CN104888864A - Honeycomb nest hydrogenation protecting agent - Google Patents
Honeycomb nest hydrogenation protecting agent Download PDFInfo
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- CN104888864A CN104888864A CN201510213109.8A CN201510213109A CN104888864A CN 104888864 A CN104888864 A CN 104888864A CN 201510213109 A CN201510213109 A CN 201510213109A CN 104888864 A CN104888864 A CN 104888864A
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Abstract
A honeycomb nest hydrogenation protecting agent is prepared from 1-60% of alumina powder, 5-50% of kaolin, 0.1-15% of talcum powder, 5-60% of clay, 0.5-10% of an alkaline solvent, and 0.1-5% of an auxiliary material. The unit cross section area of the above product has more and denser through holes, so the external specific surface area of the product is greatly increased and reaches above 5000m<2>/m<3>, so a reaction raw material and the protecting agent have a larger contact and reaction area. The void fraction of the product reaches 30-70%, the water absorption rate reaches 10-50%, and the appropriate water absorption rate makes the protecting agent adsorb more active substances, so the absorption rate of adsorbed impurities is improved, and the catalysis effect is improved; and the radial crushing strength of the product is 50-500N/granule of the product, the product cannot be fragmented when 50-500N is applied to the two axial ends of the product, and maintains integrity, so the strength is improved, and the service life is prolonged.
Description
Technical field
The present invention relates to a kind of hydrogenation protecting agent for refining oil, in the industry fixed bed hydrogenation reactor such as petrochemical industry, chemical industry.Be specifically related to a kind of cellular Bird's Nest hydrogenation protecting agent (or claiming Bird's Nest honeycomb ceramic body, Bird's Nest honeycomb propping agent or Bird's Nest proppant etc.).
Background technology
In the fixed bed hydrogenation reactors of industry especially to residual oil, the impure more feedstock oil gas disposal of coal tar wet goods such as oil refining, petrochemical industry, chemical industry, solid deposits main in its raw material is carbon deposit and metal sulfide, wherein a part enters into the duct of catalyst, and another part is then deposited on catalyst granules outer surface.Through long term accumulation, beds pressure drop is increased gradually, finally blocks reactor.Therefore, for extending the cycle of operation and major catalyst service life of commercial plant, the hydrogenation protecting agent of certain altitude must above the major catalyst bed in fixed bed hydrogenation reactor, generally all be loaded.
And development of new protective agent; its fundamental guiding ideology uses the protective agent of difformity, character and performance to carry out rational gradation composition; farthest effectively can filter, adsorb and remove in raw material and react the various impurity such as carbon deposit, metal impurities generated; the pressure reduction that the major catalyst of protection lower bed layer prevents its local stoppages and causes increases rapidly, and final purpose is the service cycle extending commercial plant.
The hydrogenation protecting agent a great variety that current market uses, its profile has spherical, the plurality of specifications product such as column, Raschig ring, vane rings, honeycomb column type, its shape, size, material, activity differ, its effect is also different, for the hydrogenation protecting agent being seated in upper strata, its Main Function is effective filtration, adsorbs the micro-solid impurity in its feedstock oil and remove the very high organic metal impurity of the reactivity such as iron, vanadium; And existing existing various hydrogenation protecting agent is not very good in this respect, although such as existing the most frequently used Raschig ring and vane rings voidage its specific area comparatively large is less, and the too large not easily impurity trapped of intermediate throughholes.The Bird's Nest ceramic honey comb applied gradually is started recent years at refining art, its outer void rate and external surface area larger, interception impurity energy force rate Raschig ring etc. also significantly improves, but due to the restriction of composition of raw materials before and manufacturing process, the density of its through hole can only accomplish 900 order (cpsi, namely interior per square inch number of openings, via densities or also can be understood as the duct number of hole density namely per square inch on cross section) below, cause the specific area contacted with reaction medium little, dust removal rate is low; And ratio of height to diameter (product height and natural scale) is generally greater than 1/4; crank, inclination can be caused after filling like this in hydrogenation protecting agent; the impurity making to flow in radial direction through hole and hydrogenation reactor, the direction of air-flow are inconsistent; cause to flutter and catch the reduction of impurity efficiency, have a strong impact on the result of use of hydrogenation protecting agent.
