CN1123392C - Alumina carrier containing Ni and its preparing process - Google Patents
Alumina carrier containing Ni and its preparing process Download PDFInfo
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- CN1123392C CN1123392C CN 01114178 CN01114178A CN1123392C CN 1123392 C CN1123392 C CN 1123392C CN 01114178 CN01114178 CN 01114178 CN 01114178 A CN01114178 A CN 01114178A CN 1123392 C CN1123392 C CN 1123392C
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Abstract
The present invention provides an alumina supporter containing nickel and a preparing method thereof. A mixture of carbon black and nickel compounds treated by alkali is mixed with dry gel powder of aluminium hydroxide, and the mixture is molded through strip extrusion, dried and calcined to prepare an alumina supporter with the nickel content of 2.0% to 14.0%. The pore volume of the alumina supporter is from 0.4cm<3>/g to 1.0cm<3>/g, the specific surface area is from 160 m<2>/g to 420 m<2>/g, and the average pore size is from 8.0 nm to 15.0 nm. Pores with sizes larger than 6.0 nm account for more than 85% of total pores, the pore volume and the average pore size are large, and large pores account for a large proportion. The alumina supporter is particularly suitable for being used as a supporter for hydrofining catalysts for heavy oil.
Description
The present invention relates to a kind of alumina carrier containing Ni and preparation method thereof, particularly be applicable to support of the catalyst of heavy-oil hydrogenation treating process and preparation method thereof.
Now, along with the further increasing of reform and opening-up paces, China refines in the crude oil each big refinery, and heavy high-sulfur oils shared proportion in the Middle East is strengthening year by year.In the hydrotreatment process,, then will bring great pollution to environment if can not effectively impurity removals such as the sulphur in the oil product, nitrogen be fallen.Therefore, in the last few years, very active in the research work of heavy-oil hydrogenation field of refinement.
As everyone knows, the Application of Catalyst field depends primarily on the pore structure character that makes support of the catalyst.At the unifining process of mink cell focus, then require carrier to have bigger pore volume and mean pore size, in order to reach this requirement, then must carry out reaming to carrier.At present, use comparatively general reaming mode to have two kinds: the one, in the extruded moulding process, add expanding agent; The 2nd, behind extruded moulding, under atmosphere such as water, ammonia, carry out pyroprocessing.For extruded moulding, the expanding method of normal employing is to add expanding agent in the extruded moulding process.
Expanding agent has a variety of, and using maximum expanding agents now is phosphorus (P) and silicon (Si).
Because itself character before catalyzer or carrier moulding, adds P contained compound, can give afterwards catalyzer or the moulding of carrier bring very big difficulty.Though expanding agent silicon reaming effect is better, because a large amount of adding silicon can make the pore distribution disperse of carrier for the purpose that reaches reaming.At the carrier of heavy-oil hydrogenation catalyst for refining, its macropore ratio is reduced, be unfavorable for the unifining process of mink cell focus.
Carbon black can improve the ratio of macropore significantly as a kind of physics expanding agent commonly used; Simultaneously, in the moulding process of carrier, add the effect that carbon black plays extrusion aid, also help the extruded moulding of carrier.
At publication number is in the patent of invention of US4448896, and at first, carbon black adds as a kind of expanding agent, but in this patent, the sooty add-on is too much, has reached the 120w% of shaping carrier gross weight at most.Carbon black is as a kind of physics expanding agent, and an amount of adding in the carrier moulding process pore structure character of carrier is improved, and excessive adding carbon black then can cause the reduction of carrier physical strength, also makes the pore distribution of carrier be tending towards disperse simultaneously.Secondly, in the patent of invention of US4448896, it does not propose to solve the catalyzer that kneading method makes, in high-temperature calcination process, and the easy and γ-Al of active metal component
2O
3Or its precursor generation intensive interacts (SMI) these problems of non-active species such as generation nickel aluminate or molybdic acid aluminium.
