CN102728374A - Preparation method of hydrotreatment catalyst - Google Patents
Preparation method of hydrotreatment catalyst Download PDFInfo
- Publication number
- CN102728374A CN102728374A CN201110093573XA CN201110093573A CN102728374A CN 102728374 A CN102728374 A CN 102728374A CN 201110093573X A CN201110093573X A CN 201110093573XA CN 201110093573 A CN201110093573 A CN 201110093573A CN 102728374 A CN102728374 A CN 102728374A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- boron
- weight
- reactive metal
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a preparation method of a hydrotreatment catalyst, comprising the following steps of: introducing silicon and boron additives in the way that an organic silicon source is added after aluminium hydroxide gel forming and then a boron-containing organic compound solution is added, so as to obtain silicon and boron containing aluminium hydroxide, mixing parts of an active metal component with boron-containing aluminium hydroxide by a kneading method, carrying out three-stage roasting to obtain a catalyst intermediate, loading residual part of the active metal onto the catalyst intermediate by dipping, and drying to obtain the hydrotreatment catalyst. By the adoption of the method provided by the invention, the silicon and boron additives and the active metal component are uniformly distributed on the surface of the catalyst. In addition, the active metal component has different existing forms in the catalyst when introduced in the two modes, loss rate of the catalyst activity is reduced by mutual cooperation, and running period of a device is prolonged. The catalyst has large pore volume, large specific surface area, appropriate pore structure and acidity, and is especially suitable for hydrodenitrogenation process of heavy hydrocarbon.
Description
Technical field
The present invention relates to a kind of preparation method of hydrotreatment catalyst, the preparation method of hydrotreatment catalyst of particularly a kind of large pore volume and bigger serface.
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 becomes day by day and heavily becomes bad with the increase of yield, and human demand to vehicle fuel but constantly increases, and causes 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 new requirement.
Hydrogenation catalyst adopts alumina support usually, but because the pore volume and the aperture of aluminium oxide itself are less, in actual application; Usually add and help catalyst component,, improve the pore structure and the acid matter of aluminium oxide like boron, silicon, phosphorus, titanium, zirconium etc.; 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-carbon deposit performance, prolong the service life of catalyst.
At present, introduce the method help catalyst component in the hydrogenation catalyst, introduce when being included in the preparation alumine hydroxide colloid, when the making beating of preparation alumina support process colloid, introduce and introduce during at alumina support supported active metal.Wherein when the preparation alumine hydroxide colloid, introducing is to adopt coprecipitation, is about to the existence of aluminium salt and boron-containing compound and adds precipitating reagent down, gets through becoming glue to react.When the making beating of preparation alumina support process colloid, introducing is preparation alumine hydroxide colloid earlier, and then boron-containing compound is sneaked in the alumine hydroxide colloid and made.When alumina support supported active metal, introducing being meant preparation alumina support earlier, together introduce with active metal component then or before or after introducing reactive metal, introduce, generally is to adopt the method for dipping to introduce.Because the adding mode of boron is different, will produce different influences to catalyst performance.
US 4,724, and 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 this method is that boron passes through coprecipitation and adds; 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 to the effect of regulating alumina surface character in addition.
CN1458232A discloses a kind of hydrotreating catalyst, and the boron-containing alumina carrier that wherein adopts is that the precursor of preparation G-aluminium oxide earlier is an aluminium hydroxide, and making beating then adds auxiliary agents such as boron.This boron additive is to adopt boric acid, fluoboric acid ammonia or boron trifluoride to introduce.This method adopts the acidity of fluoboric acid ammonia or boron trifluoride stronger, and with the intensity and the specific area of heavy losses catalyst, activity of such catalysts will reduce greatly, and this is fluorine-containing poisonous with compound boron, and working environment is worsened.In addition, this method need be heated to 50 ~ 90 ℃ and carry out when mixing, and complicated operating process increases production cost.And adopting boric acid if at room temperature carry out, boric acid is separated out easily, causes the decentralization of boron in aluminium oxide relatively poor, and when boron content was above above 2%, major part was converted into inactive tetrahedral coordination B.Adopt boric acid as auxiliary agent; Though can play the reaming effect, the pore volume of its resultant aluminium oxide and specific area increasing degree are little, and if operating condition control is improper; Or the control of boron content is improper; Also can influence aluminium hydroxide and become glue, and then make the intensity variation of the catalyst of alumina support and preparation, reduce activity of such catalysts and service life.