Summary of the invention
The present invention is directed to the above-mentioned deficiency of prior art, provide a kind of via densities to reach more than 900 orders, ratio of height to diameter is less than 1/4, can also reach the cellular Bird's Nest hydrogenation protecting agent of higher finished product sintering qualified rate simultaneously.
In order to solve the problems of the technologies described above; the technical solution used in the present invention is: the agent of a kind of cellular Bird's Nest hydrogenation protecting; the raw materials of this hydrogenation protecting agent comprises: alumina powder 1 ~ 60%, kaolin 5 ~ 50%, talcum powder 0.1-15%, clay 5 ~ 60%; basic solvent material 0.5 ~ 10%, auxiliary material 0.1 ~ 5%.
As preferably, the raw materials of described cellular Bird's Nest hydrogenation protecting agent comprises: alumina powder 5 ~ 50%, kaolin 10 ~ 45%, talcum powder 1-12%, clay 10 ~ 55%, basic solvent material 2 ~ 8%, auxiliary material 0.5 ~ 4%.
Basic solvent material of the present invention is the mixture of albite, potassic feldspar, calcium carbonate and magnesium carbonate.
Auxiliary material of the present invention are cellulose; The present invention adopts cellulose main purpose for increasing the cohesive of proppant, more easy-formation, and is more conducive to shaping, the cutting of proppant, and not cracky, improves yield rate.
The final products of cellular Bird's Nest hydrogenation protecting of the present invention agent, its main chemical compositions comprises: Al
2o
315-90%, SiO
215-90%, CaO+MgO 0.2-11%, K
2o+Na
2o 0.2-11%, Fe
2o
3+ TiO
20.2-5.5%.
The final products of cellular Bird's Nest hydrogenation protecting agent of the present invention, it meets: (1) external form is cellular cylinder, and its external diameter is at 3-45mm; (2) density of its cellular through hole is greater than 900 order cpsi; (3) its ratio of height to diameter is less than 1/4; (4) cross-sectional area of its cellular through hole is triangle.
The present invention also provides the preparation method of a kind of above-mentioned cellular Bird's Nest hydrogenation protecting agent, and preparation process comprises:
(1) pug formula: according to formula rate: alumina powder 1 ~ 60%, kaolin 5 ~ 50%, talcum powder 0.1-15%, clay 5 ~ 60%, basic solvent material 0.5 ~ 10%, auxiliary material 0.1 ~ 5%;
Or
Alumina powder 5 ~ 50%, kaolin 10 ~ 45%, talcum powder 1-12%, clay 10 ~ 55%, basic solvent material 2 ~ 8%, auxiliary material 0.5 ~ 4%, take each raw material;
(2) batch mixing: the powder of step (1) is dropped into kneader or batch mixer, adds water and oil carries out pug kneading, the pug be uniformly mixed;
(3) by the honeycomb porcelain mold of corresponding order number by extruded for the pug processed;
(4) cut: by regulating cutting wire and cutter spacing, semi-finished product base substrate and the extruded pug of step (3) are directly cut into the cylinder of certain length, then roasting becomes the agent of cellular Bird's Nest hydrogenation protecting; Or then first for pug extruded for step (3) roasting is cut into the small cylinder that ratio of height to diameter is less than 1/4, be the agent of cellular Bird's Nest hydrogenation protecting.
The amount that step of the present invention (2) adds water is the 12-20% of step (1) raw material weight, and the amount adding oil is the 0.5-10% of step (1) raw material weight; The oils that described oil is rapeseed oil, trench wet goods plays lubrication; Why the present invention adds oil mainly conveniently lubricating release in this step, improves the water retention property of pug, dry, not cracked, can also improve the plasticity of pug simultaneously, be more conducive to machine-shaping.
Honeycomb porcelain mold (the ceramic honey comb mould of the corresponding order number of above-mentioned steps of the present invention (3), industry traditional dies product, be generally the stainless steel mould with multiple hole on panel, specifically can with reference to the introduction of industry about ceramic honey comb mould) order number be the ceramic honey comb mould molding product of 600 orders (cpsi), pug squeezes out from above-mentioned honeycomb die the hydrogenation protecting agent initial model that rear formation has hole count; Because the shrinkage factor after the present invention has selected suitable ceramic raw materials formulation to make its product roasting (is mainly axial shrinkage rate, radial contraction can be ignored) reach more than 25%, thus ensure that its via densities of finished product after burning till can reach more than 900 orders.