And being the patent of invention of US4032433, publication number introduced a kind of hydrogenization catalyst preparation method, the method of modifying that has wherein also related to alumina supporter: use tensio-active agent and organic compound as expanding agent, change the pore structure of aluminum oxide, though this method can be improved the pore structure of carrier effectively, but intensity is lower, can not satisfy industrial requirements.
Publication number is that the patent of invention of JP57-123820 has been introduced a kind of employing aluminum oxide or its precursor aluminium hydrate powder, come modified aluminas by adding carbon black, but the amounts of carbon black that adds requires greater than 30w%, and its physical strength also is difficult to reach the requirement that industry is used.
After the problem in pore volume, aperture solved, people can focus on sight on the hydrogenation activity that how to improve catalyzer again.
At present, the Preparation of catalysts method mainly contains two kinds, and a kind of is pickling process; Another kind is a kneading method.Pickling process is meant that the solution impregnation that contains active metal component that will prepare is to the carrier of moulding, then drying, the prepared catalyzer of roasting, the catalyst activity metal component that pickling process makes dispersive on the surface of carrier is better, but, for the catalyzer of preparation high activity metal component concentration, pickling process has certain degree of difficulty; Kneading method is to adopt directly mixed form of pinching that active metal component, expanding agent and auxiliary agent are directly mixed with the aluminum hydroxide solid elastomer powder, and then, extruded moulding on banded extruder makes catalyzer.The preparation process of kneading method is easy, and is with short production cycle, the production efficiency height, the cost of prepared catalyzer is low, but it also has the deficiency of self: (1) is in order to guarantee the intensity of catalyzer, in the extruded moulding process, add the Aci-Jel solvent, so the catalyzer aperture of gained is less; (2) in roasting process, active metal component and γ-Al
2O
3Or its precursor generation intensive interacts the generation non-active species.As: nickel aluminate or molybdic acid aluminium etc., this will have influence on the hydrogenation activity of catalyzer.
These problems that prior art occurs all are stubborn problems comparatively in the heavy-oil hydrogenation field now, therefore are necessary to prepare a kind of carrier, make it can solve the existing in prior technology problem.
Usually preparation has the catalyzer of higher hydrogenation activity, requires the content of active metal component to want high.Use pickling process, come shaping carrier is flooded by preparation high-content active metal component solution, make the catalyzer with higher hydrogenation activity, its difficulty is bigger.And if in the preparation process of support of the catalyst, the compound that a part is contained active metal component adds to mix the form of pinching, make the compound that contains a certain amount of active metal component in the carrier that makes, then can reduce high-content active metal component Preparation of catalysts difficulty, the hydrogenation activity of catalyzer is guaranteed.
Therefore purpose of the present invention will prepare a kind of pore volume exactly, the aperture is bigger, and nickel compound containing is finely disseminated alumina carrier containing Ni in carrier, and its carrier that can be used as a kind of heavy-oil hydrogenation catalyst for refining is used.
The principal feature of alumina carrier containing Ni of the present invention is:
Weight with carrier is benchmark, and the percentage composition of NiO is 2.0%～14.0%,, all the other are aluminum oxide; But preferably the percentage composition of NiO is 5.0%～8.0%.
The physico-chemical property of described alumina carrier containing Ni is: pore volume is 0.4cm
3/ g～1.0cm
3/ g, specific surface area are 160m
2/ g～420m
2/ g, mean pore size are 8.0nm～15.0nm, greater than the ratio in 6.0nm hole account for its total hole 85% more than; But preferably pore volume is 0.7cm
3/ g～1.0cm
3/ g, specific surface area are 300m
2/ g～370m
2/ g, mean pore size are 10.0nm～13.0nm
The preparation main points of above-mentioned carrier mainly are to have added nickel compound containing and sooty mixture after alkaline purification to mix the form pinch in the moulding process of carrier, after the carrier moulding, and drying, roasting and make alumina carrier containing Ni of the present invention.
