CN103055944A - Preparation method of phosphorus-containing alumina carrier - Google Patents
Preparation method of phosphorus-containing alumina carrier Download PDFInfo
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- CN103055944A CN103055944A CN2011103211782A CN201110321178A CN103055944A CN 103055944 A CN103055944 A CN 103055944A CN 2011103211782 A CN2011103211782 A CN 2011103211782A CN 201110321178 A CN201110321178 A CN 201110321178A CN 103055944 A CN103055944 A CN 103055944A
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Abstract
The invention discloses a preparation method of a phosphorus-containing alumina carrier. The method comprises: first pulping aluminum hydroxide or alumina into a slurry, and adding concentrated phosphoric acid for reaction to obtain sol; and then taking the sol as a binder, kneading it with macropore alumina and micropore alumina, and carrying out molding, drying and roasting to obtain the alumina carrier. According to the method provided in the invention, phosphorus is introduced into the alumina carrier in the form of a binder, and can place a structural promoter role to improve the active metal dispersity on the alumina carrier. The weak acid amount of the carrier can be increased, the medium-strong acid amount can be reduced, and the total acid amount can be decreased. Especially, the corrosive effect of the phosphorus-containing binder on an alumina carrier skeleton is greatly reduced, and the pore structure and the mechanical strength of the alumina carrier can be significantly improved. Meanwhile, the consumption of a phosphorus-containing sol binder is less, and the preparation process is environment-friendly and pollution-free.
Description
Technical field
The present invention relates to a kind of preparation method of phosphorus-containing alumina carrier, this carrier has high specific surface area, and large pore volume can be used as the carrier that wax oil hydrogenation is processed catalyst.
Background technology
Contain sulphur, nitrogen, oxygen and metal impurities in crude oil and the distillate that from crude oil, obtains.The existence of these impurity not only affects the stability of oil product, and in use also can discharge SO
X, NO
XDeng the pernicious gas contaminated environment.In the secondary processing process of oil product, the existence of sulphur, nitrogen, oxygen and metal impurities can make catalyst poisoning.Therefore, removing above-mentioned impurity is significant process in the oil product processing.Distillate hydrogenation is processed and is referred to that under uniform temperature and pressure feedstock oil contacts with catalyst with hydrogen, imurity-removal, and the process of aromatic saturation.
As everyone knows, the pore structure of catalyst has important impact to the serviceability of catalyst.Process catalyst for wax oil hydrogenation, generally need to have larger aperture and pore volume, be beneficial to the interior diffusion of macromolecular reaction thing in the wax oil, avoid or slow down because the deposition of metal impurities and blocking catalyst duct, cause the catalyst activity fast-descending, shorten the service cycle of device.Because the pore structure of catalyst depends primarily on the pore structure of carrier, so, at first to prepare the alumina support that has than large pore volume and aperture.
Phosphorus as auxiliary agent in being usually used in hydrotreatment carrier and catalyst, it is conducive to improve the decentralization of alumina carrier surface metal, and suitable phosphorus content can make the weak acid amount increase, and middle strong acid amount reduces, total acid content reduces, and can effectively improve the denitrification activity of wax oil hydrogenation catalyst.Phosphorus can become in the glue process to add at aluminium oxide during as structurally-modified auxiliary agent, also can add in the kneading process of alumina support preparation.Simultaneously, traditional carrier of hydrogenating catalyst often uses the strongly acidic solutions such as nitric acid as binding agent in preparation process, nitric acid has strong oxidizing property and highly acid, can make the aperture pore volume that very large loss is arranged in the process of bonding, corrodes the specific area of carrier; Contain the nitrogen element in the nitric acid and can in the process of roasting, produce NO
x, etching apparatus, contaminated environment; Moreover in order to obtain the carrier of high pore volume, usually necessary through high-temperature roasting, but such high-temperature roasting will inevitably make the carrier sintering, and cause the surface area of carrier very little.Therefore to reach the requirement of the high pore volume catalyst of high-specific surface area, must prepare have the high-ratio surface large pore volume carrier to satisfy the demand.
