improved, in decades, research and development of the various countries researchers to new catalst for synthesis of methanol are done a lot of work, two aspects are concentrated mainly on to copper-based catalysts research：Other components beyond addition copper removal zinc-aluminium are modified, and on the other hand improve the preparation method and technique of optimization catalyst.
The content of the invention
It is an object of the present invention to provide a kind of preparation method of high temperature resistant catalst for synthesis of methanol, further improves the high-temperature heat-resistance activity and stability of conventional synthesis catalyst for methanol.
The method is mainly characterized in that during prepared by catalyst carrier, adulterated by rich aluminium profiles spinelle micropowder, rich aluminium profiles spinelle is present with interval body form, the catalyst pore structure is relatively large, catalyst body internal diffusion efficiency factor is high, institute's load active component is not easily runed off, moreover it is possible to facilitate the recycling of catalyst.
High temperature resistant methanol synthesis catalyst of the present invention is respectively adopted two methods of co-precipitation and wet mixing, parent precipitant addition Cu, Zn mixed nitrate solution is co-precipitated, parent precipitate is obtained after aging washing；Same add carrier precipitation agent is co-precipitated in aluminum soluble salt and soluble metallic salt M mixed solutions, and carrier precipitation thing is obtained after aging washing；Rich aluminium profiles spinelle is mixed into beating by proportioning with above-mentioned parent precipitate, carrier precipitation thing, subsequent sucking filtration, drying, roasting obtain high temperature resistant catalst for synthesis of methanol.
The parent precipitant and carrier precipitation agent are Na2CO3、NaHCO3、NaOH、K2CO3、KHCO3、KOH、NH3·H2One kind in O, carbamide.
Preferably, preparation technology flow process is as follows：
At a temperature of 30 DEG C ~ 90 DEG C, parent precipitant of the concentration for 0.3 ~ 1.5mol/L is added in Cu, Zn mixed nitrate solution, coprecipitation reaction is carried out, control endpoint pH 6.0 ~ 7.5, aging 10 ~ 80min is obtained reactive precursor after deionized water wash.
Equally, according to above-mentioned steps, at a temperature of 30 DEG C ~ 90 DEG C, carrier precipitation agent of the concentration for 0.3 ~ 1.5mol/L is added to into aluminum nitrate and metal M（Wherein M is the one kind in Zn, Mg, Mn, Ca）In soluble-salt mixed solution, coprecipitation reaction is carried out, control endpoint pH 6.0 ~ 12, aging 10 ~ 80min is obtained carrier paste after deionized water wash.
It is prepared by rich aluminium profiles Spinel：Spinel chemical molecular formula is MAl2O4, wherein M be Zn, Mg, Mn, Ca, in one kind, its M/Al mol ratio be 1:2~1:8.It is 1 that the solubility salt of metal M is pressed mol ratio:2~1:8 ratio mixes co-precipitation with aluminum nitrate, different according to metal precipitates ionization constant, and it is 6.0 ~ 12.0 to adjust endpoint pH, and mixed solution temperature control is between 20 DEG C ~ 100 DEG C, then Jing is aging, washing, sucking filtration obtain filter cake；The filter cake is in the advance 1h ~ 6h of 100 DEG C ~ 120 DEG C dryings, then is rapidly heated to 600 DEG C ~ 1200 DEG C calcining 0.5h ~ 1h with 20 DEG C/min in revolving burner, and rich aluminium profiles spinelle is obtained, and pulverizer is crushed to micropowder（100 mesh ~ 200 mesh）It is stand-by；
The high temperature resistant catalst for synthesis of methanol that the present invention program is prepared, the atmosphere of higher temperatures is resistant to than the catalyst that traditional method is prepared, suitable for synthesising gas systeming carbinol technique under high-speed, it is particularly suitable for the use of mesohigh synthesizing methanol maximization device, that is, the big methanol industry device of now common megaton.
Specific embodiment
Below example is to further illustrate related content of the invention.
Embodiment 1
Potassium bicarbonate solution of the concentration for 0.3mol/L is added in Cu, Zn mixed nitrate saline solution of 0.2mol/L, coprecipitation reaction is carried out, co-precipitation temperature is 50 DEG C, parent precipitate Jing deionized water wash, cleaner liquid endpoint pH is 7.2, obtains parent precipitate slurry；Same step is added to the ammonia of 0.6mol/L in aluminum nitrate and metal M solubility mixed aqueous solutions, and carrier precipitation thing slurry is obtained after co-precipitation, and endpoint pH is controlled to 7.0；
It is 1 that the solubility salt of metal Zn is pressed mol ratio:2 ratio mixes co-precipitation with aluminum nitrate, different according to metal precipitates ionization constant, and it is 9.0 to adjust endpoint pH, and mixed solution temperature control is at 20 DEG C, then Jing is aging, washing, sucking filtration obtain filter cake；The filter cake is in the advance 1h of 100 DEG C ~ 120 DEG C dryings, then is rapidly heated to 800 DEG C of calcining 0.5h with 20 DEG C/min in revolving burner, and rich aluminium profiles spinelle is obtained, and pulverizer is crushed to micropowder（100 mesh ~ 200 mesh）It is stand-by.
