CN102451699B - Method for preparing catalyst by hydrotreatment - Google Patents
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- CN102451699B CN102451699B CN 201010514277 CN201010514277A CN102451699B CN 102451699 B CN102451699 B CN 102451699B CN 201010514277 CN201010514277 CN 201010514277 CN 201010514277 A CN201010514277 A CN 201010514277A CN 102451699 B CN102451699 B CN 102451699B
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Abstract
The invention discloses a method for preparing a catalyst by hydrotreatment. The method comprises the following steps: gelatinizing aluminum hydroxide and adding a stable boron-containing organic compound solution, introducing a boron auxiliary agent to obtain the boron-containing aluminum hydroxide, mixing active metal ingredients with boron-containing aluminum hydroxide by a wet-mixing-kneading method, three-segment roasting to obtain a catalyst intermediate, dipping the residual partial active metal and loading on the catalyst intermediate, drying to obtain the hydrotreatment catalyst. According to the invention, the boron auxiliary agent and the active metal ingredients are uniformly distributed on the surface of the catalyst, active metal ingredients introduced by two modes has different forms in the catalyst, mutual cooperation enables reduction of activity loss rate of the catalyst, and the running period of the apparatus can be prolonged. The catalyst has the characteristics of large pore volume and large specific surface area, and possesses proper pore structure and acidity, is especially suitable for hydrodenitrogenation process of heavy hydrocarbon.
Description
Technical field
The present invention relates to a kind of preparation method of hydrotreating catalyst, particularly a kind of preparation method of the hydrotreating catalyst for the heavy hydrocarbon hydrodenitrogeneration.
Background technology
At present, countries in the world are more and more stricter to the requirement of vehicle fuel, especially to the content of sulphur, nitrogen and aromatic hydrocarbons.And oil day by day becomes and heavily becomes bad with the increase of yield, and the mankind but constantly increase the demand of vehicle fuel, cause each refinery increasing to the difficulty of processing of oil.Wherein hydrogen addition technology is one of important technology of producing proper fuel, and under above-mentioned background, the raw material that this technology is processed is also heavy in the bad change of change, like this hydrogenation catalyst is also constantly proposed Secretary.
Hydrogenation catalyst adopts alumina support usually, but because pore volume and the aperture of aluminium oxide itself are less, in actual application, usually add and help catalyst component, as boron, silicon, phosphorus, titanium, zirconium etc., improve pore structure and the Acidity of aluminium oxide, improve the interaction relationship between reactive metal decentralization and reactive metal and carrier, and then the reactivity worth of raising catalyst, improve anti-coking or anti-Coking Behavior, the service life of extending catalyst.
At present, introduce the method help catalyst component in hydrogenation catalyst, introduce when being included in the preparation alumine hydroxide colloid, introduce when the making beating of preparation alumina support process colloid and introduce during at alumina support supported active metal.Wherein introducing when the preparation alumine hydroxide colloid is to adopt coprecipitation, is about to add precipitating reagent under the existence of aluminium salt and boron-containing compound, gets through the plastic reaction.Introducing when the making beating of preparation alumina support process colloid is first to prepare alumine hydroxide colloid, and then boron-containing compound is sneaked in alumine hydroxide colloid and makes.Introducing when alumina support supported active metal and refer to first prepare alumina support, then together introduce with active metal component or introduced before or after introducing reactive metal, is generally to adopt the method for dipping to introduce.Due to boron add mode different, will produce different impacts to catalyst performance.
US 4,724,226 disclose a kind of B catalyst that contains, its carrier is to contain the aluminium oxide that boron oxide is 0.1～5.0wt%, and the boracic carrier adopts aluminum sulfate and sodium metaaluminate and kodalk coprecipitation to prepare, and the subject matter of the method is that boron adds by coprecipitation, boron mainly be distributed in alumina body mutually in, be unfavorable for that catalyst forms suitable pore structure on the one hand, specific area is less, can't give full play in addition the effect of regulating alumina surface character.