CN1325942A discloses a kind of preparation method of Hydrobon catalyst, is to adopt a kind of dipping solution that contains group VIB, metal component of group VIII, organic carboxyl acid and polyalcohol mixed twine mixture and auxiliary agent B simultaneously to make through the oxide impregnation alumina supporter.Add organic complexing agent in this method, improved the stability of boron, but owing to flood with reactive metal simultaneously, boron and reactive metal are existing competitive Adsorption with carrier, influence the decentralization of reactive metal on carrier.Simultaneously boron certainly will weaken the facilitation of the active in opposite directions higher active phase transformation of II type of I type activity, and then the raising of the type catalyst activity is restricted.In addition, because boron is less to the pore structure and the duct influence of alumina support in carrying alumina body formed back introducing, 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
To the deficiency of prior art, the invention provides the preparation method of hydrotreatment catalyst of a kind of large pore volume, bigger serface, pore distribution concentration.This method is evenly distributed in the catalyst boron additive, has strengthened the facilitation to active phase transformation, improves activity of such catalysts and stability.
Preparation method of hydrotreatment catalyst of the present invention comprises:
(1) inorganic salt containing aluminium solution and precipitating reagent are neutralized into the glue reaction;
(2) in the system of step (1) gained, add the organosilicon source, aging then;
(3) in the system that step (2) obtains, add the boracic solution of organic compound, adjustment pH is 7.0～10.0, and temperature is 50 ~ 90 ℃, wears out, and ageing time is 30～200min; The method of described boracic solution of organic compound is following: boric acid is dissolved in the water, adds organic alcohol then and make the boracic solution of organic compound;
(4) the aging slurries of step (3) gained are filtered, wash;
(5) step (4) gained filter cake is carried out drying, make siliceous and aluminum hydroxide solid elastomer boron;
(6) with siliceous and boron aluminum hydroxide solid elastomer, the precursor that contains the part active metal component and adhesive mixedly pinch, moulding; Under 110 ~ 160 ℃, carry out drying 1 ~ 20h then; Again 180 ~ 240 ℃ of constant temperature calcinings 0.5 ~ 3.0 hour; 270 ~ 380 ℃ of constant temperature calcinings 1.0 ~ 4.0 hours,, obtain catalyst intermediate 400 ~ 530 ℃ of constant temperature calcinings 2.0 ~ 5.0 hours;
(7) the remainder active metal component loads to infusion process on the catalyst intermediate of step (6) gained, at 60 ~ 300 ℃ of drying 0.5 ~ 10.0h, obtains hydrotreating catalyst then.
In the inventive method; Described inorganic salt containing aluminium solution of step (1) and precipitating reagent are neutralized into the glue reaction; Can adopt the conventional precipitation method to prepare the method for aluminium hydroxide; Such as inorganic salt containing aluminium is in aluminium chloride, aluminum nitrate, aluminum sulfate, the sodium metaaluminate one or more, and precipitating reagent is ammoniacal liquor, sodium metaaluminate or carbon dioxide.Be controlled to the glue reaction temperature at 40 ~ 80 ℃, become the glue reaction pH value to be controlled in 7.0～9.5 the scope.Step (1) can wear out after becoming glue, also can not wear out, and wherein aging condition is following: 30 ~ 80 ℃ of aging temperatures, ageing time 60 ~ 300min.
The said adding organosilicon of step (2) source can be to comprise in organic silicone oil or the estersil class etc. one or more; Wherein organic silicone oil is one or more in methyl-silicone oil, the dimethyl-silicon wet goods, and estersil is one or more in silester, the ethyl orthosilicate etc.Step (2) control aging temperature is 30 ~ 80 ℃, and ageing time is 60 ~ 300min.
In the step (3), the addition of silicon and boron is a benchmark with the weight of final gained hydrotreating catalyst, and boron oxide content is 0.5%～8.0%, is preferably 1.0%～7.0%, and the weight content of silica is 1.0% ~ 15.0%, is preferably 1.0%～7.0%.
The method of the described boracic solution of organic compound of step (3) is following: boric acid is dissolved in the water, adds organic alcohol then and make the boracic solution of organic compound.Wherein said organic alcohol is one or more in sweet mellow wine, ethylene glycol and the 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 ~ 10 g/100mL.
The described washing of step (4) is to wash with deionized water, and the control temperature is between 50 ~ 90 ℃ during washing, and washing times is 2-5 time, and each wash time is 30～60min.
The described drying of step (5) is under 100 ~ 150 ℃, to carry out drying 1 ~ 20h.