The concrete preparation of alumina carrier containing Ni of the present invention comprises the steps:
(1) with the alumina carrier containing Ni is benchmark, mix accounting for the carbon powder of total weight of carrier 10.0%～35.0% and required nickel compound containing and alkali cpd solution, fully stir, the solution of alkali is fully contacted with the solid powder mix, and the add-on of described alkali cpd and the mol ratio of nickel compound containing are 1.0: 0.10～1.50;
(2) add required aluminum hydroxide solid elastomer powder and account in the powder mix of total weight of carrier 2.0%～8.0% extrusion aid through the carbon black of alkaline purification and the mixture of nickel compound containing what prepared in (1) step, again to wherein adding the peptizing agent account for total weight of carrier 0.5%～10% (this peptizing agent can be a kind of can also be the combination of several peptizing agents), mix pinch into uniform plastic paste after, extruded moulding.This shaping carrier can be columniform, also can be (as trifolium, the Herba Galii Bungei etc.) of special-shaped bar; The peptizing agent that is adopted can be a kind of in nitric acid, hydrochloric acid, oxalic acid, formic acid, acetate, citric acid, the aluminum nitrate, also can be the wherein combination of several peptizing agents; 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;
(3) with prepared shaping carrier in (2) step between 80 ℃～150 ℃, dry 1 hour～10 hours, roasting was 2 hours～8 hours between 300 ℃～1000 ℃, makes alumina carrier containing Ni of the present invention.
In described (1) step through the carbon black of alkaline purification and the mixture of nickel compound containing, its used alkali both can be mineral alkali, as ammoniacal liquor, sodium hydroxide, potassium hydroxide, etc., can also be organic bases, as TBAH.But the ammoniacal liquor in the mineral alkali preferably.Described nickel compound containing can be basic nickel carbonate, nickelous chloride, nickelous nitrate, single nickel salt etc., but basic nickel carbonate preferably; Actual employed nickel compound containing generally can be milled into the nickel compound containing powder by runner milling.
Mixture alkaline purification with carbon black and nickel compound containing, nickel compound containing is surrounded by carbon black, the chance that makes nickel compound containing and aluminum oxide directly contact reduces, under higher maturing temperature, and the strong interaction between the active ingredient that can weaken and the aluminum oxide (SMI).
Compared with prior art, pore volume, the mean pore size of carrier of the present invention are bigger, and the macropore proportion is many; In addition because carrier of the present invention is in moulding process, to mix the mixture that the form of pinching adds alkali-treated carbon black and nickel compound containing, thereby make carrier itself have certain nickel content, reduced the difficulty for preparing high activity metal component concentration catalyzer afterwards; In addition, compared with prior art, the present invention can also effectively improve the pore structure character of carrier, the strong interaction (SMI) between reduction active metal component and the aluminum oxide, make the active metal component good dispersion, the catalyzer that carrier is thus made has higher hydrogenation activity.
Because the peculiar property of carrier of the present invention makes it can be suitable for a lot of fields.For example, because it has bigger pore volume and aperture, use so can be used as a kind of carrier of heavy-oil hydrogenation catalyst for refining.In the last few years, very active in the research work in refining this field of heavy-oil hydrogenation, its extensive market, have a high potential, so the application prospect of carrier of the present invention makes us good.
Further specify the preparation process of advantage of the present invention, technical characterictic and carrier below by embodiment, but invention should not be deemed limited to this.
Embodiment 1
Present embodiment has been introduced the preparation process of alumina carrier containing Ni.
