CN1089039C - Macroporous alumina carrier and preparing process thereof - Google Patents
Macroporous alumina carrier and preparing process thereof Download PDFInfo
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- CN1089039C CN1089039C CN98114347A CN98114347A CN1089039C CN 1089039 C CN1089039 C CN 1089039C CN 98114347 A CN98114347 A CN 98114347A CN 98114347 A CN98114347 A CN 98114347A CN 1089039 C CN1089039 C CN 1089039C
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Abstract
The present invention relates to a macroporous high-intensity alumina supporter and a preparation method thereof. The macroporous high-intensity alumina supporter has high compressive resistance, large pore diameter, proper double pore canal and pore diameter distribution and low cost. The preparation method of the macroporous high-intensity alumina supporter comprises: one or some of pseudo-boehmite solid elastomer powders prepared from different raw materials by the path method, carbon black powder and surfactants are mixed, and then, the mixture is prepared into the macroporous high-intensity alumina supporter by peptizing, forming, drying and roasting.
Description
The present invention relates to a kind of preparation method of alumina support, particularly have the preparation method of structure of double peak holes feature macropore high-strength alumina carrier.
At present, in the production process of mink cell focus HDM, owing to contain impurity such as a certain amount of vanadium, sulphur, arsenic, nickel in the feedstock oil, very easily form deposition, thereby the duct of blocking catalyst causes catalyst activity to descend rapidly, so that inactivation influences commercial Application.This shows that the good pore structure of carrier has extremely special contribution to the metal removal activity of catalyst for hydroprocessing of heavy oil.By transferring the pore structure of knot catalyst carrier, particularly improving the aperture accounts in rate greater than the pore volume more than the 100nm, formation is beneficial to the big metal migration of molecular diameter and can holds macromolecular macropore, when the inner surface of catalyst is fully used, improve the metal removal activity of hydrotreating catalyst.Characteristics such as in order to adapt to industrial needs, carrier also must possess the mechanical strength height in addition, is suitable for manufacturing, and price is low.
Chinese patent 93114901.0 has been introduced a kind of preparation method with double-hole alumina support.By adopting two kinds of different aluminium hydrate powders of pore-size distribution to make the precursor of preparation aluminium oxide, adopt carbon black and surfactant to do expanding agent, to prepare aluminium oxide with double-hole.But the method is to aluminium hydroxide ingredient requirement harshness, the addition of surfactant also more (alumina raw material: surfactant=100: 5～6) and surfactant to select best unazotized linear primary alcohol polyethers or polyesters non-ionic surface active agent.And carrier aperture has only 14～40% greater than the ratio that the pore volume of 10nm accounts for total pore volume, also only accounts for less than 5% greater than the pore volume of 100nm, and like this, when removing the big minute period of the day from 11 p.m. to 1 a.m that is similar to arsenic one class, this kind carrier just can't be satisfied the demand.
USP4,448,896 have introduced that to adopt a kind of activated alumina or its precursor be raw material, add carbon black and the organic polymer preparation method as the alumina support of expanding agent.But the amounts of carbon black that the method need add is more, is preferably＞20wt%, and cause intensity relatively poor, not shock-resistant, if be used for industrial production, then reach suitable efflorescence, bed pressure drop is improved, can't carry out normal running.
The preparation method that EP237240 has introduced a kind of structure of double peak holes carrier adds the charcoal fiber therein, and the aperture is concentrated on respectively less than 5nm with greater than in two scopes of 100nm.Though this carrier has the double hole channel structure, aperture part aperture is less, and the pore volume occupancy volume is bigger again, is unfavorable for the diffusion of macromolecular compound.And very easily stopped up, cause active decline by the metal accumulation thing.The manufacturing cost of the method is higher simultaneously.
