CN102441439B - Effective, environment-friendly and high-strength nest type support protecting agent and preparation method thereof - Google Patents
Effective, environment-friendly and high-strength nest type support protecting agent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an effective, environment-friendly and high-strength nest type support protecting agent. The agent comprises a main body (2), wherein the two ends of the main body are of a shape of a flat circular body with an externally convex curved surface; honeycomb holes (3) distributed in a mesh structure are formed in the main body; reinforced ribs (4) are arranged among the honeycomb holes at intervals; and the main body consists of the following components in percentage by weight: a composition prepared from 70 to 90 percent of environment-friendly fine silicon carbide powder and 10 to 30 percent of organic clay, 5 to 10 percent of hydroxymethyl cellulose, 5 to 10 percent of Chinese wood oil, 5 to 10 percent of silica sol and 4 to 8 percent of magnesium stearate. Mine resources can be saved; environmental protection is beneficial; the agent has high hardness, compressive resistance, acid and alkali resistance, corrosion resistance, thermal erosion resistance, heat conductivity and heat stability; support protecting ability can be greatly improved; the utilization period of a catalyst is prolonged; the activity of the catalyst can be ensured; the reaction speed is increased; the production cost is reduced; and the working efficiency of a reactor is improved.
Description
Technical field
The present invention relates to the industries such as petrochemical industry, Coal Chemical Industry for supporting and the high-strength nido support protective agent of high-efficiency environment friendly of covering protection catalyst.
Background technology
Chemical catalyst is the widely used staple product of a kind of all kinds of chemical industry, particularly most important to the use of the industries such as petrochemical industry, Coal Chemical Industry, fine chemistry industry and chemical fertilizer, smelting, light industry, medicine, environmental protection.In order to protect valuable catalyst, make catalyst be difficult for crushing and damaging, extending catalyst life cycle, accelerate catalytic, reduce production costs, enhance productivity, now all to use the difform products such as ball-type that each type oxide makes, ring-like, column type, cartwheel pattern, hole column type, perforate ball-type, foam type and honeycomb type, the one, as bottom cushion, be used for support catalyst, play support catalyst effect; The 2nd, as cover layer, be used for protecting top catalyst, play guard catalyst effect, with cover layer, filter the small solid impurities such as the colloid of absorption in gas-liquid, coke powder, prevent that catalyst crushing, deposition, coking, caking from producing and block, avoid tower internal pressure to raise, prevent catalyst activity component sintering; This product also can be used as partitioning agent for gas-liquid shunting in the middle of catalyst, plays distributional effects.As the product category of support protective agent, have much at present, formed the proppant with supporting role, there is the protective agent of protective effect and the partitioning agent of shunting action, also different with their different roles in position in tower, be referred to as support protective agent, as porcelain ball, Pored ceramic ball, little ring-type, hole column, gear-like, the ceramic honey comb that particularly use amount just progressively increases now, they also have his own strong points, respectively there is shortage, but no matter that, all owing to choosing material, the restriction of the reasons such as shape and structure and other manufacturing process, all have some common shortcomings: the one, the compression strength of existing support protective agent, wearability and antiscour (hitting) ability is high not enough, specific area is also not enough, the strainability of scape sound to medium, cause gas-liquid maldistribution, the 2nd, existing support protective agent heat conductivility is not high, specific area is not enough and heat endurance is not very good.
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Summary of the invention
The problem existing for support protective agent in above-mentioned prior art, not only hardness is high, compression strength is high to the invention provides one, and acid and alkali-resistance and corrosivity are good, and wearability is good, thermal conductivity and the high high-strength nido support protective agent of high-efficiency environment friendly of heat endurance.
The present invention adopts and with active constituent, any " green silicon carbide " reacting does not occur to replace existing oxide be primary raw material, through scientific formula, produces a kind of support protective agent with support, protection and distributional effects.
The technical scheme that the technical problem to be solved in the present invention is taked is: the high-strength nido support protective agent of described high-efficiency environment friendly comprises body, described body is the flat cylindrical that two ends are outer convex surface, described body interior is provided with and is the honeycomb hole that network structure distributes, between honeycomb hole, be arranged at intervals with reinforcement, the composition that described body is formed by the green silicon carbide fine powder of 70-90%wt and the organic clay of 10-30%wt, and account for the CMC of composition total weight 5-10%wt, the tung oil of 5-10%wt, the Ludox of 5-10%wt and the dolomol of 4-8%wt composition are also prepared from as follows:
(1) first various powder material are mixed in proportion, then add in proportion various liquid materials, be fully uniformly mixed, mediate, the old clod of making,
(2) clod is put into fully automatic vacuum injection press, by mould, is crushed to the wet base substrate of nido,
(3) base substrate that will wet carries out nature or heated-air drying and is less than 2% to moisture content wherein, makes dry body body,
(4) dry body body is cut into pieces, polishes and blow ash by technological requirement, make semi-finished product,
(5) by semi-finished product loading of kiln, first to be no less than 16 hours, be warming up to 900 ℃, be then warming up to again 1350-1450 ℃ and be incubated 4-8 hour, then after being cooled to be less than 150 ℃, come out of the stove and become support protective agent.