The described reactive metal of step (6) adopts conventional hydrogenation active metals, generally is to be active metal component with group vib and group VIII metal, and the group vib metal is preferably tungsten and/or molybdenum, 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 also preferably adopt the solution that contains reactive metal for containing the solution of reactive metal for containing active metallic compound.The solution that contains reactive metal can adopt that the soluble-salt that contains reactive metal is soluble in water to be processed.
Adhesive when used adhesive can adopt conventional preparation catalyst among the present invention is generally little porous aluminum oxide.The addition of adhesive can be selected according to the moulding situation and the practical application of catalyst, is benchmark with the weight of hydrotreating catalyst, is 3% ~ 30% in oxide content.Among the present invention in the preparation 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 the sulfuric acid, and extrusion aid is generally sesbania powder, starch etc.
In the hydrotreating catalyst of the present invention, the addition of hydrogenation active metals is selected according to actual conditions and general knowledge.Generally be to be active metal component with group vib and group VIII metal, the group vib metal is preferably tungsten and/or molybdenum, and the group VIII metal is preferably nickel and/or cobalt.Weight with final hydrotreating catalyst is benchmark, and 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 (6) is introduced reactive metal accounts for 1% ~ 95% of reactive metal weight in the final catalyst, and is preferred 50% ~ 90%, and wherein reactive metal is in oxide.Remaining reactive metal is introduced in the catalyst by step (7).
In the hydrotreating catalyst of the present invention, can also contain other auxiliary agent as required, like in phosphorus, titanium, zirconium, the fluorine etc. one or more, 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 can in the preparation of aluminium hydroxide process of siliceous and boron, introducing; Also can mix introducing when pinching with siliceous and boron aluminium hydroxide during catalyst intermediate in preparation; Can also load on the catalyst intermediate with infusion process separately, perhaps prepare the solution that contains reactive metal and auxiliary agent and load on the catalyst intermediate with infusion process.
Siliceous and the boron aluminium hydroxide that hydrotreating catalyst of the present invention adopted is after aluminium hydroxide becomes glue, successively to introduce silicon and boron additive; And silicon additive is to adopt the mode in organosilicon source to introduce; The introducing mode of boron additive is to adopt boracic organic solution to be about to boric acid to join after water-soluble in organic alcohol and make; Make boric acid and organic alcohol reaction generate stable material like this; The boric acid temperature is low to be separated out easily thereby overcome, boron in aluminium hydroxide skewness, can not with the fine shortcoming that cooperates of silicon.The part active metal component is introduced catalyst and three sections roastings under given conditions to mix the mode of pinching; The remainder active metal component is introduced in the catalyst and through not roasting of drying with infusion process, and the method can make the mixed earlier reactive metal of pinching with siliceous and aluminum hydroxide solid elastomer three sections roastings under given conditions boron, and the organic solution of organosilicon source and boracic is slowly decomposed; Make the pore structure of catalyst more regular; Pore size distribution is more even, and improves the specific area and the pore volume of catalyst, and the back is less relatively with the reactive metal of infusion process load; And high degree of dispersion, make the catalyst of gained have the advantages that pore volume is big, specific area big, pore size distribution is concentrated.Have again,, help the dispersion of reactive metal on carrier because boron additive has weakened the interaction between reactive metal and the carrier; Strengthened the facilitation of reactive metal simultaneously to active phase transformation; Improved activity of such catalysts, and the active metal component that dual mode is introduced exists form different in catalyst; Cooperatively interact and make activity of such catalysts loss speed reduce prolong operating period.
The hydrotreating catalyst pore volume of the inventive method gained is big, specific area is big, 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, on existing equipment, just can realize.
The specific embodiment
Among the present invention, specific area, 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 one-tenth glue reaction filling that temperature is 60 ℃ of stirrings, and keeping the pH value is 7.6, reaction contact time 40min.In temperature is 70 ℃, and the pH value is to wear out for 8.0 times.Ageing time is 1h.Product is filtered, use of the deionized water washing of solid-liquid volume ratio then, 80 ℃ of wash temperatures, washing times 3 times as 1:20.To gained filter cake dry 3h under 120 ℃, obtain aluminium hydroxide.
Get above-mentioned aluminium hydroxide 100g, sneak into the SB alumina powder of 110g by the nitric acid peptization, mix pinch 20min after, process the plasticity paste, through the clover orifice plate extrusion of φ 1.4mm.Wet bar is behind 130 ℃ of dry 8h, and roasting 4h under 520 ℃ of conditions obtains alumina support S-1.
