CN1049800A - The preparation of nickel/aluminium oxide catalyst - Google Patents
The preparation of nickel/aluminium oxide catalyst Download PDFInfo
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- CN1049800A CN1049800A CN 89106476 CN89106476A CN1049800A CN 1049800 A CN1049800 A CN 1049800A CN 89106476 CN89106476 CN 89106476 CN 89106476 A CN89106476 A CN 89106476A CN 1049800 A CN1049800 A CN 1049800A
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Abstract
The present invention relates to contain heavy % nickel (in NiO) of 10-40 and surplus Al
2O
3Nickel/alumina load type Preparation of catalysts, method be (1) with the formed alumina carrier at 500-750 ℃ of following roasting 1-4 hour, (2) immerse again in the nickel amine complex solution (100-280 gram NiO/ liter), room temperature-60 ℃ following maintenance 1-5 hour, filter, drying, and then repeated impregnations 0-6 time is in the time of also need flooding behind every dipping secondary, must first roasting continue dipping again, (3) were at 220-340 ℃ of following roasting 4-10 hour.The catalyst that this method is made reacts hydrocarbons hydrogenation, and especially edible white oil is produced in the hydrofinishing of fraction oil, has good activity and intensity.
Description
The present invention relates to nickel/alumina load type hydrocarbons hydrogenation Preparation of catalysts method.
Nickel/alumina load type catalyst is a kind of hydrocarbons hydrogenation catalyst commonly used.Nickel content is more in nickel/aluminium oxide hydrogenation catalyst, generally is higher than 20%, mostly is 30～60%(in NiO), this just makes Preparation of catalysts increase difficulty.Prepare the catalyst needs with traditional infusion process (making maceration extract with nickel salt solution) and repeatedly flood and roasting, the pore volume of catalyst is very low as a result.The heat endurance relatively poor (USP4191644) of the catalyst of preparing with coprecipitation.In order to overcome these shortcomings, USP4191644 has proposed a kind of preparation method: hydrated alumina is mixed with nickel amine complex solution, heating is decomposed complex compound, the nickel hydroxide precipitate that decomposites is on aluminium oxide, again after filtration, washing, drying, 400-1000 roasting, moulding, 750～1200 roastings 1～2 hour, promptly get and close nickel 5～70 heavy %(in NiO) Ni/Al
2O
3Catalyst; This activity of such catalysts Ni surface area can reach 50～55 meters
2/ gram methanation reaction is had good catalytic activity, but its anti-wear performance and service life can not meet the demands.Introduced among the USP4490480 and had 80～300 meters
2The Ni/Al of/gram active nickel surface area
2O
3Catalyst, its preparation method is; The water slurry that filters the attitude aluminium oxide is mixed with nickel amine complex solution, add thermal decomposition then and make nickel hydroxide precipitate arrive Al
2O
3On, more after filtration, washing, dry, 300～500 ℃ of roastings get final product; When this catalyst is used for fluidized-bed reactor, good abrasion resistance is arranged, long service life, however will be when being used for fixing bed bioreactor after its moulding, easy-formation, intensity are not relatively poor.
At the deficiencies in the prior art, the purpose of this invention is to provide a kind of Ni/Al
2O
3The Preparation of catalysts method makes the catalyst of preparing that good activity and intensity be arranged, and is applicable to fixed bed reactors.
Ni/Al provided by the invention
2O
3The Preparation of catalysts method is as follows:
(1),, promptly gets carrier 500～750 ℃ of following roastings 1～4 hour with the moulding of aluminium oxide precursor.
(2) carrier is immersed in the nickel amine complex solution that concentration is 100～280 grams per liters (in NiO), ℃ following the maintenance 1～5 hour, filter in room temperature～60, and 60～150 ℃ were descended dry 2-10 hour; Flood repeatedly and dry 0～6 time by said sequence so that catalyst contains 10～40 heavy %, best 25～35 heavy %, nickel (in NiO).In the time of behind carrier impregnation and dry secondary, also will continuing dipping, must be earlier at 220～340 ℃ best 240～300 ℃, following roasting 4～10 hours, and then continue dipping next time.
(3) 220～340 ℃, best 240～300 ℃, following roasting 4-10 hour, promptly get nickeliferous 10～40 heavy %, best 25～35 heavy %, the nickel/aluminium oxide catalyst of (in NiO) and surplus aluminium oxide.