Parent precipitate, aluminium riched spinel are mixed into beating with carrier precipitation thing slurry again, sucking filtration, drying, roasting, molding procedure make high temperature resistant methanol synthesis catalyst A.
Embodiment 2
Potassium bicarbonate solution of the concentration for 0.5mol/L is added in Cu, Zn mixed nitrate saline solution of 0.2mol/L, coprecipitation reaction is carried out, co-precipitation temperature is 50 DEG C, parent precipitate Jing deionized water wash, cleaner liquid endpoint pH is 6.0, obtains parent precipitate slurry；Same step is added to the ammonia of 0.6mol/L in aluminum nitrate and metal M solubility mixed aqueous solutions, and carrier precipitation thing slurry is obtained after co-precipitation, and endpoint pH is controlled to 6.0；
It is 1 that the solubility salt of metal Mg is pressed mol ratio:4 ratio mixes co-precipitation with aluminum nitrate, different according to metal precipitates ionization constant, and it is 6.0 to adjust endpoint pH, and mixed solution temperature control is at 50 DEG C, then Jing is aging, washing, sucking filtration obtain filter cake；The filter cake is in the advance 2h of 100 DEG C ~ 120 DEG C dryings, then is rapidly heated to 600 DEG C of calcining 1h with 20 DEG C/min in revolving burner, and rich aluminium profiles spinelle is obtained, and pulverizer is crushed to micropowder（100 mesh ~ 200 mesh）It is stand-by.
Parent precipitate, aluminium riched spinel are mixed into beating with carrier precipitation thing slurry again, sucking filtration, drying, roasting, molding procedure make high temperature resistant methanol synthesis catalyst B.
Embodiment 3
Sodium hydroxide solution of the concentration for 0.3mol/L is added in Cu, Zn mixed nitrate saline solution of 0.2mol/L, coprecipitation reaction is carried out, co-precipitation temperature is 50 DEG C, parent precipitate Jing deionized water wash, cleaner liquid endpoint pH is 6.5, obtains parent precipitate slurry；Same step is added to the ammonia of 0.6mol/L in aluminum nitrate and metal M solubility mixed aqueous solutions, and carrier precipitation thing slurry is obtained after co-precipitation, and endpoint pH is controlled to 9.0；
It is 1 that the solubility salt of metal Mn is pressed mol ratio:6 ratio mixes co-precipitation with aluminum nitrate, different according to metal precipitates ionization constant, and it is 8.0 to adjust endpoint pH, and mixed solution temperature control is at 80 DEG C, then Jing is aging, washing, sucking filtration obtain filter cake；The filter cake is in the advance 6h of 100 DEG C ~ 120 DEG C dryings, then is rapidly heated to 1000 DEG C of calcining 0.5h with 20 DEG C/min in revolving burner, and rich aluminium profiles spinelle is obtained, and pulverizer is crushed to micropowder（100 mesh ~ 200 mesh）It is stand-by.
Parent precipitate, aluminium riched spinel are mixed into beating with carrier precipitation thing slurry again, sucking filtration, drying, roasting, molding procedure make high temperature resistant methanol synthesis catalyst C.
Embodiment 4
Potassium bicarbonate solution of the concentration for 0.3mol/L is added in Cu, Zn mixed nitrate saline solution of 0.2mol/L, coprecipitation reaction is carried out, co-precipitation temperature is 50 DEG C, parent precipitate Jing deionized water wash, cleaner liquid endpoint pH is 7.5, obtains parent precipitate slurry；Same step is added to the ammonia of 0.6mol/L in aluminum nitrate and metal M solubility mixed aqueous solutions, and carrier precipitation thing slurry is obtained after co-precipitation, and endpoint pH is controlled to 12.0；
It is 1 that the solubility salt of metal Ca is pressed mol ratio:8 ratio mixes co-precipitation with aluminum nitrate, different according to metal precipitates ionization constant, and it is 12.0 to adjust endpoint pH, and mixed solution temperature control is at 100 DEG C, then Jing is aging, washing, sucking filtration obtain filter cake；The filter cake is in the advance 3h of 100 DEG C ~ 120 DEG C dryings, then is rapidly heated to 1200 DEG C of calcining 1h with 20 DEG C/min in revolving burner, and rich aluminium profiles spinelle is obtained, and pulverizer is crushed to micropowder（100 mesh ~ 200 mesh）It is stand-by.
