CN1350888A - Alumina carrier containing Zr and its preparing process - Google Patents
Alumina carrier containing Zr and its preparing process Download PDFInfo
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- CN1350888A CN1350888A CN 00123133 CN00123133A CN1350888A CN 1350888 A CN1350888 A CN 1350888A CN 00123133 CN00123133 CN 00123133 CN 00123133 A CN00123133 A CN 00123133A CN 1350888 A CN1350888 A CN 1350888A
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Abstract
A Zr-contained alumina carrier for hydrorefining catalyst of fractional oil is prepared by adding Zr-contained compound in kneading manner in the process to shape alumina carrier. Its advantages include higher lateral pressure strength, stable acidity and narrow range of pore diameters.
Description
The present invention relates to a kind of alumina carrier containing Zr and preparation method thereof, particularly a kind of carrier that is applicable to catalyst for hydrorefining distillate oil and preparation method thereof.
Comparatively typical catalyst for hydrorefining distillate oil carrier is normally based on aluminum oxide, for the catalyzer that carrier is thus made reaches higher hydrogenation activity and stability thereof, can adopt various treatment processs to carrier, as: carrier is carried out modification, improve preparation condition, add auxiliary agent etc.At present, the most widely used method is to add auxiliary agent.These auxiliary agents mainly contain phosphorus (P), fluorine (F), boron (B), titanium (Ti) etc., and selecting comparatively general auxiliary agent now for use is phosphorus (P) and boron (B).
Phosphorus (P) is owing to itself character, and when adding auxiliary agent phosphorus (P) in the aluminum hydroxide solid elastomer powder, can giving afterwards, the shaping work of carrier brings very big difficulty; Boron (B) is though be a kind of comparatively ideal auxiliary agent, and at room temperature, the solubleness of boric acid is very little, join the high solution of boron-containing quantity, process is comparatively complicated, difficulty is also very big.
At present, in the preparation process of catalyzer and carrier, some technology is to adopt the auxiliary component of zirconium as catalyzer, but zirconium generally all is to support on the support of the catalyst with the form of flooding, and its at be the hydrogenation process of mink cell focus, simultaneously zirconium-containing compound therein role also have nothing in common with each other.
At publication number is in the patent of invention of JP60025545, it is intensity for the enhanced activity alumina supporter that the saturated solution of zirconium-containing compound is impregnated into purpose on the formed alumina with the form of dipping, and the pore diameter range of this carrier is between 40nm～100nm, belong to the macropore scope, at be the shortening reforming process of mink cell focus.Zirconium-containing compound is in zirconic form simultaneously, and zirconium white accounts for 10%～50% of total weight of carrier, and the content of zirconium is higher.
At publication number is in the United States Patent (USP) of US4724227 and US4681869, zirconium is as the active ingredient of a kind of active ingredient with VIII family and group vib, form with dipping is immersed on the formed alumina carrier, its objective is in order to prepare a kind of hydrogenation activity higher, and at the catalyzer of the unifining process of mink cell focus.
As mentioned above, in the existing and disclosed patent, the technology that adds zirconium in catalyzer mainly is to be applicable to the mink cell focus hydrogenation catalyst, and mostly zirconium-containing compound is to be impregnated on the formed alumina carrier with the form of dipping.
Purpose of the present invention will prepare a kind of pore distribution concentration exactly, and intensity and acidity is the ideal carrier comparatively, makes it be particularly suited for using as a kind of carrier of catalyst for hydrorefining distillate oil.
The principal feature of alumina carrier containing Zr of the present invention is:
Total weight percent with carrier is a benchmark, comprising: ZrO
22.0%～14.0%, SiO
20.0%～10.0%, aluminum oxide 40.0%～98.0%, preferably ZrO
24.0%～8.0%, SiO
22.0%～6.0%, aluminum oxide 55.0%～86.0%.