Semi-finished product base substrate and the extruded pug of step (3) are directly cut into the cylinder of certain length by above-mentioned steps of the present invention (4), described certain length specifically reaches more than 25% this rule according to the shrinkage factor (being mainly axial shrinkage rate) after product roasting and cuts, ensure that its ratio of height to diameter of finished product after roasting meets and be less than 1/4, as half-finished diameter be 5mm, high be 2.5mm, now ratio of height to diameter is 1/2, shrinkage factor is 60%, then burning till rear ratio of height to diameter is 1/5.Thus cut half-finished length according to customer requirement and shrinkage factor.
The above-mentioned sintering temperature of the present invention is 1200-1400 DEG C, and roasting time is 15-25h.
Product of the present invention can directly use as the agent of inertia Bird's Nest hydrogenation protecting also can make the agent of active Bird's Nest hydrogenation protecting by a certain amount of active catalyst component of dipping.
Advantage of the present invention and beneficial effect:
1. the present invention utilize shrinkage factor large material as raw material; by matching suitable composition of raw materials; make its product can have good extruded effect; can ensure again to produce the cellular Bird's Nest protective agent that via densities reaches more than 900 orders when percent of firing shrinkage is very large, higher finished product sintering qualified rate can also be reached simultaneously.
2. its unit section area of product of the present invention is interior by having more closeer through holes, can considerably increase the external surface area of product, reach 5000m
2/ m
3above, reaction raw materials and protective agent is made to have larger contact and response area.Its voidage of product of the present invention reaches 30-70%, and water absorption rate reaches 10-50%, and suitable water absorption rate can make protective agent can adsorb more active material, thus improves the absorptivity of adsorbing contaminant, improves catalytic effect; The radial crushing strength of product of the present invention is 50-500N/, i.e. one or a title product, and the dynamics applying 50-500N at axial two ends is not cracked, keeps integrality, improves intensity and service life.
3. the present invention is due to the increase of via densities, then the less effect that can significantly improve filtration and adsorbing contaminant of the area of each through hole, and for better adsorbing interception impurity, its through hole generally adopts triangle.
4. protective agent of the present invention be ratio of height to diameter be less than 1/4 slim, most protective agent cross section can be made when reactor charge upwards, be conducive to reducing reactor pressure decrease, and improve interception impurity effect.
5. the present invention is because of its denser mesh-structured and more bigger serface, fine and closely woven cutting can be carried out to greatest extent to the gas-liquid flowed through, and make the contact of cold hydrogen and raw material and heat exchange more abundant, thus farthest reduce gas-liquid bias current and channeling, reduce reactor radial temperature difference.
6. base substrate roasting: the present invention due to aluminium content formula compared with before-improvement in raw material low, its sintering temperature also reduces accordingly, and roasting firing time also suitably shortens, and has fuel saving, extends the advantages such as furnace equipment service life.
Accompanying drawing explanation
Fig. 1 product structure schematic diagram of the present invention.
Detailed description of the invention
Below by embodiment, the present invention is described in further detail, but the present invention is not only confined to following examples.
The final products of Bird's Nest proppant of the present invention, its main chemical compositions comprises: Al
2o
315-90%, SiO
215-90%, CaO+MgO 0.2-11%, K
2o+Na
2o 0.2-11%, Fe
2o
3+ TiO
20.2-5.5%.
The raw material that the following embodiment of the present invention adopts and plant equipment, do not do specified otherwise, is industry routine or commercially available prod.
Embodiment 1
More protection agent prescription of the present invention: alumina powder 40%, kaolin 40%, talcum powder 5%, clay 10%, basic solvent material 4%, auxiliary material 1%.
Basic solvent material of the present invention is the mixture of albite, potassic feldspar, calcium carbonate and magnesium carbonate; Auxiliary material of the present invention are cellulose.
