CN104888864B - A kind of cellular Bird's Nest hydrogenation protecting agent - Google Patents
A kind of cellular Bird's Nest hydrogenation protecting agent Download PDFInfo
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- CN104888864B CN104888864B CN201510213109.8A CN201510213109A CN104888864B CN 104888864 B CN104888864 B CN 104888864B CN 201510213109 A CN201510213109 A CN 201510213109A CN 104888864 B CN104888864 B CN 104888864B
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Abstract
A kind of cellular Bird's Nest hydrogenation protecting agent, preparing raw material includes：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%.It will possess more closeer through holes in its unit section area of the product of the present invention, the external surface area of product can be considerably increased, 5000m is reached2/m3More than, reaction raw materials and protective agent is had bigger contact and response area.The product voidage of the present invention reaches 30 70%, and water absorption rate reaches 10-50%, and suitable water absorption rate can allow protective agent to adsorb more active materials, so as to improve the absorptivity of adsorbing contaminant, improves catalytic effect；The radial direction crushing strength of product of the present invention is 50 500N/, i.e. a granule product applies 50 500N two ends not fragmentation at axial two ends, keeps integrality, improves intensity and service life.
Description
Technical field
The present invention relates to it is a kind of be used to refining oil, the hydrogenation protecting agent in the industry fixed bed hydrogenation reactor such as petrochemical industry, chemical industry.
A kind of specifically related to cellular Bird's Nest hydrogenation protecting agent (or Bird's Nest honeycomb ceramic body, Bird's Nest honeycomb propping agent or Bird's Nest support
Agent etc.).
Background technology
In the industries such as oil refining, petrochemical industry, chemical industry more raw material oil vapor treatment especially impure to residual oil, coal tar etc.
In fixed bed hydrogenation reactor, main solid deposits are carbon deposit and metal sulfide in its raw material, and a portion enters
Into the duct of catalyst, another part is then deposited on catalyst granules outer surface.Through long term accumulation, it is laminated catalyst bed
Drop gradually increases, and finally blocks reactor.Therefore, the cycle of operation for extension commercial plant and major catalyst service life,
Major catalyst bed in fixed bed hydrogenation reactor must all load the hydrogenation protecting agent of certain altitude in general above.
And novel protective agent is developed, its fundamental guiding ideology is carried out using the protective agent of different shape, property and performance
Rational gradation composition, farthest can effectively filter, adsorbs and remove carbon deposit, metal impurities that in raw material and reaction is generated etc.
Various impurity, protection lower bed layer major catalyst prevent its local stoppages caused by pressure difference increase rapidly, final purpose is to prolong
The service cycle of long commercial plant.
The hydrogenation protecting agent a great variety that current market is used, its profile has spherical, column, Raschig ring, vane rings, honeycomb
The plurality of specifications product such as cylindrical type, its shape, size, material, activity differ, and it is acted on and effect is also different, to filling
For the hydrogenation protecting agent on upper strata, its main function be effectively filter, adsorb micro-solid impurity in its feedstock oil and
Remove iron, the reactivity such as vanadium very high organic metal impurity；And the various hydrogenation protecting agent that there is now are not in this respect
It is very good, although for example existing the most frequently used Raschig ring and its larger specific surface area of vane rings voidage are smaller, and it is middle logical
Kong Tai great is difficult impurity trapped.Recent years starts the Bird's Nest ceramic honey comb of gradually popularization and application, its outer void in refining art
Rate and external surface area are larger, intercept impurity ability and are also significantly improved than Raschig ring etc., but due to composition of raw materials before and manufacture
The limitation of technique, the density of its through hole can only accomplish 900 mesh (cpsi, i.e. interior number of openings per square inch, via densities or
It can be appreciated that hole density is duct number per square inch on cross section) below, cause the ratio table contacted with reaction medium
Area is small, and dust removal rate is low；And ratio of height to diameter (product height and natural scale) is generally higher than 1/4, so in hydrogenation protecting agent
Crank, inclination can be caused after filling so that the impurity of flowing in radial direction through hole and hydrogenation reactor, air-flow direction not
Unanimously, cause to flutter and catch the reduction of impurity efficiency, have a strong impact on the using effect of hydrogenation protecting agent.