The physico-chemical property of described alumina carrier containing Zr is: pore volume is 0.20cm
3/ g～0.75cm
3/ g, specific surface area is 180m
2/ g～350m
2/ g, mean pore size is 5.0nm～12.0nm;
The characteristics of the pore distribution of above-mentioned carrier are: the hole of＜4.0nm accounts for 1.5%～15.0% of total hole, and the hole between 4.0nm～15.0nm accounts for 83.0%～95.0% of total hole, and the hole of＞15.0nm accounts for 1.0%～11.5% of total hole; But preferably: the hole of＜4.0nm accounts for 1.5%～4.0% of total hole, and the hole between 4.0nm～15.0nm accounts for 88.5%～95.0% of total hole, and the hole of＞15.0nm accounts for 1.0%～3.5% of total hole.
The infrared acidity of above-mentioned carrier is generally: between 0.250mmol/g～0.320mmol/g (the indication meleic acid is the total acid under 160 ℃ herein) but be preferably: between 0.255mmol/g～0.300mmol/g.
The side pressure strength of above-mentioned carrier is generally: 12.0N/mm～25.0N/mm is preferably: 16.0N/mm～22.5N/mm.
The preparation main points of above-mentioned carrier mainly are to have added zirconium-containing compound to mix the form of pinching in the moulding process of carrier, and at a certain temperature then, drying, roasting make alumina carrier containing Zr of the present invention.
The concrete preparation process of alumina carrier containing Zr of the present invention comprises the steps:
(1) compound of zirconium is soluble in water, stirring is mixed with the solution that contains zirconium after making its dissolving;
(2) solution prepared in (1) added contain in the aluminum hydroxide solid elastomer powder of extrusion aid, mix pinch evenly after, extruded moulding.(extrusion aid can be a kind of, also the combination of multiple extrusion aid);
(3) with the carrier of extruded moulding in (2) between 100 ℃～130 ℃ temperature dry 2 hours～6 hours, roasting 2 hours～8 hours between 500 ℃～700 ℃ and make alumina carrier containing Zr of the present invention.
(peptizing agent can be a kind of generally all will to add a certain amount of peptizing agent in the process for preparation of zirconium-containing compound mixing solutions in described (1) step, can also be the combination of multiple peptizing agent), so that the kneading and compacting of carrier, if but the zirconium-containing compound that is added has certain acidity, then can not add peptizing agent or add peptizing agent less.Wherein, peptizing agent can be a kind of in mineral acid, organic acid, the strongly-acid negatively charged ion aluminium salt, such as: nitric acid, hydrochloric acid, oxalic acid, formic acid, acetate, citric acid, aluminum nitrate or the like also can be the wherein combinations of several peptizing agents.The water that described obtain solution process adds is deionized water preferably.
Described zirconium-containing compound can be a variety of, and used zirconium-containing compound is basic zirconium chloride, bromine zirconium white, zirconium sulfate, hydrogen sulfate zirconium white, zirconium nitrate, carboxylic acid zirconium etc. usually, but preferably selects basic zirconium chloride (ZrOCl for use
2.8H
2O).At first, zirconium is to add in the aluminum hydroxide solid elastomer powder to mix the form of pinching as a kind of auxiliary agent, and it also makes the side pressure strength of carrier be improved when playing promoter effect; Secondly, because basic zirconium chloride has certain acidity, can play the peptized acidic effect, the help carrying alumina is body formed, therefore, other plays the acid or the acidic substance of peptization just can not add or add less some, has reduced the negative impact to the carrier physico-chemical property of these acid or acidic substance.In addition, in the moulding process of carrier, add basic zirconium chloride, the physico-chemical property of carrier is improved, can also make its acidity maintain a comparatively stable scope simultaneously to mix the form of pinching.Therefore, use this basic zirconium chloride that plays difunctional effect that the preparation alumina carrier containing Zr is had very big benefit.
Above-mentioned (2) step alumina carrier containing Zr the extruded moulding detailed process can for:
Take by weighing aluminum hydroxide solid elastomer powder and a certain amount of extrusion aid of aequum, after mixing, adding (1) step has therein prepared the mixing solutions of the zirconium-containing compound that finishes, mix pinch into uniform plastic paste after, on banded extruder, be extruded into stripe shape carrier with certain outward appearance.This stripe shape carrier can be columniform, also can be (as trifolium, the Herba Galii Bungei etc.) of special-shaped bar; The extrusion aid that is adopted can be sesbania powder, starch, Mierocrystalline cellulose, powdered carbon etc., also can be the wherein combination of several extrusion aids.
