CN103406157B - Hydrogenation protective agent having higher impurity capability - Google Patents
Hydrogenation protective agent having higher impurity capability Download PDFInfo
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- CN103406157B CN103406157B CN201310356011.9A CN201310356011A CN103406157B CN 103406157 B CN103406157 B CN 103406157B CN 201310356011 A CN201310356011 A CN 201310356011A CN 103406157 B CN103406157 B CN 103406157B
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Abstract
The invention discloses a hydrogenation protective agent having higher impurity capability. The hydrogenation protective agent having higher impurity capability comprises 20-30wt% of pseudo-boehmite, 20-30wt% of alumina powder, 10-20wt% of quartz sand, 10-20wt% of magnesium oxide and 10-20wt% of kaolin. A preparation method of the hydrogenation protective agent comprises the following steps of adding polystyrene, a binder and water into the above materials, wherein the volume of polystyrene is 1-1.1 times volume of the above materials and the weight of the binder is 3-5wt% of the weight of the above materials, carrying out ball-milling slurry preparation and aging, and carrying out molding, drying setting and high-temperature sintering. The hydrogenation protective agent comprises a main body (1). The main body (1) is cylindrical. A through hole (3) is arranged in a shaft direction of the main body (1). The surface and the interior of the main body (1) are provided with cellular apertures (2). The hydrogenation protective agent can reduce bed layer load by more than 30%, can prevent fast increasing of pressure, has a large pore volume, a large specific surface area and large aperture distribution, can greatly improve the space for receiving metals and impurities, can effectively avoid catalyst obstruction, can improve catalyst activity and a service life, can reduce an operation cost and can improve economic benefits.
Description
Technical field
The present invention relates to catalyst protective agent, relate in particular to the hydrogenation protecting agent with higher appearance impurity ability.
Background technology
Key in residual hydrogenation protective agent and resid Fixed Bed Hydrotreating Technology; in process; metal impurities (as V, Ni, Ca, Fe etc.) and dirty thing (as coke) in residual oil processing procedure feedstock oil are easy to be deposited in the space of urging between part agent surface and catalyst granules; on the one hand it from the beginning can blocking catalyst aperture; cause catalysqt deactivation; cause again on the other hand pressure drop of column to raise fast; cause frequent shutdowns or need more catalyst changeout; reduce bed service efficiency and catalyst life, cause economic loss.For this reason; run well for ensureing to produce; according to catalyst position difference in reactor; on catalyst, must cover a certain amount of high performance hydrogenation protecting agent; make the protective agent that contacts at first residual oil raw material there is maximum bed voidage; prevent that catalyst from stopping up, and is not only conducive to improve catalyst activity, and can prevents that pressure drop of column from raising fast.Residual hydrogenation protective agent mostly adopts ceramic material to make Raschig ring formula at present; but the agent of existing Raschig ring hydrogenation protecting than great, pore volume is low, pore-size distribution is single; can not provide larger space for the reaction of metal and impurity and deposition, the ability that makes catalyst hold metal and dirty thing reduces.
Summary of the invention
For the existing problem of Raschig ring formula residual hydrogenation protective agent in above-mentioned prior art; the invention provides that a kind of light specific gravity, pore volume are large, the bimodal pore size distribution of macropore and super big hole structure; can improve and hold impurity ability, catalyst be played to the hydrogenation protecting agent of fine protective effect.
The technical scheme that the technical problem to be solved in the present invention is taked is: described in there is the hydrogenation protecting agent of higher appearance impurity ability by the boehmite of 20-30wt %, the alumina powder of 20-30wt %, the quartz sand of 10-20wt %, 10-20wt % magnesia and 10-20wt % kaolin are raw material composition, after above-mentioned raw materials ball milling is mixed, add again the polystyrene of 1～1.1 times of above-mentioned raw materials cumulative volume and the bonding agent of above-mentioned raw materials 3～5wt% and water to make compound through ball milling mixed grind, by compound vacuum mud refining, after old, carry out again compression molding, drying and shaping and high-temperature firing form, described hydrogenation protecting agent comprises body, described body is cylindrical, in body shaft to being provided with through hole, described body surface and inside have honeycomb hole.