The aluminium oxide precursor can be hydrated alumina or aluminium hydroxides such as boehmite, gibbsite.The moulding of aluminium oxide precursor can be adopted the conventional forming method of supported catalyst agent carrier, as dripping a ball forming, extrusion modling etc., can glomeration or strip, and strip can be garden type strip or special-shaped strip, as trilobal cross, four blade profiles, dumbbell shape etc.; When adopting the method for extrusion modling, can add peptizing agent commonly used, as inorganic or organic acids such as nitric acid, citric acid, oxalic acid, and extrusion aid, as sesbania powder, starch, cellulose etc.Can contain auxiliary agent in the aluminium oxide precursor,, improve the pore volume and the stability of aluminium oxide as phosphorus, silica etc.Nickel amine complex can make (general materialization handbook or USP4191664) by nickel salt, ammoniacal liquor and its anion ammonium salt identical with the nickel salt anion according to the conventional preparation method of nickel amine complex, wherein nickel salt nickelous carbonate preferably.
Method provided by the invention takes one to be earlier with aluminium oxide precursor elder generation's moulding roasting again, and the 2nd, adopt the precursor of nickel amine complex as nickel, the 3rd, the low-temperature bake activated measure makes catalyst carrier have to be suitable for the intensity and the switch of fixed bed reactors.Nickel is evenly distributed on the catalyst, and nickel crystallite is little, thereby catalyst has good hydrogenation activity and intensity, especially produces edible white oil for the hydrofinishing of fraction oil such as lubricating base oil, hydrocracking tail oil, and its activity is higher than existing activity of such catalysts.
Following embodiment will the present invention will be further described.
Example 1～4
Aluminium hydroxide and an amount of nitric acid, citric acid, sesbania powder and water are mediated evenly, extrusion modling, 500 ℃～750 ℃ following roastings 1～4 hour promptly get trilobal cross strip carrier a～c.
Table 1
| Carrier | Aluminium hydroxide | HNO 3Gram | Grams of citric acid | Sesbania powder gram | The water milliliter | Roasting | ||
| Heavy, gram | Trade names | ℃ | Hour | |||||
| a b c d | 100 SB 100 HP 20 3822 80 HP 30 3822 70 HP | 1.8 1.4 4.2 5.2 | 4.0 4.4 3.0 3.0 | 3.0 3.0 3.0 2.0 | 65 80 64 64 | 600 4 650 3 580 4 680 2 | ||
The manufacturer of aluminium hydroxide: SB is West Germany's import, and HP is produced by Fushun No.3 Petroleum Factory; 3822 by Fushun No.3 Petroleum Factory's production, phosphorous 1.7 heavy % and SiO
25.0 heavy %.HNO
3Concentration is 65 heavy %, chemical pure; Citric acid is a food-grade, and the sesbania powder is that Shanghai local products company produces.
Example 5
With nickelous carbonate (Fushun No.3 Petroleum Factory), ammonium carbonate (Red Star chemical plant, Beijing) and ammoniacal liquor (concentration 25 heavy %) respectively in 1: 0.6: 1.1 and 1: 0.85: the ratio mixing 1.6(weight ratio) is mixed with nickel amine complex solution I and II.
A certain amount of carrier is immersed in a certain amount of nickel amine aqueous solution, and ℃ following the maintenance 1～5 hour, filter in room temperature～60,60～150 ℃ were descended dry 2～10 hours, repeated for several times by above order, 220～340 ℃ of following roastings 4～10 hours, the catalyst that gets product, details sees Table 1.
Example 6
On continuous micro-reactor (U.S. CBS Corp. 804 types), come the activity of evaluate catalysts with benzene hydrogenation.Reaction condition is: 75 ℃ of reaction temperatures, and normal pressure, the catalyst loading amount is 0.15 gram (catalyst dilutes with the quartz sand of 6.0 gram one-sizes), with hydrogen reduction 4 hours, reaction result saw Table 2 to the reaction procatalyst under 300 ℃.
Contrast the-1st is with the Ni/Al of immersion process for preparing
2O
3Catalyst, nickeliferous 27.9 heavy %(are in NiO), the preparation method is: 280 gram support C are immersed 445 milliliters of nickel nitrate solutions (/ 100 milliliters of concentration 30.5 grams, in NiO) in, filter 120 ℃ of dryings 4 hours, 260 ℃ of roastings 6 hours, repeated impregnations, filtration, drying, roasting once get final product again by above order.