The preparation method of a kind of large-pore alumina carrier that Chinese patent 96103297.9 is introduced adds physics expanding agent such as carbon black and chemical enlargement agent such as phosphide in the boehmite dry glue powder, by the kneading method moulding, the carrier that finally obtains can several bore dias be 15.0～20.0nm.But do not form double hole channel, the pore volume that the hole had greater than 100nm only accounts for about 5% of total pore volume, simultaneously the support strength that makes of method is lower thus, thereby when the required catalyst of reaction required carrier to possess double hole channel and will higher compressive resistance be arranged, then the prepared carrier of method just had been subjected to considerable restraint thus.
The object of the present invention is to provide a kind of macropore high-strength alumina carrier and preparation method thereof, make the alumina support that obtains have higher compressive resistance, bigger aperture, suitable double hole channel pore-size distribution, the cost of reduction.
Alumina support of the present invention has bimodal pore passage structure, and its rerum natura is: pore volume 0.70～1.50ml/g, specific area 150.0～300.0m
2/ g, the above pore volume of bore dia 10nm accounts for 30～70% of total pore volume, and wherein the pore volume greater than 100nm accounts for 10～40% of total pore volume, bulk density 0.40～0.60g/ml, crushing strength 120～155N/cm.
The best rerum natura of the invention described above alumina support is: pore volume 0.80～1.30ml/g, specific area 170.0～230.0m
2/ g, the above pore volume of bore dia 10nm accounts for 45～65% of total pore volume, and wherein the pore volume greater than 100nm accounts for 15～30% of total pore volume, bulk density 0.42～0.52g/ml, crushing strength 130～145N/cm.
Method of the present invention is in common alumina supporter preparation process, introduce suitable surface reactive material, utilize its amphiphilic structure to make mixtures dispersions such as aluminium oxide, carbon powder more even,, improve the regularity and the mechanical strength of product pore structure in conjunction with tightr.
Specifically, characteristics of the present invention are that one or more of the boehmite dry glue powder of different material path of preparing are mixed with carbon powder, surface reactive material, by the effect extrusion molding of water, peptizing agent and extrusion aid, promptly make carrier after drying, the roasting again.
The used carbon black of the present invention can be industrial channel carbon black commonly used, high abrasion carbon black, acetylene method carbon black etc.Granularity is 20～40 μ m.
Described surface reactive material is anion surfactant (comprising sulfonate type anion surfactant and sulfuric acid type anion surfactant etc.), cationic surfactant (the alkylamine salt type cationic surfactant of carbon number between 12～18), non-ionic surface active agent (comprising polyethylene glycol type non-ionic surface active agent and polyol-based non-ionic surfactant) and the polymer substance with surfactant properties (comprise cellulose, hard ester acid, polyacrylamide, polyvinyl alcohol, polyethylene glycol etc.).
The present invention in the process of preparation alumina support, in order to make material peptization and extruding better, can be to wherein adding peptizing agent, extrusion aid and water.Peptizing agent can be an organic acid, comprises formic acid, acetate, citric acid, malonic acid etc.; Can be inorganic acid also, comprise nitric acid, hydrochloric acid etc.; Can also be other salt, comprise ammonium phosphate, ammonium sulfate, ammonium nitrate, aluminum nitrate, aluminium chloride, aluminum sulfate etc.Extrusion aid can be starch, methylcellulose, sesbania powder, formic acid, tartaric acid, citric acid; It also can be compound extrusion aid citric acid-sesbania powder etc.
The concrete preparation method of alumina support of the present invention is: take by weighing a certain amount of boehmite dry glue powder and carbon powder (by weight 100: 3～10, based on Al
2O
3) and fully mix with an amount of extrusion aid, add the aqueous solution (ratio of aluminium oxide and surfactant is 100: 0.5～5) that is dissolved with surface reactive material and peptizing agent, mix and pinch evenly, formation pseudoplastic behavior material is by the banded extruder extrusion molding.Strip wet feed after the moulding after 2～4 hours, place muffle furnace through 650～950 ℃ of following roastings 2～4 hours again, thereby the rerum natura of the alumina support that makes is: pore volume 0.70～1.50ml/g, specific area 150.0～300.0m through 100～130 ℃ of dryings
2/ g, the above pore volume of bore dia 10nm accounts for 30～70% of total pore volume, and wherein the pore volume greater than 100nm accounts for 10～40% of total pore volume, bulk density 0.40～0.60g/ml, crushing strength 120～155N/cm.
