CN109092308A - A kind of extruded moulding method of silicon dioxide carried copper oxide catalyst - Google Patents
A kind of extruded moulding method of silicon dioxide carried copper oxide catalyst Download PDFInfo
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- CN109092308A CN109092308A CN201811183046.6A CN201811183046A CN109092308A CN 109092308 A CN109092308 A CN 109092308A CN 201811183046 A CN201811183046 A CN 201811183046A CN 109092308 A CN109092308 A CN 109092308A
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- copper oxide
- oxide catalyst
- silicon dioxide
- mixed
- dioxide carried
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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Abstract
The present invention provides a kind of extruded moulding methods of silicon dioxide carried copper oxide catalyst, including following component: powdered silica loaded copper oxide catalyst, strength agents, extrusion aid, silica solution and water will obtain plastic body after the above components are mixed；Or said components are divided into material A and material B, then material A and material B are mixed again, plastic body is obtained, wherein material A: powdered silica loaded copper oxide catalyst and silica solution being mixed, material A is obtained；Material B: strength agents, extrusion aid, water are mixed, and obtain material B；Plastic body mediates banded extruder using stainless steel, is then dried, then roast, obtains the preformed catalyst product of cylinder strip.The present invention can satisfy the requirement to catalyst strength.
Description
Technical field
The invention belongs to petrochemical catalyst technical fields, more particularly, to a kind of silicon dioxide carried copper oxide catalyzation
The extruded moulding method of agent.
Background technique
Silicon dioxide carried copper oxide catalyst is in preparing cyclohexanone by cyclohexanol dehydrogenation, dimethyl oxalate catalyst hydrogenolysis second
There is excellent catalytic performance in the reaction such as glycol.The processing and forming of catalyst is the important link of its application.Due to titanium dioxide
Reactor applied by silicon loaded copper oxide catalyst is mostly fixed-bed type shell-and-tube reactor, it is desirable that catalyst has centainly strong
Degree, prevent catalyst because in own wt pressure and reactor material impact due to breaking and Dusting, influence catalyst reaction performance and
Normal production safety.Extruded moulding is one of common shaping of catalyst technology.The silica supports class of extruded moulding is catalyzed
Often intensity is lower for agent, needs to be added strength aid and improves preformed catalyst intensity, to meet the actual needs standard.
Summary of the invention
In view of this, the present invention is directed to propose a kind of extruded moulding method of silicon dioxide carried copper oxide catalyst, energy
Enough requirements met to catalyst strength.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
A kind of extruded moulding method of silicon dioxide carried copper oxide catalyst, including following component: powdered silica
Loaded copper oxide catalyst, strength agents, extrusion aid, silica solution and water,
Plastic body will be obtained after the above components are mixed；
Or said components are divided into material A and material B, then material A and material B are mixed again, obtain plastic body,
In
Material A: powdered silica loaded copper oxide catalyst and silica solution are mixed, material A is obtained；
Material B: strength agents, extrusion aid, water are mixed, and obtain material B；
Plastic body mediates banded extruder using stainless steel, is then dried, then roast, obtains the shaped catalyst of cylinder strip
Agent product.Above-mentioned mixed process include but is not limited to ground and mixed, sieving mix, be stirred, mixing drum mix etc. mixing side
One of formula is a variety of, more preferably to be stirred.
Further, strength agents be selected from one of Bromide, stearate, tetraborate, metaborate and boric acid or
It is a variety of.
Further, extrusion aid be selected from soluble cellulose, organic multicomponent acid, organic polyhydric alcohol, atoleine, starch and
One of sesbania powder is a variety of.
Further, silica solution selection alkaline silica sol, neutral one of silica solution and acidic silicasol or a variety of, it is excellent
Choosing, silica solution is ammonia type silica solution and/or neutral silica solution.
Further, the quality of powdered silica loaded copper oxide catalyst account for preformed catalyst product quality 1~
50%, strength aid accounts for mediate after wet plastic body gross mass 0.1~50%, preferably 1%~20%, extrusion aid, which accounts for, to be pinched
The 0.5~50% of wet plastic body gross mass, preferably 1~30% after conjunction, the quality of silica solution is with SiO2Meter, accounts for molding and urges
The 0.1~50% of agent gross mass, preferably 1~30%.
Further, being mixed to get the temperature during plastic body is 10~100 DEG C.
Further, drying temperature is 50~150 DEG C；2~48h of drying time；Dry atmosphere is vacuum, inert gas gas
Atmosphere or air atmosphere, preferably air atmosphere.