Contrast the-2nd, the trade names of Nanjing catalyst plant production are 0501Ni/Al
2O
3Catalyst, nickeliferous 58.5 heavy %(are in NiO), prepare with coprecipitation.
Contrast the-3rd, the trade names that Fushun No.3 Petroleum Factory produces are 3842Ni/Al
2O
3Catalyst, nickeliferous 43.5 heavy %(are in NiO), prepare with kneading method.
Contrast the-4th is with reference to the Ni/Al of the preparation of the method among USP4191644 and the USP4490480
2O
3Catalyst, nickeliferous 70 heavy %(are in NiO), its preparation method is:
Table 1
* behind impregnation drying 2 times,, carry out the 3rd dipping again 220～340 ℃ of following roastings 4～10 hours.
Table 2
| Catalyst | The heavy % of NiO | Conversion ratio % | Pore volume milliliter/gram | Specific surface rice 2/ gram | The intensity kilograms per centimeter 2 |
| A B C D E F G H I J K L contrast-1 contrast-2 contrasts-3 contrasts-4 | 26.6 27.2 28.3 27.7 26.2 26.2 26.2 10.3 19.2 27.7 27.0 27.2 27.9 58.5 43.5 70.0 | 58.8 56.4 65.6 57.5 66.7 66.3 55.3 26.4 45.4 67.6 50.1 51.0 31.5 45.9 17.4 70.2 | 0.26 0.29 0.29 0.33 0.29 0.28 0.23 0.27 | 221 220 218 212 198 152 132 212 | 23 14.0 14.7 14.2 10.0 5.1 |
With 90 gram ammonium carbonates, 365 milliliters of ammoniacal liquor (26.3 heavy %) and 120 gram nickelous carbonates are made into nickel amine complex solution; Under agitation add 2 premium on currency, 30 gram aluminium hydroxides and 10 gram γ-Al
2O
3, warming while stirring dropwise adds 80 ml water glass then and (contains 12.5 heavy %SiO
2) and the mixture of 100 ml waters, continue warming while stirring, rise to 85 ℃, kept 4 hours, filter, wash 8 times with the deionization of 80 ℃ of temperature, 120 ℃ of dryings 4 hours, grinding; Fine powders (＜200 order) after 60 grams grind add 2.4 gram sesbania powder, and 2.4 milliliters of nitric acid (65 heavy %) and 23.6 ml waters mix, extrusion modling, 120 ℃ of dryings 4 hours, 360 ℃ of roastings 5 hours.
The catalyst prepared of the present invention has good activity and intensity as can be seen from Table 2.Catalyst fourth nickeliferous 27.7 heavy %(are in NiO), contrast-4 catalyst nickeliferous 70.0 heavy %(are in NiO), though nickel content differs greatly, both activity are very approaching to be respectively 67.6% and 70.2%.
The specific surface and the pore volume of catalyst have been measured with low-temperature nitrogen adsorption method, measure the intensity of catalyst with the intensity meter of Dalian soda plant production, the results are shown in Table 2, can see that from table the surface area of the catalyst that the present invention prepares and pore volume all are higher than with surface area and the pore volume of spreading the catalyst that infusion process and coprecipitation make.
Example 7
In 300 milliliters of downflow system continuous flow fixed bed reactors, carry out the hydrofinishing of hydrocracking tail oil and produce edible white oil, the reactivity worth of comparison catalyst J and contrast-3 (oil three factories, usefulness contrast-3 catalyst are as the catalyst of producing cosmetic white oil).
Reaction condition is: 220～240 ℃ of reaction temperatures, hydrogen dividing potential drop 13.5 MPas, air speed 0.6～1.5(hour)
-1, H
2/ oil ratio is 300: 1, and catalyst is used hydrogen reduction 24 hours under 280 ℃ before reaction, and reaction result sees Table 3.
Every performance indications of feedstock oil and product are measured with following each standard method in the table: viscosity GB265, and colourity GB3555, freezing point GB510, flash-point is used West Germany pharmacopeia DAB-7 method with the easy carbon compound SY2867 of GB267, ultraviolet light absorption.(GB is a national standard, and SY is petroleum department's standard).