Alumina support of the present invention can be used as the carrier of hydrogenation catalyst, is specially adapted to the higher feedstock oil of big molecular impurity such as nickel, vanadium, arsenic equal size or the carrier of mink cell focus hydrogenation catalyst.
Carrier of the present invention is owing to add surface reactive material in kneading process, by its amphiphilic structure make between the compound particles such as aluminium oxide, carbon black in conjunction with more firm, make shortcomings such as support strength that expanding agent causes is low, rough surface thereby overcome independent employing carbon black.Simultaneously, the adding with surface-active substance molecule of HMW has also been created advantage for the further formation of carrier macropore.Thereby have features such as high strength, macropore and bimodal pore distribution by the alumina support that the present invention makes.And,, can make high-strength alumina carrier according to industrial different needs with different big hole characteristics distributions by the type and the ratio of modulation aluminium oxide, carbon powder, surface reactive material.
Used surfactant title, type and produce producer and see Table 1 among the embodiment.
Table 1 surfactant is introduced name type and is produced auxiliary reagent factory, auxiliary reagent factory SA-20 non-ionic surface active agent Tianjin, auxiliary reagent factory, producer Ninol non-ionic surface active agent Tianjin lauryl sodium sulfate anion surfactant Tianjin, auxiliary reagent factory, 1227 cationic surfactant Tianjin auxiliary reagent factory, stearic acid polymer substance Tianjin, auxiliary reagent factory polyacrylamide (molecular weight 500～6,000,000) auxiliary reagent factory, polymer substance Tianjin polyvinyl alcohol (mean molecule quantity 60,000) polymer substance Tianjin
Embodiment 1
With 72.5g boehmite powder (U.S. L﹠amp; The V-250 brand is sold by Z trade bloc, aluminium oxide butt content 69%) with channel black powder 3g, Ninol 1g and 2.5g aluminum nitrate, 2.5g sesbania powder, 1.5g citric acid, 55ml water mix, after fully mixed the pinching, on the screw rod banded extruder, be extruded into the trifolium-shaped of diameter 1.8mm, in 120 ℃ of oven dry 3 hours, in muffle furnace, 800 ℃ of following roastings 3 hours, obtain carrier A.
Embodiment 2
With example 1, just surfactant changes 1227 into, and consumption 0.4g obtains carrier B.
Embodiment 3
72.5g boehmite powder (Shenyang Catalyst Plant produces, aluminium oxide butt content 65%) is mixed with channel black powder 3g, lauryl sodium sulfate 0.5g and 1.2g ammonium phosphate, 2g sesbania powder, 77ml water, and pacifying according to the facts, the method for example 1 obtains support C.
Embodiment 4
With 101gV-250 boehmite powder and channel black powder 3.5g, stearic acid 1.4g, and citric acid 2.1g, sesbania powder and each 3.5g of aluminum nitrate, water 90ml mix, obtain carrier D according to the method for embodiment 1.
Embodiment 5
(Shandong Qilu Petroleum Chemical Corporation Institute produces with the boehmite powder, aluminium oxide butt content 70%) 100g and high wear-resistant carbon black powder 4.2g, polyacrylamide 2.1g, citric acid 2.1g, sesbania powder and each 3.5g of aluminum nitrate, water 92.5ml mix, and obtain carrier E according to the method for embodiment 1.
Embodiment 6
Boehmite powder 72.5g and high wear-resistant carbon black powder 4g, Ninol 1g and 7ml nitric acid (20g/100ml, d with the production of Shandong Qilu Petroleum Chemical Corporation Institute
4 25=1.103), 2g sesbania powder, 69ml water mix, and obtains carrying a F according to the method for example 1.