The present invention also provides a kind of preparation method of above-mentioned Bird's Nest proppant, and preparation process comprises:
(1) pug formula: take each raw material according to formula rate;
(2) batch mixing: the powder that the mixing of step (1) raw material is formed is dropped into kneader or batch mixer, add water (15% of powder weight) and oil (as waste oil, rapeseed oil, for 5% of powder weight) carry out pug kneading, the pug be uniformly mixed;
(3) by the honeycomb porcelain mold of 600 order numbers by extruded for the pug processed;
(4) cut: by regulating cutting wire and cutter spacing, semi-finished product base substrate and the extruded pug of step (3) are directly cut into the cylinder of certain length, then roasting becomes the agent of cellular Bird's Nest hydrogenation protecting; Or then first for pug extruded for step (3) roasting is cut into the small cylinder that ratio of height to diameter is less than 1/4, be the agent of cellular Bird's Nest hydrogenation protecting.Above-mentioned sintering temperature is 1300 DEG C, and roasting time is 20h.
Embodiment 2
The raw materials of hydrogenation protecting agent: alumina powder 30%, kaolin 40%, talcum powder 10%, clay 15%, basic solvent material 3%, auxiliary material 2%.Preparation process is with embodiment 1.
Embodiment 3
The raw materials of hydrogenation protecting agent mainly comprises: alumina powder 50%, kaolin 30%, talcum powder 5%, clay 10%, basic solvent material 4%, auxiliary material 1%.Preparation process is with embodiment 1.
The performance of table 1 embodiment of the present invention sample and specification
Note: the radial crushing strength of above-mentioned table 1 is get a diameter and highly certain hydrogenation protecting agent, length and axial two ends apply the intensity that pressure can bear.
Known by above-described embodiment, more closeer through holes will be had in its unit section area of product of the present invention, and the external surface area of product can be considerably increased, reach 5000m
2/ m
3above, reaction raw materials and protective agent is made to have larger contact and response area.Its voidage of product of the present invention reaches 30-70%, and water absorption rate reaches 10-50%, and suitable water absorption rate can make protective agent can adsorb more active material, thus improves the absorptivity of adsorbing contaminant, improves catalytic effect; The radial crushing strength of product of the present invention is 50-500N/, i.e. a granule product, and the two ends applying 50-500N at axial two ends are not cracked, keeps integrality, improves intensity and service life.
The present invention will be described for above-described embodiment, instead of limit the invention, and in the protection domain of spirit of the present invention and claims, to any amendment of the present invention and change, all will fall into protection scope of the present invention.
Claims (9)
1. cellular Bird's Nest hydrogenation protecting agent; it is characterized in that: the raw materials of this hydrogenation protecting agent comprises: alumina powder 1 ~ 60%, kaolin 5 ~ 50%, talcum powder 0.1-15%, clay 5 ~ 60%; basic solvent material 0.5 ~ 10%, auxiliary material 0.1 ~ 5%.
2. cellular Bird's Nest hydrogenation protecting according to claim 1 agent; it is characterized in that: the raw materials of described hydrogenation protecting agent comprises: alumina powder 5 ~ 50%, kaolin 10 ~ 45%, talcum powder 1-12%, clay 10 ~ 55%; basic solvent material 2 ~ 8%, auxiliary material 0.5 ~ 4%.
3. cellular Bird's Nest hydrogenation protecting according to claim 1 and 2 agent, is characterized in that: described basic solvent material is the mixture of albite, potassic feldspar, calcium carbonate and magnesium carbonate.
4. cellular Bird's Nest hydrogenation protecting according to claim 1 and 2 agent, is characterized in that: described auxiliary material are cellulose.
5. cellular Bird's Nest hydrogenation protecting according to claim 1 agent, is characterized in that: the final products of described cellular Bird's Nest hydrogenation protecting agent, and it meets: (1) external form is cellular cylinder, and its external diameter is at 3-45mm; (2) density of its cellular through hole is greater than 900 orders; (3) its ratio of height to diameter is less than 1/4; (4) cross-sectional area of its cellular through hole is triangle.