The main chemical weight of described support protective agent is SiC:70-85%, SiO
2: 10-25%, Fe
2o
3: 0.5-0.8%.
Described support protective agent has the effect of support, covering protection and distribution; this product mainly plays support catalyst effect at catalyst bottom; or cover catalyst top and mainly play guard catalyst effect, or mainly play gas-liquid uniform distribution effect in the middle of being arranged on catalyst.
Because gas-liquid enters from catalyst top, for further improving the support protective agent effect that covers catalyst top, make support protective agent can fully adsorb the colloid in gas-liquid, the small solid impurity such as coke powder, avoid small solid impurity to be deposited in catalyst, prevent that catalyst from blocking and burning, extending catalyst life cycle, guarantee catalyst result of use, the present invention by described body under 400-600 ℃ of high temperature by repeatedly activating impregnation process, make to adhere to one deck active layer on the honeycomb hole surface of body interior, active constituent total content in described active layer is no less than 2.8%wt, thereby prepare the another kind of support protective agent that is mainly used in covering catalyst top with active constituent.Described active constituent is one or more combinations of molybdenum, cobalt, tungsten, nickel, five kinds of elements of phosphorus, specifically combines visual catalyst service condition and determines.
Green silicon carbide of the present invention: fineness is greater than 250 orders, SiC content is no less than 99.5%, and its crystal is α type, and crystallization content is greater than 98%.
Described honeycomb hole shape of cross section can be triangle, circle or orthohexagonal etc.
Described methylol fiber belongs to adhesive, is a kind of white powder; Described organic clay is the product that can buy on market.It mainly contains kaolin type organic clay, bentonite organic clay and montmorillonite organic clay, and in organic clay, iron oxide content is less than 0.8%; Described Ludox is neutral, contains SiO in Ludox
2amount is greater than 25%; Described tung oil is lubricant, and described dolomol is releasing agent.
The present invention can make full use of discarded green silicon carbide grinding tool and the Hightemperature Kiln Furniture of existing part, through pulverizing, magnetic separation, powdery green silicon carbide is made in screening and classification processing, it is high that it has thermal conductivity factor, thermal coefficient of expansion is little, stable chemical nature, and under the conditions such as HTHP, there is good high-temperature oxidation resistance, the performances such as resistance to thermal shock stability height, therefore the support protective agent of preparing as primary raw material with carborundum is in catalyst use procedure, can guarantee catalyst overall performance, especially at catalyst under unsteady state, can avoid catalyst to be subject to the disturbance of operating parameter and cause the local or overall temperature runaway phenomenon that produces of reactor, make the catalyst can be by coking and caking.Regeneration condition is superior, has extended catalyst service life and on-stream time, has improved the operating efficiency of reactor.
The present invention compared with prior art has the following advantages
1, the present invention can make full use of discarded green silicon carbide grinding tool and the Hightemperature Kiln Furniture of part, saves mineral resources, is conducive to environmental protection and the ecological balance,
2, the present invention has selected that hardness is high, compression strength is high, acid and alkali-resistance and corrosive power are strong, the high-quality SiC material that heat resistanceheat resistant scouring capability is strong, and increase reinforcement, can greatly improve enabling capabilities and compression strength, bear catalyst load-carrying, guarantee that catalyst is difficult for crushing, pulverizes and damages, increased the life cycle of catalyst
3, the present invention has good thermal conductivity and heat endurance, can guarantee catalyst activity performance, avoids temperature runaway phenomenon, catalyst can be by coking, caking, can extending catalyst service life, accelerate catalytic, reduce production costs, improve the operating efficiency of reactor
4, carrier body ringwise, pressure drop resistance is little, is conducive to reactor operation and control.
The physics and chemistry performance indications that the present invention has:
1, physical property
Bulk density: 0.95-0.98 ton/m3 (specification is: diameter is 25mm, 300 order holes)
Overall dimensions: A type, φ 6 × 4, φ 10 × 6, φ 13 × 7, φ 15 × 8, φ 18 × 9.
Type B, φ 20 × 10, φ 25 × 12, φ 30 × 14, φ 35 × 16.
Honeycomb cell densities range; 100-300 hole/cm2, pass is regular vertical triangle, circle or circle square opening.