Produce in the process of food white oil at hydrocracking tail oil as seen from Table 3, the catalyst made from the present invention has good activity, double than catalyst in the air speed comparison, and during low 20 ℃ of reaction temperature, the white oil of being produced still meets standard-required.
Table 3
Example 8
Press the reactivity worth of the method evaluate catalysts J of example 7 to different material oil, reaction condition: 220 ℃ of temperature, hydrogen/oil ratio are 300: 1, air speed 0.4～2.0.Reaction result sees Table 4.
Table 4
To different material oil, the catalyst made from method provided by the invention has excellent activity as seen from Table 4, and its product satisfies standard-required.
Example 9
Respectively with on the more Ni-W catalyst of arene saturating activity in catalyst J and the hydrogenation catalyst commonly used, carry out the hydrofinishing of grand celebration wax oil, to reduce the content of its aromatic hydrocarbons and readily carbonizable substance, improve its light stability, satisfy the requirement of packing usefulness or food grade paraffin wax.Reaction condition: 200～290 ℃ of reaction temperatures, hydrogen dividing potential drop 2.3 MPas, air speed 1.0(hour)
-1, hydrogen/oil ratio 200: 1, before the catalyst J reaction 280 ℃ of following hydrogen reductions 28 hours, the Ni-W catalyst before reaction with containing 2%CS
2Lam-oil under 290 ℃, give the sulfuration 8 hours, reaction unit is identical with example 7.Reaction result sees Table 5.
The physico-chemical property of oil is measured with following method in the table: oil content GB3554, and light stability SY2854, readily carbonizable substance SY2861, look number use GB6540, ultraviolet absorptivity SY2860.
Table 5
| J | Ni-W | Feedstock oil | ||||
| Reaction temperature, ℃ | 200 | 230 | 250 | 290 | 250 | |
| Oil content, % light stability readily carbonizable substance look ultraviolet absorptivity, 280nm | 1.64 1.93 1.64 2.66 3324 qualified 1111 0.264 0.231 0.135 0.129 | 1.75 29 defective 1-2/ | 1.63/defective＞9/ | |||
The Ni-W catalyst is by 2.5 heavy %NiO, 24.5 heavy %WO
3With surplus r-Al
2O
3Form, make with infusion process, r-Al
2O
3Immerse in the mixed liquor of nickel nitrate and ammonium metatungstate, again drying and roasting is got final product.
As can be known, the catalyst made from the present invention carries out paraffin oil hydrofinishing from table, and indexs such as the light stability of its product, readily carbonizable substance, ultraviolet absorptivity all meet the demands, and is better than the product with Ni-W catalyst reaction gained.
Claims (9)
1, contain the nickel/alumina load type Preparation of catalysts method of 10～40 heavy % nickel (in NiO) and surplus aluminium oxide, it is characterized in that:
(1) with the precursor moulding of aluminium oxide,, promptly gets carrier 500～750 ℃ of following roastings 1～4 hour.
(2) carrier is immersed in the nickel amine complex solution that concentration is 100～280 grams per liters (in NiO), ℃ following the maintenance 1～5 hour in room temperature～60, filter, drying is 2～10 hours under 60～150 ℃, flood repeatedly and dry 0～6 time by said sequence, so that catalyst contains 10～40% heavy nickel (in NiO), in the time of behind carrier impregnation and dry secondary, also will continuing to flood, necessary earlier 220～340 ℃ of following roastings 4～10 hours, and then continue dipping next time.
(3) 220～340 times roastings 4～10 hours get final product.
2, by the described method of claim 1, it is characterized in that said aluminium oxide precursor is the salic or aluminium hydroxide of water in (1).
3, by claim 1 or 2 described methods, it is characterized in that containing phosphorus in the said aluminium oxide precursor in (1).
4, by claim 1 or 2 described methods, it is characterized in that containing SiO in the said aluminium oxide precursor in (1)
2
5, by the described method of claim 1, it is characterized in that said moulding is extrusion modling in (1).
6, by the described method of claim 1, it is characterized in that said nickel amine complex is to be made according to the conventional preparation method of nickel amine complex by nickel salt, ammoniacal liquor and its anion ammonium salt identical with the nickel salt anion in (2).
7, by the described method of claim 7, it is characterized in that said nickel salt is a nickelous carbonate.