Further, maturing temperature is 250~700 DEG C；2~12h of calcining time；Calcination atmosphere is vacuum, inert gas
Atmosphere, air atmosphere, oxygen content 0.1~50% mixed atmosphere, mixed atmosphere includes but is not limited to oxygen/nitrogen, oxygen/helium
The gaseous mixture of gas, oxygen/argon composition, the preferably mixed atmosphere or air atmosphere of oxygen content 0.1~50%.
Silicon dioxide carried copper oxide catalyst can be prepared according to existing patent and open source literature.Referenced patent and ginseng
Examine document: CN98812476.9, CN104511277A, CN106890641A, CN104437488A, chemical industry and engineering skill
Art, 03 (2013) 10-13；Jilin University's journal, 02 (2007) 293-296 etc..
Due to carrier nature and requirement of the industrial application to catalyst strength, carrier is done with silica
Catalyst is usually formed with tabletting method especially using amorphous silica as the catalyst of carrier.In actual production
Tabletting molding process usually requires to be granulated and the two-step processs processes such as tabletting, relatively complicated, the high requirements on the equipment；And it squeezes
Moulding process flow process is simple, and general add after auxiliary agent is mediated can carry out extrusion, relatively low to equipment requirement.Molecular sieve
Catalyst relatively easily carries out extruded moulding, but for using silica as the catalyst of carrier, simply by extruded moulding institute
The catalyst strength of preparation is lower, is easily broken, and anti-pressure ability is poor, it is difficult to meet practical application, need to investigate and add centainly
The mechanical strength of auxiliary agent raising extruded moulding catalyst.
Compared with the existing technology, the extruded moulding method of silicon dioxide carried copper oxide catalyst of the present invention has
Following advantage:
The preformed catalyst product tool that the extruded moulding method of inventive silica loaded copper oxide catalyst is prepared
There is preferable anti-pressure ability, it is non-breakable, transport in industrial actual production, filling and use process are able to satisfy to catalyst strength
Requirement.
Specific embodiment
In addition to being defined, technical term used in following embodiment has universal with those skilled in the art of the invention
The identical meanings of understanding.Test reagent used in following embodiment is unless otherwise specified conventional biochemical reagent；It is described
Experimental method is unless otherwise specified conventional method.
Below with reference to comparative example and embodiment, the present invention will be described in detail.
The mechanical strength of preformed catalyst product is tested on the intelligent testing machine for particle of ZQJ II.
Comparative example 1:
Mass fraction is accounted for the ammonia type silica solution (SiO of preformed catalyst quality 25%230%) and powdery mass content is
Silicon dioxide carried copper oxide catalyst is sufficiently mixed to obtain material A；The starch of material A mass fraction 2%, 1% lemon will be accounted for
Sour and 10% water is sufficiently mixed to obtain material B；It is sufficiently mixed material A and material B under continuous stirring condition and is kneaded into wet modeling
Property body, using stainless steel mediate banded extruder, wet strip solid cylinder is extruded by the orifice plate of φ 2.0mm, then 120 DEG C
Under the conditions of dry 12h, then roast 5h at 450 DEG C in air atmosphere and obtain cylinder strip preformed catalyst sample.
Embodiment 1
Comparative example 1 is repeated, but changes neutral silica solution into ammonia type silica solution, the composition of material B is changed to and accounts for material A quality
The starch of score 2%, 1% citric acid, 5% glycerol, 2% boric acid and 10% water obtain preformed catalyst sample,
Mechanical strength increases 191.5% than 1 sample of comparative example.
Embodiment 2
Comparative example 1 is repeated, but changes neutral silica solution into ammonia type silica solution, the composition of material B is changed to and accounts for material A quality
The starch of score 2%, 1% citric acid, 5% glycerol, 2% dipotassium tetraborate and 10% water obtain preformed catalyst sample
Product, mechanical strength increase 195.8% than 1 sample of comparative example.
Embodiment 3
Comparative example 1 is repeated, but changes neutral silica solution into ammonia type silica solution, the composition of material B is changed to and accounts for material A quality
The starch of score 2%, 1% citric acid, 5% glycerol, 2% potassium metaborate and 10% water obtain preformed catalyst sample
Product, mechanical strength increase 172.3% than 1 sample of comparative example.
Embodiment 4
Comparative example 1 is repeated, but the mass fraction of dipotassium tetraborate is increased to 5%, obtains preformed catalyst sample, it is mechanical
Intensity increases 200.9% than 1 sample of comparative example.
Embodiment 5
Comparative example 1 is repeated, but the mass fraction of boric acid is increased to 5%, obtains preformed catalyst sample H, it is mechanical strong
Degree increases 196.4% than 1 sample of comparative example.