Embodiment 7
Boehmite powder, 3.5g channel black powder and 1.4g1227,2g citric acid, 2g sesbania powder, 3.5g aluminum nitrate, 77ml water that 58.5gV-250 boehmite powder and 42.5g Shandong Qilu Petroleum Chemical Corporation Institute are produced mix, and obtain carrier G according to the method for example 1.
Embodiment 8
With 20g boehmite powder (the German condea SB of company brand, aluminium oxide butt content 73%) and after 50gV-250 boehmite powder mixes, add high wear-resistant carbon black powder 3g, stearic acid 0.5g and mix with 2.5g aluminum nitrate, 2g sesbania powder and 40ml water, after fully mixed the pinching, on the screw rod banded extruder, be extruded into the trifolium-shaped of diameter 1.8mm, in 120 ℃ of oven dry 3 hours, in muffle furnace, 700 ℃ of following roastings 3 hours, obtain carrier H.
Comparative Examples 1
This Comparative Examples is by USP4, the alumina support of the method preparation of describing in 448,896.
Add 270g among the SB boehmite powder 250g and contain the aqueous solution 72 minutes of 7.5g polyvinyl alcohol, and then add high wear-resistant carbon black powder 67.5g (30% (wt) that is equivalent to SB powder amount) 40g water and mixed 30 minutes, be extruded into the cloverleaf pattern bar of diameter 1.8mm, drying is 3 hours under 120 ℃, 600 ℃ of following roastings 3 hours obtain carrier I.
Comparative Examples 2
This Comparative Examples is the alumina support by the preparation of the method described in the Chinese patent 93114901.0.
Adopt the boehmite dry glue powder of aluminum sulfate method production to mix back adding 2.8g high wear-resistant carbon black powder, 2g surfactant SA-20,1.2g aluminum nitrate in 16.7gSB boehmite powder and 27.6g Chang Ling oil plant, and fully mix with 30ml water and to be extruded into diameter 1.8mm cloverleaf pattern bar after pinching, in 120 ℃ of oven dry 8 hours, 600 ℃ of roastings obtained carrier J in 4 hours.
Comparative Examples 3
This Comparative Examples is the alumina support by Chinese patent 96103297.9 described method preparations.
After the boehmite powder that 135g Shandong Qilu Petroleum Chemical Corporation Institute is produced and 8g channel black powder, 4.5g sesbania powder mix, the solution that adding is made into by 216g water and 0.9g phosphoric acid, mix and to be extruded into diameter 1.8mm cloverleaf pattern bar after pinching evenly, and it is following dry 4 hours at 120 ℃, 900 ℃ of following roastings 2 hours obtain carrier K.
Example 9
This example is to be used for comparison by example carrier E and Comparative Examples carrier I, the dearsenification reactivity of the prepared nickel-loaded type of J catalyst (nickel oxide content is 20%) and the situation of change of reaction back support strength.
The dearsenification activity rating carries out on the single tube small test device of diameter 25mm.The loadings of catalyst is 50ml.Feedstock oil (character sees Table 3) is with 8h
-1The air speed charging, be warming up to 290 ℃, pressure keeps 2.0MPA, hydrogen-oil ratio is 150, stablizes and measures the oily arsenic content of outlet after 24 hours as its initial activity.Improve then and dissolve in organo-arsenic raw material oil (arsenic content 25000ppb), when the long-pending arsenic amount on the catalyst reaches 7.0%, advance feedstock oil again.After a period of stabilisation, survey it and export oily arsenic content, and as the later stage activity of catalyst.Catalyst is measured its intensity under driving then, and result of the test sees Table 4.