CN1458232A discloses a kind of hydrotreating catalyst, and the boron-containing alumina carrier that wherein adopts is that the precursor that first prepares gama-alumina is aluminium hydroxide, and then making beating, add the auxiliary agents such as boron.This boron additive is to adopt boric acid, fluoboric acid ammonia or boron trifluoride to introduce.The method adopts the acidity of fluoboric acid ammonia or boron trifluoride stronger, and with intensity and the specific area of heavy losses catalyst, the activity of catalyst will reduce greatly, and this is fluorine-containing and compound boron is poisonous, and working environment is worsened.In addition, the method need to be heated to 50～90 ℃ and carry out when mixing, and operating process is complicated, increases production cost.And if employing boric acid at room temperature carries out, boric acid is easily separated out, and causes the decentralization of boron in aluminium oxide relatively poor, and when boron content was above over 2%, major part was converted into inactive tetrahedral coordination B.Adopt boric acid as auxiliary agent, although can play the reaming effect, but the pore volume of its resulting aluminium oxide and specific area increasing degree are little, if it is improper that operating condition is controlled, or the control of boron content is improper, also can affect the aluminium hydroxide plastic, and then make the intensity variation of the catalyst of alumina support and preparation, reduce activity and the service life of catalyst.
CN1325942A discloses a kind of preparation method of Hydrobon catalyst, is to adopt a kind of dipping solution that contains simultaneously group vib, group VIII metal component, organic carboxyl acid and polyalcohol mixed twine mixture and auxiliary agent B to make through the oxide impregnation alumina supporter.Add organic complexing agent in the method, improved the stability of boron, but owing to flooding with reactive metal simultaneously, boron and reactive metal are existing competitive Adsorption with carrier, affect the decentralization of reactive metal on carrier.In addition, in the body formed rear introducing of carrying alumina, less on pore structure and the duct impact of alumina support due to boron, do not play the effect of reaming; The acid site type to carrier is not adjusted before the supported active metal; Abated effect is not played in interaction stronger between reactive metal and carrier, make catalyst activity reduce.
Summary of the invention
For the deficiencies in the prior art, the invention provides the preparation method of the hydrotreating catalyst of a kind of large pore volume, bigger serface, pore distribution concentration.The method is evenly distributed in catalyst boron additive and active metal component, has strengthened the facilitation to active phase transformation, has improved the active and stable of catalyst.
The preparation method of hydrotreating catalyst of the present invention comprises:
(1) react with plastic during inorganic salt containing aluminium solution and precipitating reagent carry out;
(2) after step (1) plastic reaction, add the boracic solution of organic compound, adjusting pH is 5.0～10.0 scopes, and temperature is 50～90 ℃, carries out agingly, and ageing time is 30～200min; The method of described boracic solution of organic compound is as follows: boric acid is dissolved in water, then adds Organic Alcohol to make the boracic solution of organic compound;
(3) the aging slurries of step (2) gained are filtered, wash;
(4) step (3) gained filter cake is carried out drying, make boron-containing aluminum hydroxide solid elastomer;
(5) with boron-containing aluminum hydroxide solid elastomer, the precursor that contains the part active metal component and adhesive kneading, moulding, then carry out drying 1～20h under 110～160 ℃, again 180～240 ℃ of constant temperature calcinings 0.5～3.0 hour, 270～380 ℃ of constant temperature calcinings 1.0～4.0 hours, 400～530 ℃ of constant temperature calcinings 2.0～5.0 hours, obtain catalyst intermediate;
(6) the remainder active metal component loads on the catalyst intermediate of step (5) gained with infusion process, then at 60～300 ℃ of drying 0.5～10.0h, preferably at 110～270 ℃ of drying 1.0～10.0h, obtain hydrotreating catalyst of the present invention.
In the inventive method, the weight that step (5) is introduced reactive metal accounts for 1%～95% of reactive metal weight in final catalyst, and is preferred 50%～90%, and wherein reactive metal is in oxide.Remaining reactive metal is introduced in catalyst by step (6).