6. a preparation method for cellular Bird's Nest hydrogenation protecting agent, is characterized in that: preparation process comprises:
(1) pug formula: according to formula rate: alumina powder 1 ~ 60%, kaolin 5 ~ 50%, talcum powder 0.1-15%, clay 5 ~ 60%, basic solvent material 0.5 ~ 10%, auxiliary material 0.1 ~ 5%;
Or
Alumina powder 5 ~ 50%, kaolin 10 ~ 45%, talcum powder 1-12%, clay 10 ~ 55%, basic solvent material 2 ~ 8%, auxiliary material 0.5 ~ 4%, take each raw material;
(2) batch mixing: the powder of step (1) is dropped into kneader or batch mixer, adds water and oil carries out pug kneading, the pug be uniformly mixed;
(3) by the honeycomb porcelain mold of corresponding order number by extruded for the pug processed;
(4) cut: by regulating cutting wire and cutter spacing, semi-finished product base substrate and the extruded pug of step (3) are directly cut into the cylinder of certain length, then roasting becomes the agent of cellular Bird's Nest hydrogenation protecting; Or then first for pug extruded for step (3) roasting is cut into the small cylinder that ratio of height to diameter is less than 1/4, be the agent of cellular Bird's Nest hydrogenation protecting.
7. the preparation method of cellular Bird's Nest hydrogenation protecting according to claim 6 agent; it is characterized in that: the amount that step (2) adds water is the 12-20% of step (1) raw material weight, the amount adding oil is the 0.5-10% of step (1) raw material weight.
8. the preparation method of cellular Bird's Nest hydrogenation protecting according to claim 6 agent, is characterized in that: the order number of the honeycomb porcelain mold of the corresponding order number of step (3) is 600 object ceramic honey comb mould molding products.
9. the preparation method of cellular Bird's Nest hydrogenation protecting according to claim 6 agent, is characterized in that: the temperature of step (4) roasting is 1200-1400 DEG C, and roasting time is 15-25h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510213109.8A CN104888864B (en) | 2015-04-30 | 2015-04-30 | A kind of cellular Bird's Nest hydrogenation protecting agent |
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|---|---|---|---|
| CN201510213109.8A CN104888864B (en) | 2015-04-30 | 2015-04-30 | A kind of cellular Bird's Nest hydrogenation protecting agent |
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| CN104888864A true CN104888864A (en) | 2015-09-09 |
| CN104888864B CN104888864B (en) | 2017-10-31 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106747350A (en) * | 2016-12-02 | 2017-05-31 | 岳阳中科特种陶瓷科技有限公司 | A kind of manufacture method of ceramic honey comb support protective agent |
| CN110394181A (en) * | 2018-04-25 | 2019-11-01 | 中国石油化工股份有限公司 | A method of preparing carrier |
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| CN2892262Y (en) * | 2006-04-29 | 2007-04-25 | 刘启红 | Porous spherical supporting protecting agent filling |
| CN201644100U (en) * | 2010-05-11 | 2010-11-24 | 谭焕斌 | Single-hole plum blossom column catalyst carrier |
| CN102513162A (en) * | 2011-10-26 | 2012-06-27 | 邬树其 | Catalyst web nest support protective agent and manufacturing method thereof |
| CN104492503A (en) * | 2014-12-25 | 2015-04-08 | 萍乡市中天化工填料有限公司 | Spherical honeycomb support protecting agent of catalyst and preparation method of spherical honeycomb support protecting agent |
-
2015
- 2015-04-30 CN CN201510213109.8A patent/CN104888864B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2892262Y (en) * | 2006-04-29 | 2007-04-25 | 刘启红 | Porous spherical supporting protecting agent filling |
| CN201644100U (en) * | 2010-05-11 | 2010-11-24 | 谭焕斌 | Single-hole plum blossom column catalyst carrier |
| CN102513162A (en) * | 2011-10-26 | 2012-06-27 | 邬树其 | Catalyst web nest support protective agent and manufacturing method thereof |
| CN104492503A (en) * | 2014-12-25 | 2015-04-08 | 萍乡市中天化工填料有限公司 | Spherical honeycomb support protecting agent of catalyst and preparation method of spherical honeycomb support protecting agent |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106747350A (en) * | 2016-12-02 | 2017-05-31 | 岳阳中科特种陶瓷科技有限公司 | A kind of manufacture method of ceramic honey comb support protective agent |
| CN106747350B (en) * | 2016-12-02 | 2019-10-25 | 岳阳中科特种陶瓷科技有限公司 | A kind of manufacturing method of ceramic honey comb support protective agent |
| CN110394181A (en) * | 2018-04-25 | 2019-11-01 | 中国石油化工股份有限公司 | A method of preparing carrier |
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| Publication number | Publication date |
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| CN104888864B (en) | 2017-10-31 |
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