Embodiment 2
Behind the one-tenth glue of embodiment 1, dropping contains SiO
22g/100mL dimethicone 100mL at 70 ℃ of down aging 80min, adds then and contains B
2O
3The solution of organic compound 100mL of 3g/100mL, boracic solution of organic compound are dissolved in boric acid in the water, are that 1:1 prepares by boric acid and sweet mellow wine mol ratio, and other obtains siliceous and aluminium hydroxide boron with embodiment 1.
Get the aluminium hydroxide 120g of above-mentioned siliceous and boron, sneak into 126g by the SB alumina powder of nitric acid peptization and contain molybdenum and the aqueous solution of cobalt, mixed pinch 20min after, process the plasticity paste, through the clover orifice plate extrusion of φ 1.4mm.Wet bar carries out dry 3h under 130 ℃, again at 210 ℃ of constant temperature calcining 2h, at 320 ℃ of constant temperature calcining 1.0h, at 530 ℃ of constant temperature calcining 3.0h, get catalyst C-2 intermediate, wherein, and MoO
3Weight content be 11.1%, the weight content of CoO is 2.7%.The molybdenum of catalyst C-2 intermediate dipping surplus and the aqueous solution of cobalt are at 210 ℃ of drying condition 3.0h.In this catalyst, MoO
3Weight content be 12.2%, the weight content of CoO is 3.0%.
Embodiment 3
Behind the one-tenth glue of embodiment 1, dropping contains SiO
22g/100mL methyl-silicone oil 100mL at 70 ℃ of down aging 80min, adds then and contains B
2O
3The solution of organic compound 100mL of 3g/100mL, boracic solution of organic compound are dissolved in boric acid in the water, are the 1.0:1.5 preparation by boric acid and ethylene glycol mol ratio; Wear out at 70 ℃ then; Ageing time is 80min, and other obtains siliceous and aluminium hydroxide boron with embodiment 1.
Get above-mentioned siliceous and boron aluminium hydroxide 110g, sneak into 118g by the SB alumina powder of nitric acid peptization and contain molybdenum and the aqueous solution of phosphorus, mixed pinch 20min after, process the plasticity paste, through the clover orifice plate extrusion of φ 1.4mm.Wet bar carries out dry 3h under 140 ℃, again at 190 ℃ of constant temperature calcining 0.5h, at 350 ℃ of constant temperature calcining 2.0h, at 530 ℃ of constant temperature calcining 2.0h, get catalyst C-3 intermediate, wherein MoO
3Weight content be 23.2%, the weight content of 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 24.6%, the weight content of NiO is 4.02%, the weight content of P is 1.21%.
Embodiment 4
Behind the one-tenth glue of embodiment 1, drip ethyl orthosilicate 100mL, at 80 ℃ of down aging 100min, add then and contain B
2O
3The solution of organic compound 100mL of 3g/100mL, boracic solution of organic compound are dissolved in boric acid in the water, are the 1.5:1.0 preparation by boric acid and glycerine mol ratio; Wear out at 80 ℃ then; Ageing time is 80min, and other obtains siliceous and aluminium hydroxide boron with embodiment 1.
Get above-mentioned siliceous and boron aluminium hydroxide 95g, sneak into the aqueous solution of 102g by the SB alumina powder of nitric acid peptization and tungstenic, molybdenum, nickel, mix pinch 20min after, process the plasticity paste, through the clover orifice plate extrusion of φ 1.4mm.Wet bar carries out dry 2.0h under 120 ℃, again at 210 ℃ of constant temperature calcining 2.0h, at 310 ℃ of constant temperature calcining 2.0h, at 520 ℃ of constant temperature calcining 2.0h, get catalyst C-4 intermediate, wherein WO
3Weight content be 20.1%, MoO
3Weight content be 2.1%, the weight content of NiO is 2.2%.The tungsten of catalyst C-4 intermediate dipping surplus and the aqueous solution of nickel at 240 ℃ of drying condition 2.0h, get catalyst C-4.In this catalyst, WO
3Weight content be 21.3%, MoO
3Weight content be 2.1%, the weight content of NiO is 2.6%.
Embodiment 5
The one-tenth glue of embodiment 1, aging after, drip and contain SiO
28g/100mL dimethicone 100mL at 70 ℃ of down aging 80min, adds then and contains B
2O
3The solution of organic compound 100mL of 6g/100mL, boracic solution of organic compound are dissolved in boric acid in the water, are the 1.0:1.5 preparation by boric acid and ethylene glycol mol ratio; Wear out at 70 ℃ then; Ageing time is 80min, and other obtains siliceous and aluminium hydroxide boron with embodiment 1.