In the preparation process of carrier, can add a certain amount of silicon sol and/or carbon black, also can not add silicon sol and/or carbon black.(above-mentioned SiO
2Content is 0.0%, promptly refers to not add silicon sol)
In the carrier moulding process, the adding of silicon sol has two kinds of methods: a kind of is silicon sol to be added earlier be mixed with in extrusion aid and the sooty aluminum hydroxide solid elastomer powder, after mixing, adds zirconium-containing compound more therein; Second method is earlier silicon sol and zirconium-containing compound to be mixed, and adds afterwards to be mixed with in extrusion aid and the sooty aluminum hydroxide solid elastomer powder; From effect, by the carrier that first method makes, it is concentrated that pore distribution more becomes.Described carbon black is as a kind of expanding agent, before the carrier moulding, mixes with aluminum hydroxide solid elastomer powder and extrusion aid, and its add-on generally is 1.0%～30% of formed alumina total weight of carrier.
Compared with prior art, the present invention is by having made a kind of alumina carrier containing Zr to mix the form adding zirconium-containing compound of pinching in the moulding process of carrier; In the moulding process of carrier, zirconium directly enters among the skeleton of aluminum oxide, the side pressure strength of alumina supporter is improved, acidity maintains a comparatively stable stage, it can also make the pore distribution of carrier comparatively concentrate on the mesopore scope, and the carrier that makes carrier of the present invention can be used as a kind of catalyst for hydrorefining distillate oil is used; Simultaneously, the present invention can be by selecting comparatively suitable zirconium-containing compound for use, the disadvantage of avoiding auxiliary agent phosphorus (P), boron (B) to be produced.
Further specify the preparation process of advantage of the present invention, technical characterictic and carrier below by embodiment, but should not think that invention only is confined to this.
Embodiment 1
Present embodiment has been introduced the moulding process of alumina carrier containing Zr.
(Shandong Province Chemical Fertilizer Factory No.1, Qilu Petrochemical Co. produces, and contains Al to take by weighing four groups of each 100g of aluminum hydroxide solid elastomer powder respectively
2O
370.8w%), after respectively adding 5.0g sesbania powder therein, take by weighing 7.8g more respectively, 12.0g, 16.4g, 20.8g basic zirconium chloride (zirconic content is 37.9w%), after the deionized water of getting four parts of 80ml dissolves respectively, add and contain in the aluminum hydroxide solid elastomer powder of sesbania powder, mix pinch into uniform paste plastic after, on banded extruder, be extruded into the trifolium-shaped bar of 1.5mm, and under 110 ℃, at the loft drier inner drying after 3 hours, respectively 500,550,600, under 700 ℃, high temperature kiln roasting 4 hours, make alumina carrier containing Zr A, B, C, D, its physico-chemical property list in the table (1).
The physico-chemical property of table (1) carrier
Roasting is average than table
Pore distribution % nm carries zirconium white meleic acid pore volume
Mmol/g ℃ of cm of temperature areal intensity aperture body burden w%
3/ g＜4.0 4.0～15.0＞15.0 m
2/ g N/mm nm A 10.0% 0.289 700 0.39 13.9 84.1 1.9 193 21 8.1 B 8.0% 0.297 600 0.43 14.4 83.2 2.4 221 16 7.8 C 6.0% 0.302 550 0.47 10.1 86.6 3.3 252 13 7.5 D 4.0% 0.284 500 0.52 7.3 90.4 2.4 281 12 7.4
Listed pore volume, specific surface area and the mean pore size of the present invention all measured by BET method (absorption of 2400 cryogenic nitrogens).
Meleic acid described in the table (1) is the total acid (adopt and pay the formula infrared spectrometer, utilize infrared spectroscopic determination catalyst surface acidity) under 160 ℃.