Parent precipitate, aluminium riched spinel are mixed into beating with carrier precipitation thing slurry again, sucking filtration, drying, roasting, molding procedure make high temperature resistant methanol synthesis catalyst D.
Claims (6)
1. a kind of preparation method of high temperature resistant catalst for synthesis of methanol, it is characterised in that：Parent precipitant addition Cu, Zn mixed nitrate solution is co-precipitated, parent precipitate after aging washing, is obtained；Same add carrier precipitation agent is co-precipitated in aluminum soluble salt and soluble metallic salt M mixed solutions, and carrier precipitation thing is obtained after aging washing；Rich aluminium profiles spinelle is mixed into beating by proportioning with above-mentioned parent precipitate, carrier precipitation thing, subsequent sucking filtration, drying, roasting obtain high temperature resistant catalst for synthesis of methanol.
2. preparation method according to claim 1, it is characterised in that parent precipitant and carrier precipitation agent are Na2CO3、NaHCO3、NaOH、K2CO3、KHCO3、KOH、NH3·H2One kind in O, carbamide.
3. preparation method according to claim 1, it is characterised in that soluble metallic salt M is one or two in Zn, Mg, Mn, Ca.
4. preparation method according to claim 1, it is characterised in that precipitation endpoint pH is 6.0 ~ 12.0.
5. preparation method according to claim 1, it is characterised in that ageing time is 10min ~ 80min.
6. preparation method according to claim 1, it is characterised in that rich aluminium profiles Spinel Preparation Method is as follows：
Spinel chemical molecular formula is MAl2O4, wherein M is the one kind in Zn, Mg, Mn, Ca, and its M/Al mol ratio is 1:2~1:8；
The solubility salt of metal M is mixed into co-precipitation by mol ratio with aluminum nitrate, different according to metal precipitates ionization constant, it is 6.0 ~ 12.0 to adjust endpoint pH, mixed solution temperature control is between 20 DEG C ~ 100 DEG C, then Jing is aging, washing, sucking filtration obtain filter cake；
Above-mentioned filter cake is in the advance 1h ~ 6h of 100 DEG C ~ 120 DEG C dryings, then is rapidly heated to 600 DEG C ~ 1200 DEG C calcining 0.5h ~ 1h with 20 DEG C/min in revolving burner, obtains rich aluminium profiles spinelle, is crushed to 100 mesh ~ 200 mesh micropowders stand-by.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107961779A (en) * | 2017-11-24 | 2018-04-27 | 江西省隆南药化有限公司 | A kind of catalyst for musk ambrette grass phenol and preparation method thereof, and the method using the catalyst preparation thymol |
| CN109420509A (en) * | 2017-08-23 | 2019-03-05 | 中国石油化工股份有限公司 | A kind of synthesising gas systeming carbinol bimetallic catalyst and preparation method thereof |
| CN115555028A (en) * | 2022-09-30 | 2023-01-03 | 四川蜀泰化工科技有限公司 | High-activity, high-selectivity and high-stability methanol synthesis catalyst and preparation method thereof |
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| CN1360973A (en) * | 2000-12-28 | 2002-07-31 | 中化化工科学技术研究总院 | Catalyst for synthetic ammonia coproducing methanol and its prepn |
| CN101157041A (en) * | 2007-07-30 | 2008-04-09 | 山东师范大学 | A preparation method of nanometer cuprum base methanol synthetic catalyst |
| CN101327431A (en) * | 2008-07-31 | 2008-12-24 | 西北化工研究院 | Process for preparing synthetic methanol catalyst |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1360973A (en) * | 2000-12-28 | 2002-07-31 | 中化化工科学技术研究总院 | Catalyst for synthetic ammonia coproducing methanol and its prepn |
| CN101157041A (en) * | 2007-07-30 | 2008-04-09 | 山东师范大学 | A preparation method of nanometer cuprum base methanol synthetic catalyst |
| CN101327431A (en) * | 2008-07-31 | 2008-12-24 | 西北化工研究院 | Process for preparing synthetic methanol catalyst |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109420509A (en) * | 2017-08-23 | 2019-03-05 | 中国石油化工股份有限公司 | A kind of synthesising gas systeming carbinol bimetallic catalyst and preparation method thereof |
| CN107961779A (en) * | 2017-11-24 | 2018-04-27 | 江西省隆南药化有限公司 | A kind of catalyst for musk ambrette grass phenol and preparation method thereof, and the method using the catalyst preparation thymol |
| CN107961779B (en) * | 2017-11-24 | 2020-10-23 | 江西省隆南药化有限公司 | Catalyst for synthesizing thymol, preparation method thereof and method for preparing thymol by using catalyst |
| CN115555028A (en) * | 2022-09-30 | 2023-01-03 | 四川蜀泰化工科技有限公司 | High-activity, high-selectivity and high-stability methanol synthesis catalyst and preparation method thereof |
| 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 |
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