Thermal conductivity factor: > 40W/MK(1200 ℃), impact resistance > 300K,
Compressive resistance; >=80Mpa, hardness: >=2000Kg/m2, voidage > 80%,
Specific area 800-2000m2/m3, water absorption rate: < 3%, acid resistance >99.8%, fastness to alkali >98%.
2, product overall appearance
Product appearance is light green color, and φ 6-φ 18 external forms are post nido, and φ 20-φ 35 is bird-nest type, is provided with three equally distributed reinforcements on each product.
3, chemical property
Carborundum 70-85%, SiO
2: 10-25%, ferric oxide 0.5-0.8%.
Active constituent total content: > 2.8% in active layer (active constituent is one or more combinations in molybdenum, cobalt, tungsten, nickel, phosphorus).
Accompanying drawing explanation
Fig. 1 is plan structure schematic diagram of the present invention,
Fig. 2 is the A-A sectional structure schematic diagram of Fig. 1.
Hole wall 2, body 3, honeycomb hole 4, reinforcement in the drawings, 1.
The specific embodiment
Embodiment 1, as depicted in figs. 1 and 2, the high-strength nido support protective agent of described high-efficiency environment friendly comprises body 2, described body is the flat cylindrical that two ends are outer convex surface, described body 2 inside are provided with and are the honeycomb hole 3 that network structure distributes, honeycomb hole cross section is triangle, also can be circle or orthohexagonal, hole wall 1 thickness is 0.3-0.5mm, between honeycomb hole, being arranged at intervals with thickness is the reinforcement 4 of 0.8-1mm, reinforcement is that six even intervals arrange, the composition that described body is formed by the green silicon carbide fine powder of 76%wt and the organic clay of 24%wt (kaolin type organic clay), and account for the CMC of composition total weight 6%wt, the tung oil of 9%wt, the Ludox of 6%wt and the dolomol of 8%wt composition are also prepared from as follows:
(1) first various powder material are mixed in proportion, then add in proportion various liquid materials, be fully uniformly mixed, mediate, the old clod of making,
(2) clod is put into full-automatic injecting press, by mould, is crushed to the wet base substrate of nido,
(3) base substrate that will wet carries out nature or heated-air drying and is less than 2% to moisture content wherein, makes dry body body,
(4) dry body body is cut into pieces, polishes and blow ash by technological requirement, make semi-finished product,
(5) by semi-finished product loading of kiln, first to be no less than 16 hours, be warming up to 900 ℃, be then warming up to again 1350-1450 ℃ and be incubated 4-8 hour, then be cooled to 150 ℃ to come out of the stove below and become support protective agent finished product.
After testing, property indices is embodiment 1 gained support protective agent finished product:
Thermal conductivity factor: 42W/MK(1200 ℃), impact resistance: 3120K,
Compressive resistance; 85Mpa, hardness: 2100Kg/m2, voidage: 85%,
Water absorption rate: 2.1%, acid resistance: 99.8%, fastness to alkali: 98%.
SiC:75.3%, SiO
2: 20.6%, ferric oxide 0.72%, all the other are impurity.
Embodiment 2, the high-strength nido support protective agent of described high-efficiency environment friendly comprises body 2, described body is the flat cylindrical that two ends are outer convex surface, described body interior is provided with and is the honeycomb hole 3 that network structure distributes, honeycomb hole cross section is triangle, hole wall 1 thickness is 0.3-0.5mm, between honeycomb hole, be arranged at intervals with reinforcement 4, Rib Thickness is 0.8-1 millimeter, reinforcement is that six even intervals arrange, described body forms composition by the green silicon carbide fine powder of 86%wt and the organic clay of 14%wt (montmorillonite type organic clay), and account for the CMC of composition total weight 9%wt, the tung oil of 6%wt, the Ludox of 9%wt and the dolomol of 5%wt are prepared from by method described in embodiment.
After testing, property indices is embodiment 2 gained support protective agent finished products:
Thermal conductivity factor: 43W/MK(1200 ℃), impact resistance: 3180K,
Compressive resistance; 84.6Mpa, hardness: 2180Kg/m2, voidage: 86%,
Water absorption rate: 2.2%, acid resistance: 99.8%, fastness to alkali: 98%.
SiC:85.3%, SiO
2: 15.6%, ferric oxide 0.58%, all the other are impurity.
By the support protective agent finished product of above-described embodiment 3 gained under 400-600 ℃ of high temperature; by existing poling processing technique; by 3 activation process; make evenly to adhere on the honeycomb hole surface of support protective agent inside one deck active layer (not shown in FIG.); active constituent total content 3.22%wt in described active layer; active constituent is molybdenum and two kinds of combinations of nickel (respectively accounting for 50%), thereby prepares the another kind of support protective agent finished product with active constituent.