(Shandong Province Chemical Fertilizer Factory No.1, Qilu Petrochemical Co. produces, and contains Al to take by weighing aluminum hydroxide solid elastomer powder 100g
2O
372w%), add 5.0g sesbania powder therein, mix; Take by weighing 25g carbon black (Fushun Carbon Black Plant produces, and granular size is 30 microns) again, sneak into 6.0g basic nickel carbonate [Ni therein
2(OH)
2CO
3.5H
2O contains nickel oxide 50w%]; Measuring density is 0.984g/cm
3Ammoniacal liquor (contain NH
3Be 3.8w%) 16.3ml, in the carbon black that adding has mixed and the mixture of basic nickel carbonate, stir with glass stick, ammoniacal liquor is fully contacted with mixture, placed 15 minutes; To join in the aluminum hydroxide solid elastomer powder that is mixed with the sesbania powder with the mixture that contains carbon black and basic nickel carbonate that ammonia treatment is crossed again, mix; (reagent one factory in Shenyang produces, and 99.5w%), is dissolved in the deionized water of 85ml to measure 9.0ml acetate (reagent one factory in Shenyang produces, acetic acid content 36w%) and 2.0g citric acid; It being joined above-mentioned being mixed with contains in the aluminum hydroxide solid elastomer powder of carbon black, basic nickel carbonate and sesbania powder again, mix pinch into uniform paste plastic after, on banded extruder, be extruded into the cloverleaf pattern bar of 2.0mm, after under 110 ℃ dry 3 hours, with in type alumina carrier containing Ni, two parts of quality such as be divided into, in 600 ℃, 500 ℃ roastings 3 hours, 4 hours respectively down, make alumina carrier containing Ni A1, A2, its physico-chemical property is listed in the table 1.
The table 1 year roasting roasting pore distribution % pore volume specific surface average body temperature time
℃ hour＜6.0nm＞6.0nm cm
3/ g amasss m
2/ g aperture nm A1 600 3 5.6 94.4 0.80 301 10.6A2 500 4 10.3 89.7 0.76 335 9.1
Annotate: basic nickel carbonate used in the present invention all is the fine powders after fully milling by runner milling.
Embodiment 2
Take by weighing aluminum hydroxide solid elastomer powder 100g (the same), add 5.0g sesbania powder (the same) therein, mix; Take by weighing 25g carbon black (the same) again, sneak into 16.1g basic nickel carbonate [Ni therein
2(OH)
2CO
3.5H
2O contains nickel oxide 50w%]; Measuring density is 0.984g/cm
3Ammoniacal liquor (the same) 16.3ml, add in the mixture of the carbon black mixed and basic nickel carbonate, stir with glass stick, ammoniacal liquor is fully contacted with mixture, placed 15 minutes; To join in the aluminum hydroxide solid elastomer powder that is mixed with the sesbania powder with the mixture that contains carbon black and basic nickel carbonate that ammonia treatment is crossed again, mix; Measure 9.0ml acetate (the same) and 2.0g citric acid (the same), be dissolved in the deionized water of 90ml; It being joined above-mentioned being mixed with contains in the aluminum hydroxide solid elastomer powder of carbon black, basic nickel carbonate and sesbania powder again, mix pinch into uniform paste plastic after, on banded extruder, be extruded into the cloverleaf pattern bar of 2.0mm, after under 110 ℃ dry 3 hours, with in type alumina carrier containing Ni, two parts of quality such as be divided into, in 600 ℃, 500 ℃ roastings 3 hours, 4 hours respectively down, make alumina carrier containing Ni B1, B2, its physico-chemical property is listed in the table 2.
Table 2 year maturing temperature roasting time pore distribution % pore volume specific surface area average body ℃ hour＜6.0nm＞6.0nm cm
3/ g m
2/ g aperture nmB1 600 3 7.4 92.6 0.76 279 10.9B2 500 4 12.9 87.1 0.80 312 10.2
Embodiment 3
Present embodiment has been introduced and has been used that a kind of organic bases comes the mixture of treated carbon black and basic nickel carbonate and the process that makes alumina carrier containing Ni.