CN99112940.7 provides a kind of preparation method of Hydrobon catalyst, the preparation method of its carrier is: with the abundant kneading of mixed solution, the moulding of a water alumina dry glue and titanium chloride and phosphorus-containing compound, then carry out drying, washing, calcination steps and obtain Ti-P-γ-Al
2O
3Carrier.This process preparation flow is complicated, and sintering temperature is higher, causes easily the destruction of pore structure.
CN93107376.6 provides a kind of method for preparing alumina support.Adopting a water aluminum oxide dry glue powder is raw material, adds nitric acid and/or acetic acid solution, through fully mixing, is kneaded into plastic shape, is extruded into strip and lower dry at 105 ℃～130 ℃.Dry sample adopts three sections constant temperature calcining programs, to make the γ-Al with better physical and chemical performance
2O
3It is that binding agent corrodes the duct easily that this process adopts nitric acid, causes the destruction of pore structure, and its nitroxylic acid is easy etching apparatus contaminated environment in the process of roasting, moreover repeatedly roasting makes the specific area loss of carrier larger easily.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of preparation method of phosphorus-containing alumina carrier.Described structural promoter phosphorus is introduced in the alumina support with the form of phosphorous binding agent, both alumina support is carried out modification, can play again the effect of binding agent simultaneously.
The preparation method of alumina support provided by the invention may further comprise the steps:
(1) preparation of binding agent
With aluminium hydroxide or aluminium oxide and deionized water making beating, be dispersed into the slurries that the aluminium oxide solid content is 10～50 % by weight, stir lower in the slurries weight ratio adding SPA according to P/Al=1～7, then be warming up to 60 ℃～100 ℃, and under this temperature, react 15min～180 min, obtain transparent sol adhesive;
(2) macroporous aluminium oxide, little porous aluminum oxide are mixed with certain proportion, add the prepared binding agent of step (1), with the abundant kneading of extrusion aid, after moulding, drying and roasting, obtain the phosphorus-containing alumina carrier.
According to the preparation method of alumina support of the present invention, wherein the sol adhesive of step (1) preparation contains the Al of 1～10 % by weight and the P of 5～20 % by weight, and its P/Al weight ratio is that 1～7, pH value is 1.0～4.0.Wherein the aluminium hydroxide described in the step (1) or aluminium oxide can be by sour peptizations.
The concrete ratio of the macroporous aluminium oxide described in the step (2) and little porous aluminum oxide can be decided according to the pore structure of prepared alumina support.Described extrusion aid is the extrusion aid commonly used of this area, and extrusion aid generally comprises the materials such as starch, sesbania powder or cellulose.The stereoscopic different various shapes that require can be made into of carrying alumina described in the step (2), for example sphere, sheet shape or bar shaped, preferably bar shaped (clover, bunge bedstraw herb etc.).
Compared with prior art, among the preparation method of alumina support provided by the invention, auxiliary agent phosphorus is introduced in the carrier with the form of binding agent and is had the following advantages:
1, phosphorus can play the effect of structural promoter, and the adding of auxiliary agent phosphorus can improve the reactive metal decentralization on the alumina support, thereby is conducive to the raising of obtained catalyst activity.And suitable phosphorus content can make the weak acid amount of alumina support increase, and middle strong acid amount reduces, and total acid content reduces, thereby can effectively improve the denitrification activity of wax oil hydrogenation catalyst.
2, because phosphoric acid is middle strong acid, after auxiliary agent phosphorus is made phosphorus-containing aluminium sol adhesive by SPA and is introduced carrier with the binding agent form, on the one hand the adhesive property of phosphorated aluminiferous collosol is better than the adhesive property that uses nitric acid or other acid and aperture aluminium oxide peptization to make binding agent in the prior art, and is can be in the mechanical strength that keeps carrier constant even also have the consumption that reduces binding agent in the situation about increasing; On the other hand, be different from the peptizing agent such as widely used nitric acid in the prior art, after phosphorus is introduced alumina support with the sol adhesive form, since its acidity a little less than, its corrosiveness to the alumina support skeleton is slowed down greatly, thereby the character such as the specific area of carrier and aperture pore volume are had no significant effect, can improve the pore structure of obtained alumina support and the crushing strength of catalyst.