The content of the invention
The present invention reaches more than 900 mesh that ratio of height to diameter is less than for the above-mentioned deficiency of prior art there is provided a kind of via densities
1/4, while the cellular Bird's Nest hydrogenation protecting agent of higher finished product sintering qualified rate can also be reached.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：A kind of cellular Bird's Nest hydrogenation protecting agent,
The preparing raw material of the hydrogenation protecting agent includes：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%.
Preferably, the preparing raw material of described cellular Bird's Nest hydrogenation protecting agent includes：Alumina powder 5~50%, height
Ridge soil 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, potassium feldspar, calcium carbonate and magnesium carbonate.
Auxiliary material of the present invention is cellulose；The present invention is used to increase proppant using cellulose main purpose
Cohesive, more easy-formation, and more conducively shaping, the cutting of proppant, cracky, does not improve yield rate.
The final products of cellular Bird's Nest hydrogenation protecting agent of the present invention, its main chemical compositions include：Al2O3
15-90%, SiO215-90%, CaO+MgO 0.2-11%, K2O+Na2O 0.2-11%, Fe2O3+TiO20.2-5.5%.
The final products of the cellular Bird's Nest hydrogenation protecting agent of the present invention, it meets：(1) external form is cellular cylinder
Body, its external diameter is in 3-45mm；(2) density of its cellular through hole is more than 900 mesh cpsi；(3) its ratio of height to diameter is less than 1/4；(4)
The cross-sectional area of its cellular through hole is triangle.
The present invention also provides a kind of preparation method of above-mentioned cellular Bird's Nest hydrogenation protecting agent, and preparation process includes：
(1) pug formula：According to formula rate：Alumina powder 1~60%, kaolin 5~50%, talcum powder 0.1-
15%th, 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% weighs each raw material；
(2) batch mixing：The powder of step (1) is put into kneader or batch mixer, water is added and oil carries out pug kneading, obtain
Mixed uniformly pug；
(3) by the honeycomb porcelain mold of corresponding mesh number by the pug extrusion forming processed；
(4) cut：It is the mud of step (3) extrusion forming by semi-finished product base substrate by adjusting cutting wire and cutter spacing
Material is cut directly into the cylinder of certain length, is then fired into cellular Bird's Nest hydrogenation protecting agent；Or extrude step (3)
The pug of shaping, which is first calcined, is then cut into the small cylinder that ratio of height to diameter is less than 1/4, as cellular Bird's Nest hydrogenation protecting agent.
The amount that step (2) of the present invention adds water is the 12-20% of step (1) raw material weight, and the amount for adding oil is step (1)
The 0.5-10% of raw material weight；Described oil is the oils that rapeseed oil, gutter oil etc. play lubrication；The present invention is at this
Why step adds oil primarily to facilitating lubricating release, improves the water retention property of pug, not dry, not fragmentation, also simultaneously
The plasticity of pug, more conducively machine-shaping can be improved.
The corresponding mesh number of above-mentioned steps (3) of the present invention honeycomb porcelain mold (ceramic honey comb mould, industry traditional dies product,
Generally on panel carry multiple holes stainless steel mould, specifically refer to introduction of the industry on ceramic honey comb mould) mesh
Number is the ceramic honey comb mould molding product of 600 mesh (cpsi), and pug is formed after being squeezed out from above-mentioned honeycomb die to be had
The hydrogenation protecting agent initial model of hole count；Because the present invention has selected appropriate ceramic raw materials formulation to make the receipts after the roasting of its product
Shrinkage (being mainly axial shrinkage rate, radial contraction can be neglected) reaches more than 25%, so as to ensure its through hole of the finished product after burning till
Density is that can reach more than 900 mesh.
The pug that semi-finished product base substrate is step (3) extrusion forming is cut directly into a fixed length by above-mentioned steps (4) of the present invention
The cylinder of degree, the shrinkage factor (predominantly axial shrinkage rate) after described certain length is calcined with specific reference to product reaches 25%
More than this rule cut, it is ensured that finished product its ratio of height to diameter after roasting, which is met, is less than 1/4, such as a diameter of 5mm, the height of semi-finished product
For 2.5mm, now ratio of height to diameter is 1/2, and shrinkage factor is 60%, then it is 1/5 to burn till rear ratio of height to diameter.So as to according to customer requirement and receipts
Shrinkage cuts the length of semi-finished product.