Take by weighing 100g aluminum hydroxide solid elastomer powder (the same) and 5.0g sesbania powder (the same), after the mixing, take by weighing again after 20g carbon black (the same) and 9.3g basic nickel carbonate (the same) mix, add therein previous with graduated cylinder measure TBAH (the emerging good fortune fine chemistry in Beijing institute, wherein C
16H
37The about 10w% of the content of NO) 38ml stirs with glass stick, and TBAH solution is fully contacted with mixture, places after 15 minutes, it is joined in the aluminum hydroxide solid elastomer powder that is mixed with the sesbania powder, once more mixing; Measure after 6.3ml acetate (the same) and 2.0g citric acid (the same) be dissolved in the deionized water of 95ml, join in the aluminum hydroxide solid elastomer powder that is mixed with basic nickel carbonate, carbon black and sesbania powder, mix pinch into uniform paste plastic after, on banded extruder, be extruded into the cloverleaf pattern bar of 2.0mm, after under 120 ℃ dry 3.5 hours, with two parts of quality such as in type carrier is divided into, respectively at 600 ℃, 500 ℃ following roastings 3 hours and 4 hours, make alumina carrier containing Ni C1, C2, its physico-chemical property is listed in the table 3.
The table 3 year average hole body of maturing temperature roasting time pore distribution % pore volume specific surface area ℃ hour＜6.0nm＞6.0nm cm
3/ g m
2/ g footpath nm C1 600 3 9.2 90.8 0.62 247 10.0C2 500 4 13.2 86.8 0.73 336 8.6
Embodiment 4
Present embodiment has been introduced the mixture that adds alkali-treated carbon black and nickel compound containing in another raw material, and makes the process of alumina carrier containing Ni.
(Shandong Province Chemical Fertilizer Factory No.1, Qilu Petrochemical Co. produces, and contains Al to take by weighing 100g aluminum hydroxide solid elastomer powder
2O
370.8m%) with 5.0g sesbania powder (the same), after the mixing, take by weighing 25g carbon black (the same) and 7.6g basic nickel carbonate (the same) again, after mixing, measuring density is 0.984g/cm
3Ammoniacal liquor (the same) 16.3ml, in the carbon black that adding has mixed and the mixture of basic nickel carbonate, stir with glass stick, ammoniacal liquor is fully contacted with mixture, place after 15 minutes, to join in the aluminum hydroxide solid elastomer powder that is mixed with the sesbania powder with the mixture that contains carbon black and basic nickel carbonate that ammonia treatment is crossed again, mix; Measure 11.0ml acetate (the same) and 4.0g citric acid (the same), after being dissolved in the deionized water of 100ml, it being joined above-mentioned being mixed with contains in the aluminum hydroxide solid elastomer powder of carbon black and basic nickel carbonate again, mix and pinch into uniform paste plastic, on banded extruder, be extruded into the cloverleaf pattern bar of 1.5mm, after under 110 ℃ dry 4 hours, with three parts of quality such as in type carrier is divided into, respectively at 700 ℃, 600 ℃, 500 ℃ following roastings 3 hours, 3 hours and 4 hours, make alumina carrier containing Ni D1, D2, D3, its physico-chemical property is listed in the table 4.
Table 4 year maturing temperature roasting time pore distribution % pore volume specific surface area mean pore size body ℃ hour＜6.0nm＞6.0nm cm
3/ g m
2/ g nm D1 700 3 5.6 94.4 0.69 239 11.6D2 600 3 7.7 92.3 0.69 273 10.1D3 500 4 11.1 88.9 0.73 300 9.8
Comparative example 1
This comparative example has been introduced the process (in this process, do not add the mixture of alkali-treated carbon black and nickel compound containing, but directly add the nickel compound containing powder in the aluminum hydroxide solid elastomer powder) of making alumina carrier containing Ni with embodiment 4 described raw materials.
Take by weighing 100g aluminum hydroxide solid elastomer powder (with embodiment 4), 5.0g sesbania powder (the same) and 7.6g basic nickel carbonate (the same), after mixing, measure 6.3ml acetate (the same) and 2.0g citric acid (the same), after being dissolved in the deionized water of 90ml, it is joined in the above-mentioned aluminum hydroxide solid elastomer powder that is mixed with basic nickel carbonate and sesbania powder, mix and pinch into uniform paste plastic, on banded extruder, be extruded into the cloverleaf pattern bar of 1.5mm, after under 110 ℃ dry 4 hours, with three parts of quality such as in type carrier is divided into, respectively at 700 ℃, 600 ℃, 500 ℃ of following roastings 3 hours, 3 hours and 4 hours, make alumina carrier containing Ni E1, E2, E3, its physico-chemical property is listed in the table 5.