3, adopt phosphorated aluminiferous collosol few as consumption of binder, preparation process is environment friendly and pollution-free.
The specific embodiment
The concrete preparation process of alumina support provided by the invention may further comprise the steps:
(1) preparation of phosphorous binding agent
With a kind of can be by the aluminium hydroxide of sour peptization or aluminium oxide and deionized water making beating, be dispersed into the slurries that the aluminium oxide solid content is 10～50 % by weight, stir lower in these slurries the weight ratio adding SPA according to P/Al=1～7, then be warming up to 60 ℃～100 ℃, and under this temperature, react 15min～180min, until become transparent colloidal sol colloid.
The prepared sol adhesive of step (1) contains the Al of 1～10 % by weight, preferably contains the Al of 2～10 % by weight; The P that contains 5～20 % by weight, the P of preferred 10～18 % by weight; Its P/Al weight ratio is 1～7, preferred 1～6; The pH value is 1.0～4.0, is preferably 1.0～3.2.
Step (1) is described can be in ρ-aluminium oxide, χ-aluminium oxide, η-aluminium oxide, gama-alumina, κ-aluminium oxide, δ-aluminium oxide and the θ-aluminium oxide one or more by the aluminium oxide of sour peptization; Described can be in aluminium hydroxide, gibbsite, surge aluminium stone, promise diaspore, boehmite and the boehmite one or more by the aluminium hydroxide of sour peptization, preferred boehmite or aluminium hydroxide.
(2) macroporous aluminium oxide, little porous aluminum oxide are mixed with certain proportion, add prepared binding agent and the extrusion aid of step (1), through kneading, roll, moulding, drying, roasting obtain required alumina support.
The specific area of the macroporous aluminium oxide described in the step (2) is general 〉=260 m
2/ g, preferred 270m
2/ g～400m
2/ g; Pore volume 〉=0.8 cm
3/ g, preferred 0.8cm
3/ g～1.2 cm
3/ g; Aperture 〉=110, preferred 120～200.The specific area of described little porous aluminum oxide is general≤210m
2/ g, excellent in selecting 170 m
2/ g～210 m
2/ g; Pore volume is general≤0.5 cm
3/ g, preferred 0.4 cm
3/ g～0.5cm
3/ g; The aperture generally≤110, preferred 90～110.
Drying condition described in the step (2) is: baking temperature is 100 ℃～300 ℃, and preferred 100 ℃～220 ℃, be 1h～5h drying time, preferred 2h～4h.Dry atmosphere can be air or other atmosphere.Described roasting condition is: sintering temperature is 350 ℃～800 ℃, and preferred 400 ℃～550 ℃, roasting time is 2h～5h, preferred 3h～5h.The roasting atmosphere is the oxygen-containing gas atmosphere.
In above-mentioned step (1) or step (2), can also add inorganic assistant, preferably (kneading process) adds inorganic assistant in step (2).Suitable inorganic assistant comprises fluorine, silicon, titanium, boron etc., or their mixture.
Other condition in the alumina support preparation process of the present invention can be determined by this area general knowledge.
Preparation method to alumina support of the present invention is described in detail below by specific embodiment.Embodiment just to the illustrating of the specific embodiment of the inventive method, does not consist of the restriction of protection domain of the present invention.
In the embodiment of the invention and the comparative example: SPA is for analyzing pure (concentration is 85wt%), and Tianjin Da Mao chemical reagent factory is produced; Nitric acid (concentration is 65wt%), citric acid (concentration is 99wt%) are that analysis is pure, and the sesbania powder is chemical pure, and power sincere chemical reagent work in Shenyang produces; Macroporous aluminium oxide (pore volume 〉=1.0 cm
3/ g, aperture 〉=150), little porous aluminum oxide (pore volume≤0.4 cm
3/ g, aperture≤110), boehmite (butt 0.75), the permanent brightness chemical industry in Yantai Co., Ltd, refining aluminium hydroxide (without Fe), the Jinan rising sun in morning chemical industry Co., Ltd.