In the inventive method, during the described inorganic salt containing aluminium solution of step (1) and precipitating reagent carry out and plastic reaction, can adopt the conventional precipitation method to prepare the method for aluminium hydroxide, such as inorganic salt containing aluminium is AlCl
3, Al (NO
3)
3, Al
2(SO
4)
3In one or more, precipitating reagent is ammoniacal liquor or sodium metaaluminate.Control the plastic reaction temperature at 40～80 ℃, the pH value of plastic reaction is 4.5～9.5.
In step (2), the addition of boron, take the weight of final gained hydrotreating catalyst as benchmark, boron oxide content is 0.5%～8.0%, is preferably 1.0%～7.0%.
The method of the described boracic solution of organic compound of step (2) is as follows: boric acid is dissolved in water, then adds Organic Alcohol to make the boracic solution of organic compound.Wherein said Organic Alcohol is one or more in sweet mellow wine, ethylene glycol and glycerine, and the mol ratio of boric acid and Organic Alcohol is 2: 1-1: 2.Contain B in the boracic solution of organic compound
2O
31～10g/100mL.
The described washing of step (3) is to wash with deionized water, controls temperature during washing between 50～90 ℃, and washing times is 2-5 time, and each wash time is 30～60min.
The described drying of step (4) is to carry out drying 1～20h under 100～150 ℃.
The described reactive metal of step (5) adopts conventional hydrogenation active metals, is generally that the group vib metal is preferably tungsten and/or molybdenum take group vib and group VIII metal as active metal component, and the group VIII metal is preferably nickel and/or cobalt.The described precursor that contains active metal component can be reactive metal oxides, also can for containing active metallic compound, can also for containing the solution of reactive metal, preferably adopt the solution that contains reactive metal.The solution that contains reactive metal can adopt that the soluble-salt that contains reactive metal is soluble in water to be made.
Adhesive when in the present invention, adhesive used can adopt conventional Kaolinite Preparation of Catalyst is generally little porous aluminum oxide.The addition of adhesive can be selected according to moulding situation and the practical application of catalyst, take the weight of hydrotreating catalyst as benchmark, take oxide content as 3%～30%.In the present invention in the Kaolinite Preparation of Catalyst kneading process, can also other conventional auxiliary agent, such as peptization acid or extrusion aid.Peptization acid is generally one or more in acetic acid, formic acid, nitric acid, hydrochloric acid, phosphoric acid and sulfuric acid, and extrusion aid is generally sesbania powder, starch etc.
In hydrotreating catalyst of the present invention, the addition of hydrogenation active metals is selected according to actual conditions and general knowledge.Be generally that the group vib metal is preferably tungsten and/or molybdenum take group vib and group VIII metal as active metal component, the group VIII metal is preferably nickel and/or cobalt.Take the weight of final hydrotreating catalyst as benchmark, the weight content of group vib metal oxide is 10%～25%, and the weight content of group VIII metal oxide is 1%～10%.In the inventive method, the weight that step (5) is introduced reactive metal accounts for 1%～95% of reactive metal weight in final catalyst, and is preferred 50%～90%, and wherein reactive metal is in oxide.Remaining reactive metal is introduced in catalyst by step (6).
In hydrotreating catalyst of the present invention, can also contain as required other auxiliary agent, as one or more in phosphorus, titanium, zirconium, silicon etc., this auxiliary agent is in oxide, and the weight content in catalyst is 0.2%～15.0%.The mode that this auxiliary agent is introduced catalyst can adopt conventional method, such as introducing in boracic aluminium hydroxide preparation process, also can be when the Kaolinite Preparation of Catalyst intermediate and introduce during boracic aluminium hydroxide kneading, can also load on catalyst intermediate with infusion process separately, perhaps prepare the solution that contains reactive metal and auxiliary agent and load on catalyst intermediate with infusion process.