As everyone knows, platinum, palladium class noble metal catalyst all require comparatively harsh for the arsenic content of feed oil.Resembling reforming raw oil arsenic content requirement must be less than 1ppb, and the charging of cracking stock oil also must not surpass 20ppb.By table 4 contrast as can be known, because carrier of the present invention is owing to possess the macroporous structure that the double hole channel feature distributes, and kept higher compressive resistance simultaneously, thereby all can keep very high dearsenification activity with the later stage in the early stage by its dearsenic catalyst that makes, and has certain impact resistance, still higher-strength can be kept through long-term operation, the industrial production needs can be satisfied.
Each carrier rerum natura carrier A B C D E F G H I J K pore volume ml/g 1.27 0.92 1.15 1.00 1.14 0.85 1.42 0.75 0.65 0.68 0.98 specific area m of table 2
2/ g 179.7 199.8 226.3 199.7 182.1 249.6 158.0 265.3 215.2 235.6 170.0 pore size distributions (accounting for the percentage of total pore volume)＞10nm 63.5% 50.4% 51.8% 48.8% 54.4% 36.2% 68.8% 42.0% 56.8% 33.2% 82.4%＞100nm 13.7% 19.6% 21.3% 22.3% 25.7% 12.5% 32.3% 11.2% 7.4% 4.8% 5.6% bulk density g/ml 0 49 0.43 0.44 0.50 0.43 0.52 0.40 0.58 0.60 0.62 0.52 intensity N/cm 137 138 122 142 131 148 124 144 83 134 85
Table 3 feedstock oil performance matter proportion arsenic content viscosity S N carbon residue boiling range d
4 20Ppb wt% wt% initial boiling point ℃ does ℃ 0.722 610 14.8 * 10
-30.6 * 10
-334 180
Table 4 activity of such catalysts and post reaction strength comparative catalyst used carrier E I J initial stage export oily arsenic content * 10
-94.1 4.0 4.2 later stages exported oily arsenic content * 10
-96.8 28.4 32.5 running rear catalyst intensity N/cm, 142 74 143 running rear catalyst outward appearance intact part efflorescence are complete
Claims (5)
1. a macropore high-strength alumina carrier is characterized in that its pore volume is 0.70～1.50ml/g, and specific area is 150.0～300.0m
2/ g, the bore dia pore volume more than 10nm accounts for 30～70% of total pore volume, and wherein the pore volume greater than 100nm accounts for 10～40% of total pore volume, and bulk density is 0.40～0.60g/ml; Crushing strength is 120～150N/cm.
2. the preparation method of the described alumina support of claim 1, it is characterized in that and to mix with carbon black powder, surface reactive material by one or more of the boehmite dry glue powder of different material path of preparing, wherein the weight ratio of boehmite dry glue powder and carbon powder and surface reactive material is: 100: 3～10: 0.5～5, after peptization, moulding, 100～130 ℃ of dryings, make at 650～950 ℃ of following constant temperature calcinings.
3. according to the preparation method of claim 2, the time that it is characterized in that constant temperature calcining is 2～4 hours.
4. according to the preparation method of claim 2, it is characterized in that carbon powder one of comprises in channel black powder, high wear-resistant carbon black powder or the acetylene carbon black powder or its mixture, granularity 20～40 μ m.
5. according to the preparation method of claim 2, it is characterized in that used surface reactive material is that cationic surface active agent, anionic surfactant, nonionic surface active agent and a part one of have in the polymer substance of surfactant properties or its mixture.
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| CN98114347A CN1089039C (en) | 1998-09-28 | 1998-09-28 | Macroporous alumina carrier and preparing process thereof |
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| CN98114347A CN1089039C (en) | 1998-09-28 | 1998-09-28 | Macroporous alumina carrier and preparing process thereof |
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| CN1296136C (en) * | 2004-01-19 | 2007-01-24 | 中国石油化工股份有限公司 | Macroporous aluminium oxide carrier and its preparing method |
| CN100346873C (en) * | 2005-09-09 | 2007-11-07 | 清华大学 | Method for preparing large pore capacity, high specific surface area alumina |
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| CN1249208A (en) | 2000-04-05 |
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