Usually alumina supporter is along with the difference of maturing temperature, and its acidity has bigger difference, from table (1) as can be seen, introduces zirconium in the moulding process of carrier, and the acidity that makes carrier is maintained in the comparatively stable scope.
Embodiment 2
Present embodiment has been introduced the process that adds citric acid and acetate in the alumina carrier containing Zr moulding process.
Take by weighing three parts of quality and be aluminum hydroxide solid elastomer powder (producer, material and the Al of 100g
2O
3Content is all as above), add 5.0g sesbania powder respectively therein, mix; Take by weighing 3 parts of 7.84g basic zirconium chlorides (the same) simultaneously, add 2.0g therein respectively, 6.0g (reagent one factory in Shenyang produces citric acid, 99.5w%) with 5.4ml acetate (Shenyang reagent one factory, acetic acid content is 36.0w%), add 75ml, 85ml more respectively, the deionized water and stirring of 90ml, after making its dissolving, add respectively in the aluminum hydroxide solid elastomer powder that contains the sesbania powder mixed, mix pinch into uniform paste plastic after, on banded extruder, be extruded into the cloverleaf pattern bar of 1.5mm, and under 100 ℃, loft drier inner drying 4.5 hours, under 550 ℃, roasting is 6 hours in High Temperature Furnaces Heating Apparatus, makes alumina carrier containing Zr E, F, G.
Take by weighing aluminum hydroxide solid elastomer powder (producer, material and the Al of same quality (100g) as mentioned above
2O
3Content is all as above) and the sesbania powder of same quality (5.0g), after mixing, taking by weighing 1 part of quality is 12.0g basic zirconium chloride (the same), add the 2.0g citric acid therein, add the 80ml deionized water and stirring again, after making its dissolving, add in the aluminum hydroxide solid elastomer powder that contains the sesbania powder that has mixed, mix pinch into uniform paste plastic after, on banded extruder, be extruded into the cloverleaf pattern bar of 1.5mm, and under 100 ℃, loft drier inner drying 4.5 hours, under 550 ℃, roasting is 6 hours in High Temperature Furnaces Heating Apparatus, makes alumina carrier containing Zr J.
The physico-chemical property of carrier E, F, G, J such as following table (2)
The physico-chemical property of table (2) carrier
Oxychlorination is than average year citric acid acetic acid pore volume pore distribution (%) nm of table
Zirconium add areal intensity aperture body g ml cm
3/ g
Go into amount g m
2/g＜4.0 4.0～15.0＞15.0 N/mm nm E 7.84 2.0 —— 0.54 262 9.6 87.5 2.9 14 8.2 F 7.84 6.0 —— 0.44 269 20.0 77.8 2.2 24 6.5 G 7.84 —— 5.4 0.53 264 9.2 88.5 2.3 17 8.1 J 12.0 2.0 —— 0.45 242 13.8 83.3 2.8 19 7.5
Embodiment 3
Present embodiment has been introduced and added the sooty process in the moulding process of alumina carrier containing Zr.
Take by weighing 100g aluminum hydroxide solid elastomer powder (producer, material and Al
2O
3Content all as above), add 5.0g sesbania powder therein, 5.0g (Fushun Carbon Black Plant produces carbon black, granular size is 30 microns), after mixing, take by weighing 7.84g basic zirconium chloride (the same) and be dissolved in the 55ml deionized water, take by weighing the acetate (Shenyang reagent one factory, acetic acid content is 36.0w%) of 1.0g citric acid (reagent one factory in Shenyang produces, 99.5%) and 2.7ml simultaneously, after being dissolved in the 20ml deionized water, with the aqueous solution of basic zirconium chloride, after stirring, adding is mixed with in sesbania powder and the sooty aluminum hydroxide solid elastomer powder, mix pinch into uniform paste plastic after, on banded extruder, extrude 1.5mm cloverleaf pattern bar, and under 110 ℃, loft drier inner drying 3 hours, under 550 ℃, roasting is 6.5 hours in High Temperature Furnaces Heating Apparatus, makes carrier H, and its physico-chemical property is listed in the table (3).