Claims (1)
1. the high-strength nido support protective agent of high-efficiency environment friendly, it comprises body (2), described body is the flat cylindrical that two ends are outer convex surface, described body interior is provided with and is the honeycomb hole (3) that network structure distributes, it is characterized in that: described body passes through repeatedly activation process under 400-600 ℃ of high temperature, make to adhere to one deck active layer on the honeycomb hole surface of body interior, in described active layer, active constituent total content is no less than 2.8%wt, described active constituent is molybdenum, cobalt, tungsten, nickel, one or more combinations of five kinds of elements of phosphorus, between honeycomb hole, be arranged at intervals with reinforcement (4), the composition that described body is formed by the green silicon carbide fine powder of 70-90%wt and the organic clay of 10-30%wt, and account for the CMC of composition total weight 5-10%wt, the tung oil of 5-10%wt, the Ludox of 5-10%wt and the dolomol of 4-8%wt composition are also prepared from as follows:
(1) first various powder material are mixed in proportion, then add in proportion various liquid materials, be fully uniformly mixed, mediate, the old clod of making,
(2) clod is put into vacuum injection press, by mould, is crushed to the wet base substrate of nido,
(3) base substrate that will wet carries out nature or heated-air drying and is less than 2% to moisture content wherein, makes dry body body,
(4) dry body body is cut into pieces, polishes and blow ash by technological requirement, make semi-finished product,
(5) by semi-finished product loading of kiln, first to be no less than 16 hours, be warming up to 900 ℃, be then warming up to again 1350-1450 ℃ and be incubated 4-8 hour, then be cooled to come out of the stove and become support protective agent lower than 150 ℃.
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| CN201110436494.4A CN102441439B (en) | 2011-12-23 | 2011-12-23 | Effective, environment-friendly and high-strength nest type support protecting agent and preparation method thereof |
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|---|---|---|---|
| CN201110436494.4A CN102441439B (en) | 2011-12-23 | 2011-12-23 | Effective, environment-friendly and high-strength nest type support protecting agent and preparation method thereof |
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| CN102924063B (en) * | 2012-11-14 | 2013-10-09 | 段文辉 | Microporous support protecting agent and manufacturing method thereof |
| CN107199016A (en) * | 2017-07-12 | 2017-09-26 | 江西安发环保新材料有限公司 | A kind of oil product special efficient Hydrodearsenic Catalyst |
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| CN101966471A (en) * | 2010-04-23 | 2011-02-09 | 周江林 | High-efficiency environmental-friendly catalyst carrier |
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| ASS | Succession or assignment of patent right |
Owner name: LI YONGZHONG Effective date: 20130111 Owner name: LI HAI Free format text: FORMER OWNER: PINGXIANG XINQUAN INDUSTRIAL FILLING INDUSTRY CO., LTD. Effective date: 20130111 |
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| C41 | Transfer of patent application or patent right or utility model | ||
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Wei Zhizhong Inventor after: Tang Guanjun Inventor after: Jiu Xiping Inventor after: Zhou Jianglin Inventor before: Peng Jun Inventor before: Li Hai Inventor before: Li Riyan Inventor before: Liu Qingguo |
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Free format text: CORRECT: INVENTOR; FROM: PENG JUN LI HAI LI RIYAN LIU QINGGUO TO: WEI ZHIZHONG TANG GUANJUN MIAO XIPING ZHOU JIANGLIN |
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| TA01 | Transfer of patent application right |
Effective date of registration: 20130111 Address after: 4, 337000, 19 Garden Street, Fenghuang street, Anyuan District, Jiangxi, Pingxiang Applicant after: Li Hai Applicant after: Li Yongzhong Address before: 337000, Lantian building, middle Park Road, Pingxiang Economic Development Zone, Jiangxi, Pingxiang, 15-25 Applicant before: Pingxiang Xinquan Industry Filling Industrial Co.,Ltd. |
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Free format text: FORMER OWNER: LI YONGZHONG Effective date: 20140318 Owner name: PINGXIANG ANFAYEHUA ENVIRONMENT PROTECTION PACKING Free format text: FORMER OWNER: LI HAI Effective date: 20140318 |
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Effective date of registration: 20140318 Address after: 337000 Anyuan town of Jiangxi province Pingxiang city Anyuan District Po Industrial Base No. 1 pock Applicant after: Pingxiang Anfayehua Environment Protection Packing Co., Ltd. Address before: 4, 337000, 19 Garden Street, Fenghuang street, Anyuan District, Jiangxi, Pingxiang Applicant before: Li Hai Applicant before: Li Yongzhong |
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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: 337000 Anyuan town of Jiangxi province Pingxiang city Anyuan District Po Industrial Base No. 1 pock Patentee before: Pingxiang Anfayehua Environment Protection Packing Co., Ltd. |