Specification of the present invention has PHR-402 and PHR-403, and various indexs are respectively:
PHR-402: external diameter: 8-9mm, internal orifice dimension; 2-3 mm, length; 8-10 mm,
Bulk density: 0.50-0.65g/ml, specific area: 30-50m
2/ g,
Pore volume: >=0.35ml/g, crushing strength: >=5.5N/mm.
PHR-403: external diameter: 6-7mm, internal orifice dimension; 1.6-2.6mm, length; 6-8 mm,
Bulk density: 0.50-0.65g/ml, specific area: 30-50m
2/ g,
Pore volume: >=0.35ml/g, crushing strength: >=4.5N/mm.
The present invention is mainly due to concrete macropore and super big hole structure, and its aperture has two peak structure, can adsorb the impurity of different grain size size.And outside have a large amount of honeycomb ducts, there is the appearance dirt ability of super large, this be because:
1, residual oil is the heaviest in crude oil and the most unmanageable part, its enrichment most of impurity in crude oil, as sulphur, nitrogen heterocyclic, soluble metal compound and dirty thing etc., particularly Middle East residual oil, its metals content impurity is much higher than domestic general residual oil.This interiors of products has a large amount of nano level through holes; can be to contaminant filters such as sulphur, nitrogen, heterocyclic compounds; there is macroscopic closed pore simultaneously; can adsorb the large granular impurity in feedstock oil, make the impurity of whole bed can when through protective agent, obtain most filtration.
2, suitable mesopore and macropore pore size distribution.For general protective agent; only to have suitable mesopore or suitable macropore; but the present invention not only has a certain proportion of mesopore; (thering is respectively the hole below 3000 nm and more than 10000 nm); also have the macropore (0.5-1 millimeter) of certain comparison and super big hole (1-1.5 millimeter and more than 1.5 millimeters), the pore-size distribution with two peak structure is conducive to the interior diffusion of reactant molecule and prevents the fast blocking in catalyst aperture.
The present invention utilizes boehmite to calcine and can obtain nano level α-Al between 1100-1200 DEG C
2o
3, make it have pore volume large, the characteristic that specific area is high, and be distributed in by alumina powder, quartz sand, on the basal body interface that magnesia and kaolin form, adopt the polystyrene of vast scale volume to be used as expanding agent pore-creating, both can make body proportion greatly reduce, can obtain again high crushing strength, increase matrix inner space, alleviate the load to catalyst, reduce bed bearing load, reduce energy resource consumption, can improve again the ability of taking impurity and dirty thing in, effectively prevent that catalyst from crushing and stopping up, quick rising falls in controlled pressure, thereby can improve activity and the life cycle of catalyst, reduce operating cost.
The present invention is compared with existing Raschig ring: the one, and honeycomb hole is large and many, and porosity is high, and bulk density little (0.50-0.65g/ml), under the covering of same volume, can reduce bed load more than 30%, can prevent that pressure drop from raising fast; The 2nd, there is large pore volume, larger specific area and large aperture distribute (maximum honeycomb aperture can reach 1-1.5 millimeter more than), greatly improve the space that holds metal and impurity, can effectively avoid catalyst to stop up, improve catalyst activity and service life, reduce operating cost, increase economic efficiency.
Brief description of the drawings
Fig. 1 is main sectional structure schematic diagram of the present invention,
Fig. 2 is top view of the present invention.
Body 2, honeycomb hole 3, through hole, 4, convex arc body or concave arc body in the drawings, 1.