The physico-chemical property of table (3) carrier
Lemon is than average year acetic acid carbon black pore volume pore distribution (%) nm of table
Acid areal intensity aperture body ml g cm
3/ g
g m
2/g ＜4.0 4.0～15.0 ＞15.0 N/mm nm?H 1.0 2.7 5.0 0.57 279 10.2 84.6 5.3 18 8.2
Embodiment 4
Present embodiment has been introduced and added silicon sol and sooty method and process in the alumina carrier containing Zr moulding process.
(1) take by weighing 100g aluminum hydroxide solid elastomer powder, add 5.0g sesbania powder and 10g carbon black (the same) therein, after the basic zirconium chloride (the same) that takes by weighing 16.4g was dissolved in the 85ml deionized water, (the new light remover in Shenyang City factory, the pH value was 9.3, contains SiO to get the 14ml silicon sol
230w%, Na
+Concentration is not more than 300ppm), dropwise add in the zirconium oxychloride aqueous solution, after stirring, add and be mixed with in sesbania powder and the sooty aluminum hydroxide solid elastomer powder, mix pinch into uniform paste plastic after, on banded extruder, be extruded into the cloverleaf pattern bar of 1.5mm, material behind the extruded moulding is under 120 ℃, loft drier inner drying 3.5 hours, dried material is divided into 3 parts places three High Temperature Furnaces Heating Apparatuss, roasting is made carrier M1, M2, M3 after 6 hours, 4 hours, 3 hours respectively under 550 ℃, 600 ℃, 650 ℃.
(2) take by weighing the aluminum hydroxide solid elastomer powder of same quality as mentioned above, after sesbania powder and carbon black mix, the aqueous solution that adds earlier silicon sol therein is 44ml (add-on of silicon sol is identical with the add-on of silicon sol as mentioned above) altogether, mix and pinch evenly, after making it become the finely powdered thing, take by weighing the basic zirconium chloride (the same) of 16.4g again, the deionized water that adds 55ml therein, after mixing, make zirconium oxychloride aqueous solution, with its be added to previous mix the finely powdered thing of pinching after, mix once more and pinch, pinch into uniform paste plastic until mixing, on banded extruder, be extruded into the cloverleaf pattern bar of 1.5mm, material behind the extruded moulding loft drier inner drying 3.5 hours, is divided into 3 parts with dried material and places three High Temperature Furnaces Heating Apparatuss under 120 ℃, at 550 ℃, 600 ℃, the difference roasting is 6 hours under 650 ℃, 4 hours, after 3 hours, make carrier N1, N2, N3.
(3) take by weighing 100g aluminum hydroxide solid elastomer powder (as above), add 5.0g sesbania powder and 10g carbon black (as above) therein, after the basic zirconium chloride (as above) of getting 7.84g is dissolved in the 80ml deionized water with the acetic acid (as above) of 2.7ml, get 7.7ml silicon sol (as above), dropwise add in the zirconium oxychloride aqueous solution, after stirring, add and be mixed with in sesbania powder and the sooty aluminum hydroxide solid elastomer powder, mix pinch into uniform paste plastic after, on banded extruder, be extruded into the cloverleaf pattern bar of 1.5mm, the material behind the extruded moulding is under 120 ℃, loft drier inner drying 4 hours, under 600 ℃,, make carrier L high temperature kiln roasting 4 hours.
The character of carrier M1, M2, M3, N1, N2, N3 and L such as following table (4)
The average hole body cm of pore distribution (%) the nm when physico-chemical property of table (4) carrier carries the roasting of pore volume specific surface roasting temperature
3/ g amasss m
2Hour between/g degree ℃＜4.0 4.0～15.0＞15.0 footpath nm M1 0.48 247 550 6.0 6.0 89.5 4.5 7.8 M2 0.48 223 600 4.0 3.4 90.5 6.2 8.7 M3 0.47 209 650 3.0 2.5 91.0 6.6 8.9 N1 0.49 249 550 6.0 4.8 91.3 3.8 7.9 N2 0.49 225 600 4.0 2.9 91.6 5.5 8.6 N3 0.49 214 650 3.0 1.8 93.6 4.5 9.1 L 0.61 252 600 4.0 2.8 87.0 10.2 9.8
As can be seen along with the rising of maturing temperature, the aperture ratio of＜4.0nm is reducing gradually from table (4), and the ratio in the hole between 4.0～15.0nm is increasing gradually, and the central tendency of pore distribution obviously strengthens.Also can find out simultaneously, add silicon sol earlier, after add zirconium-containing compound and add simultaneously than silicon sol and zirconium-containing compound, it is concentrated that pore distribution more becomes.