Embodiment 6
Comparative example 1 is repeated, but changes neutral silica solution into ammonia type silica solution, the composition of material B is changed to and accounts for material A quality
The starch of score 4%, 5% glycerol, 5% boric acid and 10% water, obtain preformed catalyst sample, mechanical strength compares
1 sample of ratio increases 200.7%.
Embodiment 7
Comparative example 1 is repeated, but changes neutral silica solution into ammonia type silica solution, the composition of material B is changed to and accounts for material A quality
The starch of score 4%, 5% glycerol, 5% dipotassium tetraborate and 10% water, obtain preformed catalyst sample, mechanical strength
205.0% is increased than 1 sample of comparative example.
Embodiment 8
Comparative example 1 is repeated, but changes neutral silica solution into ammonia type silica solution, the composition of material B is changed to and accounts for material A quality
The starch of score 4%, 5% glycerol, 5% potassium metaborate and 10% water, obtain preformed catalyst sample, mechanical strength
194.0% is increased than 1 sample of comparative example.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of extruded moulding method of silicon dioxide carried copper oxide catalyst, it is characterised in that: including following component: powdery
Silicon dioxide carried copper oxide catalyst, strength agents, extrusion aid, silica solution and water,
Plastic body will be obtained after the above components are mixed；
Or said components are divided into material A and material B, then material A and material B are mixed again, obtain plastic body, wherein
Material A: powdered silica loaded copper oxide catalyst and silica solution are mixed, material A is obtained；
Material B: strength agents, extrusion aid, water are mixed, and obtain material B；
Plastic body mediates banded extruder using stainless steel, is then dried, then roast, and the preformed catalyst for obtaining cylinder strip produces
Product.
2. the extruded moulding method of silicon dioxide carried copper oxide catalyst according to claim 1, it is characterised in that: strong
It spends agent and is selected from one of Bromide, stearate, tetraborate, metaborate and boric acid or a variety of.
3. the extruded moulding method of silicon dioxide carried copper oxide catalyst according to claim 1, it is characterised in that: help
It squeezes agent and is selected from one of soluble cellulose, organic multicomponent acid, organic polyhydric alcohol, atoleine, starch and sesbania powder or more
Kind.
4. the extruded moulding method of silicon dioxide carried copper oxide catalyst according to claim 1, it is characterised in that: silicon
Colloidal sol selects alkaline silica sol, neutral one of silica solution and acidic silicasol or a variety of, it is preferred that silica solution is ammonia type silicon
Colloidal sol and/or neutral silica solution.
5. the extruded moulding method of silicon dioxide carried copper oxide catalyst according to claim 1, it is characterised in that: powder
The quality of the silicon dioxide carried copper oxide catalyst of shape accounts for the 1~50% of preformed catalyst product quality, and strength aid accounts for kneading
The 0.1~50% of wet plastic body gross mass afterwards, preferably 1%~20%, extrusion aid accounts for mediate after the wet total matter of plastic body
The 0.5~50%, preferably 1~30% of amount, the quality of silica solution is with SiO2Meter, account for preformed catalyst gross mass 0.1~
50%, preferably 1~30%.
6. the extruded moulding method of silicon dioxide carried copper oxide catalyst according to claim 1, it is characterised in that: mixed
Closing the temperature during obtaining plastic body is 10~100 DEG C.
7. the extruded moulding method of silicon dioxide carried copper oxide catalyst according to claim 1, it is characterised in that: dry
Dry temperature is 50~150 DEG C；2~48h of drying time；Dry atmosphere for vacuum, inert gas atmosphere or air atmosphere, preferably
Air atmosphere.
8. the extruded moulding method of silicon dioxide carried copper oxide catalyst according to claim 1, it is characterised in that: roasting
Burning temperature is 250~700 DEG C；2~12h of calcining time；Calcination atmosphere is vacuum, inert gas atmosphere, air atmosphere, oxygen content
0.1~50% mixed atmosphere, mixed atmosphere include but is not limited to oxygen/nitrogen, oxygen/helium, oxygen/argon composition it is mixed
Close gas, the preferably mixed atmosphere or air atmosphere of oxygen content 0.1~50%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113426447A (en) * | 2021-06-22 | 2021-09-24 | 中石化南京化工研究院有限公司 | Method for forming high-strength copper-silicon catalyst |
| WO2023104563A1 (en) * | 2021-12-08 | 2023-06-15 | Evonik Operations Gmbh | Catalytic shaped bodies comprising copper phyllosilicate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113426447A (en) * | 2021-06-22 | 2021-09-24 | 中石化南京化工研究院有限公司 | Method for forming high-strength copper-silicon catalyst |
| WO2023104563A1 (en) * | 2021-12-08 | 2023-06-15 | Evonik Operations Gmbh | Catalytic shaped bodies comprising copper phyllosilicate |
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