8, by the described method of claim 1, it is characterized in that said sintering temperature is 240～300 ℃ in (2) and (3).
9,, it is characterized in that containing on the said finished catalyst in (2) nickel (in NiO) of the heavy % of 25-35 by the described method of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89106476 CN1016319B (en) | 1989-08-28 | 1989-08-28 | Process for preparation of nickel-aluminium oxide catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89106476 CN1016319B (en) | 1989-08-28 | 1989-08-28 | Process for preparation of nickel-aluminium oxide catalyst |
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| Publication Number | Publication Date |
|---|---|
| CN1049800A true CN1049800A (en) | 1991-03-13 |
| CN1016319B CN1016319B (en) | 1992-04-22 |
Family
ID=4856753
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89106476 Expired CN1016319B (en) | 1989-08-28 | 1989-08-28 | Process for preparation of nickel-aluminium oxide catalyst |
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|---|---|
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| CN1046435C (en) * | 1995-06-15 | 1999-11-17 | 华南理工大学 | Catalyst for producing synthetic gas by methane selectively oxidizing |
| US7238276B2 (en) | 2000-05-19 | 2007-07-03 | China Petroleum Corporation | Medium-pressure hydrocracking process |
| CN100335165C (en) * | 2004-12-21 | 2007-09-05 | 中国科学院山西煤炭化学研究所 | Hydrogenation catalyst, its process and use |
| CN100337752C (en) * | 2006-02-14 | 2007-09-19 | 钢铁研究总院 | Gas phase permeation precipitation method for preparation of supported nanometer nickel hydrogenation catalyst |
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| CN104122128A (en) * | 2014-07-22 | 2014-10-29 | 中国石油大学(华东) | Aluminum oxide supported sulfurized molybdenum (tungsten) base hydrogenation catalyst activity phase sample preparing method |
| CN104383948A (en) * | 2014-10-31 | 2015-03-04 | 常州大学 | Preparation method of siliceous mesocellular foams (MCFs) loaded nano Ni2P hydrogenation catalyst |
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| CN1046435C (en) * | 1995-06-15 | 1999-11-17 | 华南理工大学 | Catalyst for producing synthetic gas by methane selectively oxidizing |
| US7238276B2 (en) | 2000-05-19 | 2007-07-03 | China Petroleum Corporation | Medium-pressure hydrocracking process |
| CN100335165C (en) * | 2004-12-21 | 2007-09-05 | 中国科学院山西煤炭化学研究所 | Hydrogenation catalyst, its process and use |
| CN100337752C (en) * | 2006-02-14 | 2007-09-19 | 钢铁研究总院 | Gas phase permeation precipitation method for preparation of supported nanometer nickel hydrogenation catalyst |
| CN101172233B (en) * | 2006-11-01 | 2011-10-12 | 中国石油化工股份有限公司 | Mineral spirit platreating catalyzer and preparation method thereof |
| CN101265419B (en) * | 2007-03-16 | 2011-05-25 | 中国石油天然气股份有限公司 | Method for producing food-grade white oil by one-stage medium-pressure hydrogenation |
| CN103212417A (en) * | 2013-04-19 | 2013-07-24 | 陕西科技大学 | Preparation method of nickel oxide/alumina and nickel/alumina nanometer compound microparticle |
| CN103212417B (en) * | 2013-04-19 | 2015-04-08 | 陕西科技大学 | Preparation method of nickel oxide/alumina and nickel/alumina nanometer compound microparticle |
| CN104122128A (en) * | 2014-07-22 | 2014-10-29 | 中国石油大学(华东) | Aluminum oxide supported sulfurized molybdenum (tungsten) base hydrogenation catalyst activity phase sample preparing method |
| CN104383948A (en) * | 2014-10-31 | 2015-03-04 | 常州大学 | Preparation method of siliceous mesocellular foams (MCFs) loaded nano Ni2P hydrogenation catalyst |
| CN104941647A (en) * | 2015-06-18 | 2015-09-30 | 四川之江高新材料股份有限公司 | Method for synthetizing N-methylmorpholine and supported catalyst used in synthesis of N-methylmorpholine |
| CN108856706A (en) * | 2017-05-10 | 2018-11-23 | 中国石油化工股份有限公司 | A kind of carbon-coating nickel aluminium composite material and its preparation method and application |
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| CN1016319B (en) | 1992-04-22 |
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