The boracic aluminium hydroxide that hydrotreating catalyst of the present invention adopts be add after the aluminium hydroxide plastic boracic solution of organic compound be about to boric acid water-soluble after, join in Organic Alcohol and make, make like this reaction of boric acid and Organic Alcohol generate stable material, the boric acid temperature is low easily to be separated out thereby overcome, and makes the shortcoming of its skewness in aluminium oxide.the part active metal component is introduced catalyst and three sections roastings under given conditions in the kneading mode, the remainder active metal component is introduced in catalyst and not roasting of drying with infusion process, the method can make reactive metal three sections roastings under given conditions together with boron-containing aluminum hydroxide solid elastomer of first kneading, the organic solution of boracic is slowly decomposed, make the pore structure of catalyst more regular, pore size distribution is more even, and specific area and the pore volume of raising catalyst, rear relatively less with the reactive metal of infusion process load, and high degree of dispersion, make the catalyst of gained have a pore volume large, specific area is large, the characteristics that pore size distribution is concentrated.Have again, because boron additive has weakened interaction between reactive metal and carrier, be conducive to the dispersion of reactive metal on carrier, strengthened simultaneously the facilitation of reactive metal to active phase transformation, improved the activity of catalyst, and the active metal component that dual mode is introduced exists form different in catalyst, the loss of activity rate reduction that cooperatively interacts and make catalyst, prolong operating period.
The hydrotreating catalyst pore volume of the inventive method gained is large, specific area is large, and has suitable pore structure and acidity, is specially adapted to the hydrodenitrogeneration process of heavy hydrocarbon.
Preparation method of the present invention is simple, and easy operating does not have special environmental issue, just can realize on existing equipment.
The specific embodiment
In the present invention, specific surface, pore volume, average pore diameter, pore size distribution are to adopt the ASAP 2420 type BET analyzer low temperature liquid nitrogen determination of adsorption method of U.S. Micromeritics company production; The meleic acid amount is to adopt the infrared absorption spectrographic determination of pyridine.
Embodiment 1
To contain Al
2O
3The AlCl of 5g/100mL
3Solution 2000mL with contain NH
3The ammoniacal liquor of 10g/100mL and drip are added in the plastic reaction filling that temperature is 60 ℃ of stirrings, and keeping the pH value is 7.6, reaction contact time 40min.Be 70 ℃ in temperature, the pH value is to carry out aging 8.0 times.Ageing time is 1h.Product is filtered, and is then the deionized water washing of 1: 20 with the solid-liquid volume ratio, 80 ℃ of wash temperatures, washing times 3 times.To gained filter cake dry 3h under 120 ℃, obtain aluminium hydroxide.
Get above-mentioned aluminium hydroxide 100g, sneak into 110g by the SB alumina powder of nitric acid peptization, after kneading 20min, make the plasticity paste, by the clover orifice plate extrusion of φ 1.4mm.Wet bar is after 130 ℃ of dry 8h, and roasting 4h under 520 ℃ of conditions obtains alumina support S-1.
Embodiment 2
After the plastic reaction of embodiment 1, add to contain B
2O
3The solution of organic compound 100mL of 3g/100mL.The boracic solution of organic compound is that boric acid is dissolved in water, is then preparation in 1: 1 by boric acid and sweet mellow wine mol ratio, and the preparation of other aluminium hydroxide obtains boracic aluminium hydroxide with embodiment 1.
Get above-mentioned boracic aluminium hydroxide 120g, sneak into 126g by the SB alumina powder of nitric acid peptization and contain molybdenum and the aqueous solution of cobalt, after kneading 20min, make the plasticity paste, by the clover orifice plate extrusion of φ 1.4mm.Wet bar carries out dry 3h under 130 ℃, then at 220 ℃ of constant temperature calcining 2h, at 320 ℃ of constant temperature calcining 2.0h, at 530 ℃ of constant temperature calcining 3.0h, gets catalyst C-2 intermediate, wherein, and MoO
3Weight content be that the weight content of 11.1%, CoO is 2.7%.The molybdenum of catalyst C-2 intermediate dipping surplus and the aqueous solution of cobalt are at 200 ℃ of drying condition 3.0h.In this catalyst, MoO
3Weight content be that the weight content of 12.2%, CoO is 3.0%.
Embodiment 3
Changing into the boracic solution of organic compound in embodiment 2 by boric acid and ethylene glycol mol ratio is preparation in 1.0: 1.5, and other aluminium hydroxide preparation obtains boracic aluminium hydroxide with embodiment 2.