Table 5 year maturing temperature roasting time pore distribution % pore volume specific surface area mean pore size
℃ hour ＜6.0nm ＞6.0nm cm
3/g m
2/g nmE1 700 3 8.2 91.8 0.57 242 9.4E2 600 3 9.6 90.4 0.58 262 8.8E3 500 4 15.9 84.1 0.58 301 7.6
Comparative example 2
The analytical results that this comparative example has been introduced the XRD of carrier D series and carrier E series compares.
This comparative example has adopted Japanese X-ray diffractometer of science, measures the crystalline phase of nickeliferous component in the carrier, and its comparing result is as shown in table 6 below.
Carrier D series refers to: carrier D1, D2, D3;
Carrier E series refers to: carrier E1, E2, E3;
700 ℃ of following roastings of 600 ℃ of following roastings of 500 ℃ of following roastings of table 6 carrier
No NiO does not have NiAl
2O
4There is NiO not have NiAl
2O
4There is NiO that NiAl is arranged
2O
4D crystalline phase crystalline phase crystalline phase crystalline phase crystalline phase crystalline phase
There is NiO not have NiAl
2O
4There is NiO that NiAl is arranged
2O
4There is NiO that NiAl is arranged
2O
4E crystalline phase crystalline phase crystalline phase crystalline phase crystalline phase crystalline phase
As can be seen from the above table, under 500 ℃ maturing temperature, carrier series D had not both had the NiO crystalline phase, did not have nickel aluminate (NiAl yet
2O
4) crystalline phase, the active ingredient good dispersion is described, and does not generate non-active species nickel aluminate (NiAl between active ingredient and the aluminum oxide
2O
4), and under 500 ℃ maturing temperature, carrier series E has the NiO crystalline phase to occur, active ingredient forms assembles; Under 600 ℃ maturing temperature, NiAl appears in carrier series E
2O
4Crystalline phase, carrier series D does not then have NiAl
2O
4Crystalline phase generates, and illustrates that carrier series D can effectively suppress non-active species nickel aluminate (NiAl
2O
4) formation.
It can also be seen that from table 6 along with the rising of maturing temperature, carrier series D has the non-active species of inhibition nickel aluminate (NiAl
2O
4) trend that forms of crystalline phase, and the dispersion of active ingredient is far better than carrier series E.
Embodiment 5
Present embodiment has been introduced the preparation of the mixing solutions that contains tungsten, nickel active metal component.
Measure the deionized water of 55ml, (technical grade contains WO to add the 70.0g ammonium metawolframate successively
385.2m%) with 45.0g nickelous nitrate (Ni (NO
3)
2.6H
2O, Liaoning Province city's chemical reagent one factory that increases income produces), make tungsten, nickel solution after the stirring and dissolving.
Tungsten, the nickel solution character of preparation see Table 7.
Table 7
Solution W O
3(mol/dm
3) NiO (mol/dm
3)
Tungsten nickel solution 2.72 1.65
Embodiment 6
Present embodiment has been introduced the preparation of molybdenum nickel phosphorus solution.
Take by weighing the molybdic oxide of 35.7g, 16.6g basic nickel carbonate (containing nickel oxide 44.3w%), (density is 1.672g/cm to measure the 9.4ml strong phosphoric acid with graduated cylinder
3, concentration is 84w%); At first the deionized water with 76ml dilutes the strong phosphoric acid of 9.4ml, strong phosphoric acid after the dilution and the molybdic oxide of 35.7g are joined respectively in the three-necked bottle of condensation reflux unit, mix, after heating makes the molybdic oxide dissolving, basic nickel carbonate with 16.6g adds wherein again, make molybdenum nickel phosphorus solution in heating under 90 ℃ after two hours.