Embodiment 5
Present embodiment has been introduced the alumina carrier containing Zr of being made by another kind of raw material and added silicon sol and sooty method and process in moulding process.
(Shandong Province Chemical Fertilizer Factory No.1, Qilu Petrochemical Co. produces, and contains Al to take by weighing 200g aluminum hydroxide solid elastomer powder
2O
372.0 w%), 10g sesbania powder and 20g carbon black (as above) mix; Measure 28 ml silicon sol (with embodiment 4) with graduated cylinder, add therein the 30ml deionized water and stirring evenly after, add and be mixed with in sesbania powder and the sooty aluminum hydroxide solid elastomer powder, mix and pinch into uniform finely powdered thing; The basic zirconium chloride (as above) that takes by weighing 32.8g again is dissolved in the deionized water of 130ml, this solution is added previous mixing in the uniform fine powder of pinching, mix once more and pinch, after making it become uniform paste plastic, with two parts of quality such as this paste plastic is divided into, be extruded into the cloverleaf pattern bar of 1.5mm and the cylindrical bar of 1.5mm again on the banded extruder, with the carrier after the moulding under 110 ℃, loft drier inner drying 3 hours, carrier with dried two kinds of profiles is divided into two parts respectively more again, respectively at 600 ℃, under 650 ℃, respectively high temperature kiln roasting 4 hours, after 3 hours, make alumina carrier containing Zr B1, B2, B3, B4.Its physico-chemical property is listed in the table (5).
The average hole of pore distribution % nm when the physico-chemical property of table (5) carrier carries the roasting of pore volume specific surface roasting temperature
Carrier outline body cm
3/ g amasss m
2Hour between/g degree ℃＜4.0 4.0～15.0＞15.0 footpath nmB1 0.57 261 650 3 clover 3.1 88.9 8.0 8.8B2 0.57 260 650 3 cylinder 3.4 87.2 9.3 8.7B3 0.57 264 600 4 clover 3.4 87.5 9.1 8.7B4 0.58 258 600 4 cylinders 2.9 88.1 9.1 8.9
Embodiment 6
Present embodiment has been introduced the compound method of tungsten, nickel solution.
Measure the deionized water of 55ml, (technical grade contains WO to add the 102.0g ammonium metawolframate successively
385.2m%) with 80.0g nickelous nitrate (Ni (NO
3)
2.6H
2O city's chemical reagent one factory that increases income in Liaoning Province produces), make tungsten, nickel solution Y after the stirring and dissolving.
The character of this kind tungsten, nickel solution Y sees Table (6)
Table (6)
Solution W O
3(mol/dm
3) NiO (mol/dm
3)
Y 3.09 2.28
Embodiment 7
Present embodiment has been introduced active metal component and has been joined method and process on the carrier.
Get alumina carrier containing Zr G, H, L among the embodiment 2,3,4 respectively, measure the mixing solutions Y that contains tungsten, nickel for preparing among the embodiment 6 by the saturated absorption of carrier, carry out spray-stain (saturated dipping) respectively, control sprays speed, making solution be vaporific sprays on the carrier, after having sprayed, in loft drier, in 110 ℃ of dryings 3 hours, in High Temperature Furnaces Heating Apparatus, in 450 ℃ of roastings 3 hours, make catalyzer of the present invention, its character is listed in the table (7)
Table (7)
The average catalysis pore volume of meleic acid mmol/g chemical constitution w% specific surface
160 ℃ of 250 ℃ of ZrO of carrier aperture agent
2SiO
2WO
3NiO cm
3/ g amasss m
2/ g
nmX1 G 0.309 0.208 2.9 —— 27.94 6.82 7.1 0.30 167X2 H 0.264 0.179 2.6 —— 29.08 6.75 7.5 0.31 165X3 L 0.293 0.188 2.8 2.43 29.73 7.39 8.7 0.34 153
From the table (7) as can be seen, X1, X2, X3 can be used as outstanding catalyst for hydrorefining distillate oil.