Get above-mentioned boracic aluminium hydroxide 110g, sneak into 118g by the SB alumina powder of nitric acid peptization and contain molybdenum and the aqueous solution of phosphorus, after kneading 20min, make the plasticity paste, by the clover orifice plate extrusion of φ 1.4mm.Wet bar carries out dry 3h under 140 ℃, then at 200 ℃ of constant temperature calcining 0.5h, at 32O ℃ of constant temperature calcining 2.0h, at 530 ℃ of constant temperature calcining 3.0h, gets catalyst C-3 intermediate, wherein MoO
3Weight content be that the weight content of 23.2%, P is 0.85%.The aqueous solution of molybdenum, nickel and the phosphorus of catalyst C-3 intermediate dipping surplus at 200 ℃ of drying condition 3.0h, gets catalyst C-3.In this catalyst, MoO
3Weight content be that the weight content of 24.6%, NiO is that the weight content of 4.02%, P is 1.21%.
Embodiment 4
Changing into the boracic solution of organic compound in embodiment 2 by boric acid and glycerine mol ratio is preparation in 1.5: 1.0, and other aluminium hydroxide preparation obtains boracic aluminium hydroxide with embodiment 2.
Get above-mentioned boracic aluminium hydroxide 95g, sneak into 102g by the aqueous solution of the SB alumina powder of nitric acid peptization and tungstenic, molybdenum, nickel, after kneading 20min, make the plasticity paste, by the clover orifice plate extrusion of φ 1.4mm.Wet bar carries out dry 2.0h under 150 ℃, then at 210 ℃ of constant temperature calcining 1.0h, at 330 ℃ of constant temperature calcining 2.0h, at 520 ℃ of constant temperature calcining 2.0h, gets catalyst C-4 intermediate, wherein WO
3Weight content be 20.1%, MoO
3Weight content be that the weight content of 2.1%, NiO is 2.2%.The tungsten of catalyst C-4 intermediate dipping surplus and the aqueous solution of nickel at 190 ℃ of drying condition 2.0h, get catalyst C-4.In this catalyst, WO
3Weight content be 21.3%, MoO
3Weight content be that the weight content of 2.1%, NiO is 2.6%.
Embodiment 5
Boracic solution of organic compound in embodiment 2 is changed into contain B
2O
3The solution of organic compound 100mL of 6g/100mL, other aluminium hydroxide preparation obtains boracic aluminium hydroxide with embodiment 2.
Get above-mentioned boracic aluminium hydroxide 100g, sneak into 105g by the SB alumina powder of nitric acid peptization and contain molybdenum and the aqueous solution of phosphorus, after kneading 20min, make the plasticity paste, by the clover orifice plate extrusion of φ 1.4mm.Wet bar carries out dry 1.0h under 140 ℃, then at 220 ℃ of constant temperature calcining 2.0h, at 320 ℃ of constant temperature calcining 2.0h, at 520 ℃ of constant temperature calcining 2.0h, gets catalyst C-5 intermediate, wherein MoO
3Weight content be that the weight content of 14.6%, P is 1.4%.The aqueous solution that catalyst C-5 intermediate dipping is nickeliferous at 240 ℃ of drying condition 3.0h, gets catalyst C-5.In this catalyst, MoO
3Weight content be that the weight content of 14.6%, NiO is that the weight content of 6.5%, P is 1.4%.
Embodiment 6
To contain Al
2O
3The Al of 5g/100mL
2(SO
4)
3Solution 1000mL with contain Al
2O
36.0g/100mL sodium aluminate solution and drip to be added to temperature be that during the plastic reaction of 65 ℃ of stirrings is filled with, keeping the pH value is 8.2, reaction contact time 50min.After cemented into bundles, add under stirring and contain B
2O
3100 milliliters of 6g/100mL solution of organic compound, this boracic solution of organic compound is that boric acid is dissolved in water, then by boric acid and sweet mellow wine mol ratio be 2: 1 the preparation.Be 8.5 with slurries in the pH value, carry out agingly under the condition of temperature 60 C, ageing time is 1.5h.Product is filtered, and is then the deionized water washing of 1: 20 with the solid-liquid volume ratio, 70 ℃ of wash temperatures, washing times 3 times.To gained filter cake dry 3h under 120 ℃, obtain boracic aluminium hydroxide.