Comparative example 1
After 230g macroporous aluminium oxide (butt 70%) and the little porous aluminum oxide of 15g (butt 75%) be dry mixed 5min, then add 10g nitric acid (concentration 65%), 14.7g SPA (concentration 85%), the 220g water purification, 4g sesbania powder and 4g citric acid carry out kneading, become plastic, then be extruded into the bunge bedstraw herb that diameter is 1.2mm at banded extruder, in 120 ℃ of dryings 3 hours, 550 ℃ of roastings 3 hours, get carrier ZT-1, its character is listed in table 1.
Comparative example 2
After 460g macroporous aluminium oxide (butt 70%) and the little porous aluminum oxide of 30g (butt 75%) be dry mixed 5min, then add 31g SPA (concentration 85%), the 440g water purification, 8g sesbania powder and 8g citric acid carry out kneading, become plastic, then are extruded into the bunge bedstraw herb that diameter is 1.2mm at banded extruder, in 130 ℃ of dryings 3 hours, 500 ℃ of roastings 3 hours get carrier ZT-2, and its character is listed in table 1.
Embodiment 1
With the refining aluminium hydroxide of 200g and 200g deionized water making beating 30 minutes, stir lower in the slurries adding 300g SPA (concentration 85%), be warmed up to 75 ℃, then under this temperature, reacted 45 minutes, namely make water white phosphorated aluminiferous collosol, its pH value is 2.8.By analysis, containing P in this phosphorated aluminiferous collosol is 11.5 % by weight, and Al is 9.9 % by weight, and the P/Al weight ratio is 1.2.
After 230g macroporous aluminium oxide (butt 70%) and the little porous aluminum oxide of 15g (butt 75%) be dry mixed 5min, then add the above-mentioned binding agent of 35g, the 220g water purification, 4g sesbania powder and 4g citric acid carry out kneading, become plastic, then are extruded into the bunge bedstraw herb that diameter is 1.2mm at banded extruder, in 120 ℃ of dryings 3 hours, 450 ℃ of roastings 3 hours get carrier ZT-3, and its character is listed in table 1.
Embodiment 2
92g boehmite and 200g deionized water were pulled an oar 30 minutes, add 300g SPA (concentration 85%) under stirring in slurries, be warmed up to 80 ℃, then reacted 50 minutes under this temperature, namely make water white phosphorated aluminiferous collosol, its pH value is 2.5.By analysis, it is 13.6 % by weight that this phosphorated aluminiferous collosol contains P, and Al is 6.2 % by weight, and the P/Al weight ratio is 2.2.
After 230g boehmite (butt 70%) and the little porous aluminum oxide of 15g (butt 75%) be dry mixed 5min, then add the above-mentioned binding agent of 30g, the 220g water purification, 4g sesbania powder and 4g citric acid carry out kneading, become plastic, then are extruded into the bunge bedstraw herb that diameter is 1.2mm at banded extruder, in 110 ℃ of dryings 4 hours, 500 ℃ of roastings 2.5 hours get carrier ZT-4, and its character is listed in table 1.
Embodiment 3
With the refining aluminium hydroxide of 68g and 160g deionized water making beating 30 minutes, stir lower in the slurries adding 300g SPA (concentration 85%), be warmed up to 95 ℃, then under this temperature, reacted 100 minutes, namely make water white phosphorated aluminiferous collosol, its pH value is 2.2.By analysis, it is 15.3 % by weight that this phosphorated aluminiferous collosol contains P, and Al is 4.5 % by weight, and the P/Al weight ratio is 3.4.
After 230g macroporous aluminium oxide (butt 70%) and the little porous aluminum oxide of 15g (butt 75%) be dry mixed 5min, then add the above-mentioned binding agent of 28g, the 220g water purification, 4g sesbania powder and 4g citric acid carry out kneading, become plastic, then are extruded into the bunge bedstraw herb that diameter is 1.2mm at banded extruder, in 150 ℃ of dryings 2 hours, 550 ℃ of roastings 2 hours get carrier ZT-5, and its character is listed in table 1.
Embodiment 4
50g boehmite and 200g deionized water were pulled an oar 30 minutes, in slurries, add 300g SPA (concentration 85%) under stirring, be warmed up to 75 ℃, then under this temperature, reacted 120 minutes, namely make water white phosphorated aluminiferous collosol, its pH value 1.7.By analysis, it is 14.7 % by weight that this phosphorated aluminiferous collosol contains P, and Al is 3.6 % by weight, and the P/Al weight ratio is 4.1.