Claims (16)
1, a kind of alumina carrier containing Zr is characterized in that the total weight percent with carrier is a benchmark, comprising: ZrO
22.0%～14.0%, SiO
20.0%～10.0%, aluminum oxide 40%～98.0%.
2, according to the described alumina carrier containing Zr of claim 1, it is characterized in that described ZrO
2Be 4.0%～8.0%, SiO
2Be 2.0%～6.0%, aluminum oxide is 55.0%～86.0%.
3, according to the described alumina carrier containing Zr of claim 1, it is characterized in that the physico-chemical property of described alumina carrier containing Zr is: pore volume is 0.20cm
3/ g～0.75cm
3/ g, specific surface area is 180m
2/ g～350m
2/ g, mean pore size is 5.0nm～12.0nm.
4, according to the described alumina carrier containing Zr of claim 1, the pore distribution that it is characterized in that described alumina carrier containing Zr is: the hole of＜4.0nm accounts for 1.5%～15.0% of total hole, 4.0nm the hole the between～15.0nm accounts for 83.0%～95.0% of total hole, the hole of＞15.0nm accounts for 1.0%～11.5% of total hole.
5, according to the described alumina carrier containing Zr of claim 1, the pore distribution that it is characterized in that described alumina carrier containing Zr is: the hole of＜4.0nm accounts for 1.5%～4.0% of total hole, 4.0nm the hole the between～15.0nm accounts for 88.5%～95.0% of total hole, the hole of＞15.0nm accounts for 1.0%～3.5% of total hole.
6,, it is characterized in that the infrared acidity of described carrier is 0.250mmol/g～0.320mmol/g according to the described alumina carrier containing Zr of claim 1.
7,, it is characterized in that the infrared acidity of described carrier is 0.255mmol/g～0.300mmol/g according to the described alumina carrier containing Zr of claim 1.
8, according to the described alumina carrier containing Zr of claim 1, the side pressure strength that it is characterized in that described carrier is 12.0N/mm～25.0N/mm.
9, according to the described alumina carrier containing Zr of claim 1, the side pressure strength that it is characterized in that described carrier is 16.0N/mm～22.5N/mm.
10, the preparation method of the described alumina carrier containing Zr of claim 1 comprises moulding, drying, calcination steps, it is characterized in that described zirconium-containing compound is to add to mix the form of pinching in the moulding process of carrier.
11,, it is characterized in that the concrete preparation process of described alumina carrier containing Zr comprises the steps: according to the described preparation method of claim 10
(1) zirconium-containing compound is soluble in water, stirring is mixed with the solution that contains zirconium after making its dissolving;
(2) solution prepared in (1) added contain in the aluminum hydroxide solid elastomer powder of extrusion aid, mix pinch evenly after, extruded moulding;
(3) with the carrier of extruded moulding in (2) between 100 ℃～130 ℃ temperature dry 2 hours～6 hours, described alumina carrier containing Zr was made in roasting in 2 hours～8 hours between 500 ℃～700 ℃.
12,, it is characterized in that also having added silicon sol in the described carrier moulding process according to the described preparation method of claim 10.
13,, it is characterized in that also having added carbon black in the described carrier moulding process according to the described preparation method of claim 10.
14,, it is characterized in that described zirconium-containing compound is selected from one or more in basic zirconium chloride, bromine zirconium white, zirconium sulfate, hydrogen sulfate zirconium white, zirconium nitrate, the carboxylic acid zirconium according to the described preparation method of claim 11.
15,, it is characterized in that described zirconium-containing compound is a basic zirconium chloride according to the described preparation method of claim 11.
16,, it is characterized in that in the described carrier moulding process it being to add silicon sol earlier, and then add zirconium-containing compound according to the described preparation method of claim 11.