Get above-mentioned boracic aluminium hydroxide 100g, sneak into 110g by the SB alumina powder of nitric acid peptization and the aqueous solution of tungstenic, molybdenum and nickel, after kneading 20min, make the plasticity paste, by the clover orifice plate extrusion of φ 1.4mm.Wet bar carries out dry 2.0h under 110 ℃, then at 230 ℃ of constant temperature calcining 1.0h, at 340 ℃ of constant temperature calcining 2.0h, at 510 ℃ of constant temperature calcining 3.0h, gets catalyst C-6 intermediate, wherein WO
3Weight content be 18.4%, MoO
3Weight content be that the weight content of 4.1%, NiO is 5.6%.The tungsten of catalyst C-6 intermediate dipping surplus and the aqueous solution of molybdenum at 260 ℃ of drying condition 2.0h, get catalyst C-6.In this catalyst, WO
3Weight content be 19.8%, MoO
3Weight content be that the weight content of 5.1%, NiO is 5.6%.
Comparative example 1
After embodiment 1 plastic reaction, add boric acid 6g, other step obtains boracic aluminium hydroxide with embodiment 1.
With embodiment 2, obtain catalyst C-A with the process of boracic aluminium hydroxide Kaolinite Preparation of Catalyst.
Comparative example 2
After embodiment 1 plastic reaction, add boric acid 11g, other step obtains boracic aluminium hydroxide with embodiment 1.
With embodiment 5, obtain catalyst C-B with the process of boracic aluminium hydroxide Kaolinite Preparation of Catalyst.
Comparative example 3
The alumina support S-1 that adopts the embodiment of the present invention 1 to obtain according to the method for CN1325942A embodiment 1, adopts infusion process load boron and reactive metal simultaneously, obtains catalyst C-C.In this catalyst, MoO
3Be that 14.6%, NiO is that 6.5%, P is 1.4%, B
2O
3Content is 6.0%.
The character of the hydrotreating catalyst of embodiment 2～6 and comparative example 1～3 preparation is seen Table 1.
The character of table 1 hydrotreating catalyst
* the pore size distribution of the catalyst C-C of comparative example 3 gained is that bore dia is the percentage that the shared pore volume of 6～11nm accounts for total pore volume.
Embodiment 7
The present embodiment is the active evaluation test of catalyst of the present invention, and carries out the activity contrast with the hydrotreating catalyst that adopts the distinct methods preparation, mainly investigates the hydrodenitrogeneration performance of catalyst.
The catalyst activity evaluation is carried out on the 200mL small hydrogenation device, and it is 2 as follows that condition sees Table:
The hydroprocessing condition that table 2 embodiment and comparative example are used
| The hydrogen dividing potential drop, MPa | 14.7 |
| Hydrogen-oil ratio (volume) | 1000 |
| Temperature, ℃ | 385 |
| Air speed, h -1 | 1.0 |
Raw materials used oil is that triumph decompressed wax oil and wax tailings are the miscella of 9: 1 by weight, and character sees Table 3.
Table 3 feedstock oil character
| Density, g/cm 3 | 0.8848 |
| Carbon residue, % (mass fraction) | 0.15 |
| S, % (mass fraction) | 0.50 |
| H/C (weight ratio) | 12.92/83.96 |
| N，μg/g | 1900 |
| Boiling range, ℃ (ASTM-D1106) | |
| IBP/10％ | 315/386 |
| 30％/50％ | 432/459 |
| 70％/90％ | 484/528 |
| 95％/EP | 553/564 |
| Group composition, % (mass fraction) | |
| Alkane | 30.9 |
| Cycloalkane | 18.9 |
| Aromatic hydrocarbons | 46.0 |
| Colloid | 4.2 |
The evaluation result of catalyst of the present invention and reference agent sees Table 4.