The character of molybdenum nickel phosphorus mixing solutions sees Table 8
Table 8
Mixing solutions MO
3(g/100ml) NiO (g/100ml) P (g/100ml)
Molybdenum nickel phosphorus mixing solutions 35.72 7.33 4.17
Embodiment 7
Present embodiment has been introduced with embodiment 5,6 solution of being prepared carrier A 1, B1 has been carried out the saturated process that sprays.
Get alumina carrier containing Ni A1, B1 among the embodiment 1,2, measure the mixing solutions that contains tungsten, nickel of preparation among the embodiment 5 and the molybdenum nickel phosphorus solution described in the embodiment 6 by the saturated absorption of carrier, respectively A1, B1 are carried out spray-stain (saturated dipping), control sprays speed, making solution be vaporific sprays on the carrier, after having sprayed, in loft drier, in 120 ℃ of dryings 3 hours, in High Temperature Furnaces Heating Apparatus, in 500 ℃ of roastings 4 hours, make catalyzer X1, X2, its character is listed in the table 9.
Table 9
The used solution of the average hole of chemical constitution w% pore volume specific surface support of the catalyst
MO
3P WO
3NiO footpath nm cm
3/ g amasss m
2--------36.4 13.1 8.9 0.38 171 X2 B1 molybdenum nickel phosphorus solutions, 24.9 2.9----7.8 9.9 0.42 170 as can be seen from the above table for/g X1 A1 tungsten nickel solution, X1, X2 can be used as outstanding heavy-oil hydrogenation catalyst for refining and use.
Claims (7)
1, a kind of alumina carrier containing Ni is a benchmark with the weight of carrier, and the percentage composition of NiO is 2.0%～14.0%, and all the other are aluminum oxide; The physico-chemical property of described alumina carrier containing Ni is: pore volume 0.4cm
3/ g～1.0cm
3/ g, specific surface area 160m
2/ g～420m
2/ g, mean pore size is 8.0nm～15.0nm, accounts for the ratio in its total hole greater than 85% greater than the ratio in 6.0nm hole.
2, according to the described alumina carrier containing Ni of claim 1, the pore volume that it is characterized in that described carrier is 0.7cm
3/ g～1.0cm
3/ g, specific surface area is 300m
2/ g～370m
2/ g, mean pore size is 10.0nm～13.0nm.
3, a kind of claim requires the preparation method of 1 described alumina carrier containing Ni, comprises the steps:
(1) with the alumina carrier containing Ni is benchmark, mix accounting for the carbon powder of total weight of carrier 10.0%～35.0% and required nickel compound containing and alkali cpd solution, fully stir, the solution of alkali is fully contacted with the mixed powder of solid, and the add-on of described alkali cpd and the mol ratio of nickel compound containing are 1.0: 0.10～1.50;
(2) add required aluminum hydroxide solid elastomer powder and account in the powder mix of total weight of carrier 2.0%～8.0% extrusion aid through the carbon black of alkaline purification and the mixture of nickel compound containing what prepared in (1) step, again to wherein adding the peptizing agent that accounts for total weight of carrier 0.5%～10%, mix pinch into uniform plastic paste after, extruded moulding;
(3) with prepared shaping carrier in (2) step between 80 ℃～150 ℃, dry 1 hour～10 hours, roasting was 2 hours～8 hours between 300 ℃～1000 ℃, makes described alumina carrier containing Ni.
4, require the preparation method of 3 described alumina carrier containing Nis according to claim, it is characterized in that described alkali cpd is an ammoniacal liquor.
5, require the preparation method of 3 described alumina carrier containing Nis according to claim, it is characterized in that described nickel compound containing is one or more in basic nickel carbonate, nickelous chloride, nickelous nitrate, the single nickel salt.
6, require the preparation method of 3 described alumina carrier containing Nis according to claim, it is characterized in that described nickel compound containing is a basic nickel carbonate.
7, the purposes of the described alumina carrier containing Ni of a kind of claim 1 is characterized in that described carrier can be used for the carrier of hydrorefining catalyst for heavy oil.
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2001
- 2001-07-02 CN CN 01114178 patent/CN1123392C/en not_active Expired - Lifetime
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