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Cited By (11)
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| CN100438980C (en) * | 2006-03-10 | 2008-12-03 | 中国石油化工股份有限公司 | Catalyst support added with hydrogen, peroxide catalyst produced by anthraquinone method and the producing process |
| CN101618346B (en) * | 2008-07-04 | 2011-04-20 | 中国石油化工股份有限公司 | Method for preparing silicon and zirconium containing aluminum oxide carrier |
| CN102233282A (en) * | 2010-04-30 | 2011-11-09 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis catalyst taking silicon oxide-aluminum oxide as carrier and application thereof |
| CN101786024B (en) * | 2010-02-06 | 2012-05-23 | 山西大学 | Alumina carrier with high hydrothermal stability and preparation method thereof |
| CN101433864B (en) * | 2007-11-15 | 2012-05-30 | 中国石油化工股份有限公司 | Method for preparing aluminum oxide dry glue powder containing silicon and zirconium |
| CN101433863B (en) * | 2007-11-15 | 2012-08-29 | 中国石油化工股份有限公司 | Composite oxide carrier and preparation method thereof |
| CN101489668B (en) * | 2006-06-20 | 2013-03-13 | 国际壳牌研究有限公司 | A sulfur tolerant noble metal-containing aromatics hydrogenation catalyst and a method of making and using such catalyst |
| CN103374393A (en) * | 2012-04-26 | 2013-10-30 | 中国石油化工股份有限公司 | Hydrotreatment method for hydrocarbon oil |
| CN103706408A (en) * | 2013-12-18 | 2014-04-09 | 宁波金远东工业科技有限公司 | Protective agent of coal tar hydrogenation catalyst and preparation method of protective agent |
| CN104926290A (en) * | 2014-03-21 | 2015-09-23 | 中国石油化工股份有限公司 | Composite material and its application |
| CN108067210A (en) * | 2016-11-17 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of zirconium-containing alumina dry glue powder and its preparation method and application |
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2000
- 2000-10-26 CN CN 00123133 patent/CN1112252C/en not_active Expired - Lifetime
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100438980C (en) * | 2006-03-10 | 2008-12-03 | 中国石油化工股份有限公司 | Catalyst support added with hydrogen, peroxide catalyst produced by anthraquinone method and the producing process |
| CN101489668B (en) * | 2006-06-20 | 2013-03-13 | 国际壳牌研究有限公司 | A sulfur tolerant noble metal-containing aromatics hydrogenation catalyst and a method of making and using such catalyst |
| CN101433864B (en) * | 2007-11-15 | 2012-05-30 | 中国石油化工股份有限公司 | Method for preparing aluminum oxide dry glue powder containing silicon and zirconium |
| CN101433863B (en) * | 2007-11-15 | 2012-08-29 | 中国石油化工股份有限公司 | Composite oxide carrier and preparation method thereof |
| CN101618346B (en) * | 2008-07-04 | 2011-04-20 | 中国石油化工股份有限公司 | Method for preparing silicon and zirconium containing aluminum oxide carrier |
| CN101786024B (en) * | 2010-02-06 | 2012-05-23 | 山西大学 | Alumina carrier with high hydrothermal stability and preparation method thereof |
| CN102233282A (en) * | 2010-04-30 | 2011-11-09 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis catalyst taking silicon oxide-aluminum oxide as carrier and application thereof |
| CN102233282B (en) * | 2010-04-30 | 2013-06-26 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis catalyst taking silicon oxide-aluminum oxide as carrier and application thereof |
| CN103374393A (en) * | 2012-04-26 | 2013-10-30 | 中国石油化工股份有限公司 | Hydrotreatment method for hydrocarbon oil |
| CN103706408A (en) * | 2013-12-18 | 2014-04-09 | 宁波金远东工业科技有限公司 | Protective agent of coal tar hydrogenation catalyst and preparation method of protective agent |
| CN104926290A (en) * | 2014-03-21 | 2015-09-23 | 中国石油化工股份有限公司 | Composite material and its application |
| CN108067210A (en) * | 2016-11-17 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of zirconium-containing alumina dry glue powder and its preparation method and application |
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