The above-mentioned sintering temperature of the present invention is 1200-1400 DEG C, and roasting time is 15-25h.
The product of the present invention can be directly as inertia Bird's Nest hydrogenation protecting agent using can also be a certain amount of by impregnating
Active Bird's Nest hydrogenation protecting agent is made in active catalyst component.
The advantages of the present invention：
1. the present invention, by matching suitable composition of raw materials, had made its product both by the use of the big material of shrinkage factor as raw material
There can be good extrusion forming effect, can guarantee that producing via densities in the case where percent of firing shrinkage is very big reaches again
Cellular Bird's Nest protective agent more than 900 mesh, while higher finished product sintering qualified rate can also be reached.
2. more closeer through holes will be possessed in its unit section area of the product of the present invention, product can be considerably increased
External surface area, reaches 5000m2/m3More than, reaction raw materials and protective agent is had bigger contact and response area.The present invention's
Its voidage of product reaches 30-70%, and water absorption rate reaches 10-50%, and suitable water absorption rate can allow protective agent to adsorb
More active materials, so as to improve the absorptivity of adsorbing contaminant, improve catalytic effect；The radial direction crushing strength of product of the present invention
For 50-500N/, i.e., one or a product apply 50-500N dynamics not fragmentation at axial two ends, keep integrality,
Improve intensity and service life.
3. the present invention is due to the increase of via densities, then the area of each through hole is smaller can significantly improve filtering and adsorb
The effect of impurity, is that more preferable absorption intercepts impurity, its through hole typically uses triangle.
4. the protective agent of the present invention is slim less than 1/4 for ratio of height to diameter, most guarantors can be made when reactor is loaded
Protect agent section upwards, advantageously reduce reactor pressure decrease, and improve interception impurity effect.
5. the present invention can enter to the gas-liquid flowed through to greatest extent because of its denser mesh-structured and more bigger serface
The fine and closely woven cutting of row, and make contact and heat exchange of the cold hydrogen with raw material more abundant, so as to farthest reduce gas-liquid bias current
And channeling, reduce reactor radial temperature difference.
6. base substrate is calcined：The present invention due in raw material the formula of aluminium content compared with before-improvement it is low, its sintering temperature is also corresponding
Reduction, the time that is fired into also suitably shortens, the advantages of having saving fuel, extension furnace equipment service life.
Brief description of the drawings
Fig. 1 product structure schematic diagrames of the present invention.
Embodiment
The present invention is described in further detail below by embodiment, but the present invention is not limited solely to following examples.
The final products of Bird's Nest proppant of the present invention, its main chemical compositions include：Al2O315-90%, SiO2
15-90%, CaO+MgO 0.2-11%, K2O+Na2O 0.2-11%, Fe2O3+TiO20.2-5.5%.
Raw material and plant equipment that the following embodiments of the present invention are used, do not do specified otherwise, are industry routine or city
Sell product.
Embodiment 1
The reinforcement protection agent prescription of the present invention：Alumina powder 40%, kaolin 40%, talcum powder 5%, clay 10%, alkali
Property solvent material 4%, auxiliary material 1%.
Basic solvent material of the present invention is the mixture of albite, potassium feldspar, calcium carbonate and magnesium carbonate；Institute of the present invention
The auxiliary material stated is cellulose.
The present invention also provides a kind of preparation method of above-mentioned Bird's Nest proppant, and preparation process includes：
(1) pug formula：Each raw material is weighed according to formula rate；
(2) batch mixing：Step (1) raw material is mixed to the powder input kneader or batch mixer constituted, water (powder weight is added
15%) and oil (such as gutter oil, rapeseed oil, be powder weight 5%) carry out pug kneading, the mud being uniformly mixed
Material；
(3) by the honeycomb porcelain molds of 600 mesh numbers by the pug extrusion forming processed；
(4) cut：It is the mud of step (3) extrusion forming by semi-finished product base substrate by adjusting cutting wire and cutter spacing
Material is cut directly into the cylinder of certain length, is then fired into cellular Bird's Nest hydrogenation protecting agent；Or extrude step (3)
The pug of shaping, which is first calcined, is then cut into the small cylinder that ratio of height to diameter is less than 1/4, as cellular Bird's Nest hydrogenation protecting agent.On
The sintering temperature stated is 1300 DEG C, and roasting time is 20h.