After 230g macroporous aluminium oxide (butt 70%) and the little porous aluminum oxide of 15g (butt 75%) be dry mixed 5min, then add the above-mentioned binding agent of 28g, the 220g water purification, 4g sesbania powder and 4g citric acid carry out kneading, become plastic, then are extruded into the bunge bedstraw herb that diameter is 1.2mm at banded extruder, in 120 ℃ of dryings 3 hours, 450 ℃ of roastings 3 hours get carrier ZT-6, and its character is listed in table 1.
Embodiment 5
With the refining aluminium hydroxide of 40g and 200g deionized water making beating 30 minutes, stir lower in the slurries adding 300g SPA (concentration 85%), be warmed up to 100 ℃, then under this temperature, reacted 160 minutes, namely make water white phosphorated aluminiferous collosol, its pH value 1.0.By analysis, it is 14.9 % by weight that this phosphorated aluminiferous collosol contains P, and Al is 2.6 % by weight, and the P/Al weight ratio is 5.7.
After 230g macroporous aluminium oxide (butt 70%) and the little porous aluminum oxide of 15g (butt 75%) be dry mixed 5min, then add the above-mentioned binding agent of 28g, the 220g water purification, 4g sesbania powder and 4g citric acid carry out kneading, become plastic, then are extruded into the bunge bedstraw herb that diameter is 1.2mm at banded extruder, in 120 ℃ of dryings 3 hours, 500 ℃ of roastings 3.5 hours get carrier ZT-7, and its character is listed in table 1.
The Main physical character of comparative example 1～2 and embodiment 1～5 gained carrier is listed in table 1.
Table 1
| Bearer number | ZT-1 | ZT-2 | ZT-3 | ZT-4 | ZT-5 | ZT-6 | ZT-7 |
| Phosphorus, % by weight | 2.3 | 2.4 | 2.3 | 2.4 | 2.5 | 2.4 | 2.4 |
| Bulk density/gmL -1 | 53 | 54 | 59 | 60 | 61 | 60 | 56 |
| Mechanical strength/Nmm -1 | 9.5 | 9.2 | 11.6 | 11.2 | 11.5 | 11.3 | 10.8 |
| Specific area/cm 2·g -1 | 313 | 298 | 300 | 305 | 299 | 309 | 301 |
| Pore volume/mLg -1 | 0.63 | 0.65 | 0.73 | 0.72 | 0.74 | 0.75 | 0.66 |
| Can several apertures/ | 90 | 99 | 113 | 112 | 112 | 114 | 101 |
| Pore volume distribution/v% | ? | ? | ? | ? | ? | ? | ? |
| ＜40 ? | 2.9 | 3.5 | 2.2 | 2.3 | 2.1 | 2.1 | 3.1 |
| 40～80 ? | 31.1 | 22.3 | 18.5 | 19.2 | 17.9 | 20.0 | 21.2 |
| 80～150 ? | 56.0 | 57.2 | 63.2 | 63.1 | 64.2 | 65.1 | 58.2 |
| ＞150 ? | 10.0 | 17.0 | 16.1 | 15.4 | 15.8 | 12.8 | 17.5 |
By as seen from Table 1, to compare with comparative example 1 and comparative example 2, the mechanical strength of embodiment gained alumina support increases obviously; Especially the pore size distribution of gained alumina support is more concentrated, and the ratio that 80～150 hole accounts for total pore volume is higher, and that 40～80 hole accounts for the ratio of total pore volume is lower; Simultaneously, embodiment gained alumina support can also will be higher than the prepared sample of comparative example method with total pore volume in several apertures.Be that the method that the present invention introduces auxiliary agent phosphorus in the binding agent mode not only can make moderate progress to the mechanical strength of alumina support, also more be conducive to prepare simultaneously the alumina support with perfect apertures structure.