Table 4 catalyst of the present invention and the contrast of reference agent nitrogen removal performance
| The catalyst numbering | C-A | C-B | C-C | C-2 | C-3 | C-4 | C-5 | C-6 |
| Type | The reference agent | The reference agent | The reference agent | The present invention | The present invention | The present invention | The present invention | The present invention |
| Generate oily nitrogen content, μ g/g | 31.0 | 18.9 | 22.7 | 11.4 | 10.8 | 11.6 | 2.8 | 8.0 |
| Relative denitrification activity | 100 | 112 | 108 | 124 | 126 | 125 | 158 | 133 |
Annotate: the hydrodenitrogenationactivity activity of regulation reference agent C-A is 100, and all the other are pressed
Relative denitrification activity=[ln (Nf/Np)]/ln (Nf/Npr)] * 100
Wherein: Nf is the raw material nitrogen content, and Npr and Np are respectively catalyst C-A and other catalyst hydrogenation is processed the oily nitrogen content of generation.
As seen from Table 4,, compare with reference catalyst and have higher hydrodenitrogenationactivity activity when supporting same metal with the reference agent through the catalyst of the present invention of boron additive modification.
Embodiment 8
The present embodiment is the life test of catalyst C-5 of the present invention and reference agent C-B, and experimental rig used, feedstock oil and evaluation process conditions the results are shown in Table 5 with embodiment 7.
Table 5 catalyst stability result of the test of the present invention
Can be seen by table 5, when 385 ℃ of lower steady running 2000h, when adopting catalyst of the present invention, the nitrogen content that generates oil slightly raises, and when adopting the reference agent, the nitrogen content that generates oil obviously raises, and the activity of this explanation catalyst of the present invention and stability are significantly better than the reference agent.
Claims (15)
1. the preparation method of a hydrotreating catalyst comprises:
(1) react with plastic during inorganic salt containing aluminium solution and precipitating reagent carry out;
(2) after step (1) plastic reaction, add the boracic solution of organic compound, adjusting pH is 5.0～10.0, and temperature is 50～90 ℃, carries out agingly, and ageing time is 30～200min; The preparation method of described boracic solution of organic compound is as follows: boric acid is dissolved in water, then adds Organic Alcohol to make the boracic solution of organic compound;
(3) the aging slurries of step (2) gained are filtered, wash;
(4) step (3) gained filter cake is carried out drying, make boron-containing aluminum hydroxide solid elastomer;
(5) with boron-containing aluminum hydroxide solid elastomer, the precursor that contains the part active metal component and adhesive kneading, moulding, then carry out drying 1～20h under 110～160 ℃, again 180～240 ℃ of constant temperature calcinings 0.5～3.0 hour, 270～380 ℃ of constant temperature calcinings 1.0～4.0 hours, 400～530 ℃ of constant temperature calcinings 2.0～5.0 hours, obtain catalyst intermediate;
(6) the remainder active metal component loads to infusion process on the catalyst intermediate of step (5) gained, then at 60～300 ℃ of drying 0.5～10.0h, obtains hydrotreating catalyst.
2. according to preparation method claimed in claim 1, it is characterized in that step (5) introduces the weight of reactive metal and account for 1%～95% of reactive metal weight in final catalyst, wherein reactive metal is in oxide; Remaining reactive metal is introduced in catalyst by step (6).
3. according to preparation method claimed in claim 1, it is characterized in that step (5) introduces the weight of reactive metal and account for 50%～90% of reactive metal weight in final catalyst, wherein reactive metal is in oxide; Remaining reactive metal is introduced in catalyst by step (6).
4. according to preparation method claimed in claim 1, it is characterized in that weight take catalyst as benchmark, boron oxide content is 0.5%～8.0%.
5. according to preparation method claimed in claim 1, it is characterized in that the described inorganic salt containing aluminium solution of step (1) and precipitating reagent react with plastic in carrying out, inorganic salt containing aluminium used is one or more in aluminium chloride, aluminum nitrate, aluminum sulfate, and precipitating reagent is ammoniacal liquor or sodium metaaluminate; Control 40～80 ℃ of plastic reaction temperatures, the pH value of plastic reaction is 4.5～9.5.