Embodiment 2
The preparing raw material of hydrogenation protecting agent：Alumina powder 30%, kaolin 40%, talcum powder 10%, clay 15%, alkalescence
Solvent material 3%, auxiliary material 2%.Preparation process be the same as Example 1.
Embodiment 3
The preparing raw material of hydrogenation protecting agent mainly includes：Alumina powder 50%, kaolin 30%, talcum powder 5%, clay
10%, basic solvent material 4%, auxiliary material 1%.Preparation process be the same as Example 1.
The performance and specification of the sample of the embodiment of the present invention of table 1
Note：The radial direction crushing strength of above-mentioned table 1 is to take a diameter and the certain hydrogenation protecting agent of height, and length is axial direction
Two ends apply the intensity that pressure can bear.
By above-described embodiment, more closeer through holes will be possessed in its unit section area of product of the invention, can
The external surface area of product is considerably increased, 5000m is reached2/m3More than, make reaction raw materials and protective agent have bigger contact and
Response area.Its voidage of the product of the present invention reaches 30-70%, and water absorption rate reaches 10-50%, and suitable water absorption rate can make
More active materials can be adsorbed by obtaining protective agent, so as to improve the absorptivity of adsorbing contaminant, improve catalytic effect；Present invention production
The radial direction crushing strength of product is 50-500N/, i.e. a granule product, and 50-500N two ends not fragmentation is applied at axial two ends, is protected
Integrality is held, intensity and service life is improved.
The present invention will be described for above-described embodiment, rather than limits the invention, in the spirit and power of the present invention
In the protection domain of sharp claim, to any modifications and changes of the present invention, protection scope of the present invention is fallen within.
Claims (7)
1. a kind of cellular Bird's Nest hydrogenation protecting agent, it is characterised in that：The preparing raw material of the hydrogenation protecting agent includes：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%；
The final products of described cellular Bird's Nest hydrogenation protecting agent, it meets：（1）External form is cellular cylinder, and its external diameter is in 3-
45mm；（2）The density of its cellular through hole is more than 900 mesh；（3）Its ratio of height to diameter is less than 1/4；（4）Its cellular through hole it is transversal
Area is triangle.
2. cellular Bird's Nest hydrogenation protecting agent according to claim 1, it is characterised in that：The system of described hydrogenation protecting agent
Standby raw material includes：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 agent according to claim 1 or 2, it is characterised in that：Described basic solvent material
For the mixture of albite, potassium feldspar, calcium carbonate and magnesium carbonate.
4. cellular Bird's Nest hydrogenation protecting agent according to claim 1 or 2, it is characterised in that：Described auxiliary material is
Cellulose.
5. the preparation method of cellular Bird's Nest hydrogenation protecting agent according to claim 1, it is characterised in that：Preparation process bag
Include：
（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% aid in material
Material 0.5 ~ 4%, weighs each raw material；
（2）Batch mixing：By step（1）Powder input kneader or batch mixer, add water and oil carry out pug kneading, obtain uniform
The pug of mixing；
（3）By the honeycomb porcelain mold of corresponding mesh number by the pug extrusion forming processed；
（4）Cutting：It is step by semi-finished product base substrate by adjusting cutting wire and cutter spacing（3）The pug of extrusion forming is straight
The cylinder for cutting into certain length is connect, cellular Bird's Nest hydrogenation protecting agent is then fired into；Or by step（3）Extrusion forming
Pug be first calcined be then cut into ratio of height to diameter be less than 1/4 small cylinder, as cellular Bird's Nest hydrogenation protecting agent.
6. the preparation method of cellular Bird's Nest hydrogenation protecting agent according to claim 5, it is characterised in that：Step（2）Plus
The amount for entering water is step（1）The 12-20% of raw material weight, the amount for adding oil is step（1）The 0.5-10% of raw material weight.
7. the preparation method of cellular Bird's Nest hydrogenation protecting agent according to claim 5, it is characterised in that：Step（4）Roasting
The temperature of burning 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 CN104888864A (en) | 2015-09-09 |
| CN104888864B true CN104888864B (en) | 2017-10-31 |
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| 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 | Priority date | Publication date | Assignee | Title |
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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 |
| CN102513162B (en) * | 2011-10-26 | 2014-01-22 | 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 |
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