Claims (11)
1. the preparation method of a phosphorus-containing alumina carrier may further comprise the steps:
(1) with aluminium hydroxide or aluminium oxide and deionized water making beating, be dispersed into the slurries that the aluminium oxide solid content is 10～50 % by weight, stir lower in the slurries weight ratio adding SPA according to P/Al=1～7, then be warming up to 60 ℃～100 ℃, and under this temperature, react 15min～180 min, obtain transparent sol adhesive;
(2) macroporous aluminium oxide, little porous aluminum oxide are mixed with certain proportion, add the prepared binding agent of step (1), with the abundant kneading of extrusion aid, after moulding, drying and roasting, obtain the phosphorus-containing alumina carrier.
2. according to preparation method claimed in claim 1, it is characterized in that the sol adhesive of step (1) preparation contains the Al of 1～10 % by weight and the P of 5～20 % by weight, its P/Al weight ratio is that 1～7, pH value is 1.0～4.0.
3. according to preparation method claimed in claim 2, it is characterized in that the sol adhesive of step (1) preparation contains the Al of 2～10 % by weight and the P of 10～18 % by weight, its P/Al weight ratio is that 1～6, pH value is 1.0～3.2.
4. according to preparation method claimed in claim 1, it is characterized in that the aluminium hydroxide described in the step (1) or aluminium oxide can be by sour peptizations.
5. according to preparation method claimed in claim 4, it is characterized in that described can be in ρ-aluminium oxide, χ-aluminium oxide, η-aluminium oxide, gama-alumina, κ-aluminium oxide, δ-aluminium oxide and the θ-aluminium oxide one or more by the aluminium oxide of sour peptization; Described can be in aluminium hydroxide, gibbsite, surge aluminium stone, promise diaspore, boehmite and the boehmite one or more by the aluminium hydroxide of sour peptization.
6. according to preparation method claimed in claim 4, it is characterized in that described can be boehmite or aluminium hydroxide by the aluminium hydroxide of sour peptization.
7. according to preparation method claimed in claim 1, it is characterized in that the Bi Biao Mian Ji of the macroporous aluminium oxide described in the step (2)＞=260 m
2/ g, Kong Rong＞=0.8 cm
3/ g, Kong Jing＞=100; Described little porous aluminum oxide than long-pending＜=210 m of table face
2/ g, Kong Rong＜=0.5 cm
3/ g, Kong Jing＜=110.
8. according to claim 1 or 7 described preparation methods, it is characterized in that the specific area of the macroporous aluminium oxide described in the step (2) is 270m
2/ g～400m
2/ g, pore volume are 0.8cm
3/ g～1.2 cm
3/ g, the aperture is 100～120; The specific area of the little porous aluminum oxide described in the step (2) is 170 m
2/ g～210 m
2/ g, pore volume are 0.4 cm
3/ g～0.5cm
3/ g, the aperture is 90～110.
9. according to preparation method claimed in claim 1, it is characterized in that add inorganic assistant in step (1) or step (2), inorganic assistant is selected from one or more in fluorine, silicon, titanium or boron and the compound thereof.
10. according to preparation method claimed in claim 1, it is characterized in that the drying condition described in the step (2) is: baking temperature is 100 ℃～300 ℃, and be 1h～5h drying time; Described roasting condition is: sintering temperature is 350 ℃～800 ℃, and roasting time is 2h～5h.
11., it is characterized in that described baking temperature is 100 ℃～220 ℃ according to preparation method claimed in claim 1, be 2h～4h drying time; Described sintering temperature is 400 ℃～550 ℃, and roasting time is 3h～5h.
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| WO2021218982A1 (en) * | 2020-04-28 | 2021-11-04 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method therefor and use thereof |
| CN114426300A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Preparation method of macroporous alumina carrier |
| EP3904286A4 (en) * | 2018-12-28 | 2022-11-30 | China Petroleum & Chemical Corporation | Pseudoboehmite, and manufacturing method therefor and application thereof |
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| WO2021218982A1 (en) * | 2020-04-28 | 2021-11-04 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method therefor and use thereof |
| CN114426300A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Preparation method of macroporous alumina carrier |
| CN114426300B (en) * | 2020-10-14 | 2023-07-28 | 中国石油化工股份有限公司 | Preparation method of macroporous alumina carrier |
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