6. according to preparation method claimed in claim 1, it is characterized in that containing B in the described boracic solution of organic compound of step (2)
2O
31～10g/100mL.
7. according to preparation method claimed in claim 1, it is characterized in that described Organic Alcohol is one or more in sweet mellow wine, ethylene glycol and glycerine, the mol ratio of boric acid and Organic Alcohol is 2: 1～1: 2.
8. according to preparation method claimed in claim 1, it is characterized in that the described washing of step (3) is to wash with deionized water, control temperature during washing between 50～90 ℃, washing times is 2～5 times, and each wash time is 30～60min.
9. according to preparation method claimed in claim 1, it is characterized in that the described drying of step (4) is to carry out drying 1～20h under 100～150 ℃.
10. according to claim 1,2 or 3 described preparation methods, it is characterized in that in described hydrotreating catalyst, reactive metal is group vib and group VIII metal, take the weight of hydrotreating catalyst as benchmark, the weight content of group vib metal oxide is 10%～25%, and the weight content of group VIII metal oxide is 1%～10%.
11. according to preparation method claimed in claim 10, it is characterized in that the group vib metal is tungsten and/or molybdenum, the group VIII metal is nickel and/or cobalt.
12. according to preparation method claimed in claim 1, it is characterized in that the described precursor that contains active metal component of step (5) is with reactive metal oxides, perhaps contain active metallic compound, contain perhaps that the form of the solution of reactive metal adds.
13. according to preparation method claimed in claim 1, it is characterized in that in described hydrotreating catalyst, contain one or more in auxiliary agent phosphorus, titanium, zirconium, silicon, this auxiliary agent is in oxide, the weight content in catalyst is 0.2%～15.0%.
14. according to preparation method claimed in claim 1, it is characterized in that described adhesive is little porous aluminum oxide, its addition is take the weight of the hydrotreating catalyst that finally obtains as benchmark, take oxide content as 3%～30%.
15. according to preparation method claimed in claim 1, it is characterized in that the described drying condition of step (6) is as follows: at 110～270 ℃ of drying 1.0～10.0h.
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| CN102451699B true CN102451699B (en) | 2013-06-05 |
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| CN104445317B (en) * | 2014-11-12 | 2016-09-14 | 中国海洋石油总公司 | A kind of preparation method of modified boehmite |
| CN106311263B (en) * | 2016-07-29 | 2018-10-23 | 武汉凯迪工程技术研究总院有限公司 | High load amount boron modification Hydrobon catalyst and preparation method thereof |
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| CN1854260A (en) * | 2005-04-27 | 2006-11-01 | 中国石油化工股份有限公司 | Heavy fractional oil hydrogenation catalyst and production thereof |
| CN101314130A (en) * | 2007-05-31 | 2008-12-03 | 中国石油化工股份有限公司 | Boron containing hydrodesulphurization catalyst and preparation method thereof |
| CN101619241A (en) * | 2008-07-04 | 2010-01-06 | 中国石油化工股份有限公司 | Method for hydrofining paraffin wax |
| CN101664688A (en) * | 2008-09-04 | 2010-03-10 | 中国石油化工股份有限公司 | Hydrogenation desilicification catalyst and preparation thereof |
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| CN1854260A (en) * | 2005-04-27 | 2006-11-01 | 中国石油化工股份有限公司 | Heavy fractional oil hydrogenation catalyst and production thereof |
| CN101314130A (en) * | 2007-05-31 | 2008-12-03 | 中国石油化工股份有限公司 | Boron containing hydrodesulphurization catalyst and preparation method thereof |
| CN101619241A (en) * | 2008-07-04 | 2010-01-06 | 中国石油化工股份有限公司 | Method for hydrofining paraffin wax |
| CN101664688A (en) * | 2008-09-04 | 2010-03-10 | 中国石油化工股份有限公司 | Hydrogenation desilicification catalyst and preparation thereof |
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