Detailed description of the invention
Embodiment 1, in Fig. 1 and Fig. 2, the described hydrogenation protecting agent with higher appearance impurity ability adopts the boehmite of 25wt %, the alumina powder of 25wt %, the quartz sand (fineness is more than 200 orders) of 20wt %, 15wt % magnesia and 15wt % kaolin are that raw material is made, add the polystyrene of stating raw material cumulative volume 1.1 times (volume ratios) as the methylcellulose (bonding agent) of expanding agent and above-mentioned raw materials 4wt% and appropriate water through ball milling, vacuum mud refining, 24 hours old, compression molding, microwave drying sizing and 1200-1300 DEG C of high-temperature firing form.It comprises body 1, described body is cylindrical, in body shaft to being provided with a through hole 3, described body surface and the inner honeycomb hole 2 with net distribution, more than described honeycomb hole aperture maximum can reach 1-1.5 millimeter, described body bottom is set to convex arc body or concave arc body 4, also convex arc body or concave arc body can be arranged to in its upper end or both ends.
Embodiment 2; it is that raw material is made that the described hydrogenation protecting agent with higher appearance impurity ability adopts the boehmite of 30wt %, the alumina powder of 20wt %, quartz sand (fineness is more than 200 orders), 20wt % magnesia and the 20wt % kaolin of 10wt %, adds that the polystyrene of stating raw material cumulative volume 1 times (volume ratio) is old through ball milling, vacuum mud refining, 24 hours as the methylcellulose (bonding agent) of expanding agent and above-mentioned raw materials 3wt% and appropriate water, compression molding, microwave drying is shaped and 1200-1300 DEG C of high-temperature firing forms.It comprises body 1, and described body is cylinder, and in body shaft, to being provided with a through hole 3, described body surface and inside have honeycomb hole 2, more than described honeycomb hole aperture maximum can reach 1-1.5 millimeter.
Claims (2)
1. one kind has the hydrogenation protecting agent of higher appearance impurity ability, it is characterized in that: it is by the boehmite of 20-30wt%, the alumina powder of 20-30wt %, the quartz sand of 10-20wt %, 10-20wt % magnesia and 10-20wt % kaolin are raw material composition, above-mentioned raw materials ball milling is mixed, add again the polystyrene of 1～1.1 times of above-mentioned raw materials cumulative volume and the bonding agent of above-mentioned raw materials 3～5wt% and water to make compound through ball milling mixed grind, by compound vacuum mud refining, after old, carry out again compression molding, drying and shaping and fire and form at 1200-1300 DEG C of temperature, described hydrogenation protecting agent comprises body (1), described body is cylindrical, in body shaft to being provided with through hole (3), described body surface and inside have honeycomb hole (2).
2. a kind of hydrogenation protecting agent with higher appearance impurity ability according to claim 1, is characterized in that: described body (1) end is convex arc body or concave arc body (4).
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| CN103406157B true CN103406157B (en) | 2014-11-26 |
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| CN104841491B (en) * | 2015-04-27 | 2017-03-01 | 萍乡市安发冶化环保填料有限公司 | A kind of silk screen hydrogenation protecting agent of pottery |
| CN116196985B (en) * | 2023-05-05 | 2023-08-22 | 中海油天津化工研究设计院有限公司 | Bird nest hydrogenation protective agent and preparation method and application thereof |
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| JPS5460288A (en) * | 1977-10-21 | 1979-05-15 | Rikagaku Kenkyusho | Catalyst carrier for isotope exchange reaction between water and hydrogen |
| CN1102077C (en) * | 1999-06-25 | 2003-02-26 | 李海 | Protectant for supporting and covering catalyst and its preparing process |
| CN102909026B (en) * | 2011-08-04 | 2016-04-27 | 中国石油化工股份有限公司 | Take titanium dioxide-aluminum oxide as Hydrogenation active protective agent and the Synthesis and applications thereof of carrier |
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Address after: 337055 Jiangxi province Pingxiang city Anyuan District Anyuan town (Ma Po Industrial Base) Patentee after: JIANGXI ANFA ENVIRONMENTAL PROTECTION NEW MATERIAL CO., LTD. Address before: 337055 Anyuan town of Jiangxi province Pingxiang city Anyuan District Po Industrial Base No. 1 pock Patentee before: Pingxiang Anfayehua Environment Protection Packing Co., Ltd. |