Get above-mentioned siliceous and boron aluminium hydroxide 100g, sneak into 105g by the SB alumina powder of nitric acid peptization and contain molybdenum and the aqueous solution of phosphorus, mixed pinch 20min after, process the plasticity paste, through the clover orifice plate extrusion of φ 1.4mm.Wet bar carries out dry 1.0h under 130 ℃, again at 200 ℃ of constant temperature calcining 2.0h, at 320 ℃ of constant temperature calcining 2.0h, at 540 ℃ of constant temperature calcining 2.0h, get catalyst C-5 intermediate, wherein MoO
3Weight content be 14.6%, the weight content of 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 14.6%, the weight content of NiO is 6.5%, the weight content of 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 keeping the pH value was 8.2, reaction contact time 50min during the one-tenth glue reaction of 65 ℃ of stirrings was irritated.After becoming glued bundle, drip the proper amount of silicon acetoacetic ester, aging.Under stirring, add and contain B
2O
3100 milliliters of 6g/100mL solution of organic compound, this boracic solution of organic compound is the 2:1 preparation by boric acid and sweet mellow wine mol ratio.Is 8.5 with slurries in the pH value, wears out under the condition that temperature is 60 ℃, and ageing time is 1.5h.Product is filtered, use of the deionized water washing of solid-liquid volume ratio then, 70 ℃ of wash temperatures, washing times 3 times as 1:20.To gained filter cake dry 3h under 120 ℃, obtain siliceous and aluminium hydroxide boron.
Get above-mentioned siliceous and boron aluminium hydroxide 100g, sneak into 110g by the SB alumina powder of nitric acid peptization and the aqueous solution of tungstenic, molybdenum and nickel, mix pinch 20min after, process the plasticity paste, through the clover orifice plate extrusion of φ 1.4mm.Wet bar carries out dry 2.0h under 110 ℃, again at 240 ℃ of constant temperature calcining 1.0h, at 340 ℃ of constant temperature calcining 2.0h, at 510 ℃ of constant temperature calcining 3.0h, get catalyst C-6 intermediate, wherein WO
3Weight content be 18.4%, MoO
3Weight content be 4.1%, the weight content of 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 5.1%, the weight content of NiO is 5.6%.
Comparative example 1
After the one-tenth glue reaction of embodiment 1, add the solution 245mL that contains the 15g sodium metasilicate, aging back adds boric acid 10g, and other is with embodiment 1.
With embodiment 2, obtain catalyst C-A with the process of boracic preparation of aluminium hydroxide catalyst.
Comparative example 2
After the one-tenth glue reaction of embodiment 1, add the solution 1000mL that contains the 15.3g sodium metasilicate, aging back adds boric acid aqueous solution, and other is with embodiment 1.
With embodiment 5, obtain catalyst C-B with the process of siliceous and boron preparation of aluminium hydroxide catalyst.
Comparative example 3
The alumina support S-1 that adopts the embodiment of the 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 14.6%, NiO is 6.5%, and P is 1.4%, B
2O
3Content is 6.0%.
The table 1 of seeing with embodiment 1 ~ 6 and comparative example 1 ~ 3 preparation.
Table 1 hydrotreating catalyst character
| ? | Comparative example 1 | Comparative example 2 | Comparative example 3 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| B 2O 3，wt% | 3.3 | 6.1 | 6.0 | 3.2 | 3.0 | 3.3 | 6.2 | 5.5 |
| SiO 2，wt% | 1.98 | 7.61 | 0 | 2.01 | 1.96 | 2.03 | 7.71 | 7.63 |
| Specific area, m 2/g | 185 | 245 | 210 | 366 | 340 | 357 | 383 | 367 |
| Pore volume, cc/g | 0.36 | 0.55 | 0.46 | 0.86 | 0.83 | 0.84 | 1.13 | 0.95 |
| Average pore diameter, nm | 7.7 | 8.3 | 8.1 | 9.9 | 11.1 | 11.2 | 12.7 | 11.8 |
| The meleic acid amount, mmol/g | 0.36 | 0.62 | 0.59 | 0.53 | 0.51 | 0.58 | 0.65 | 0.55 |
| Pore size distribution, % | ? | ? | ? | ? | ? | ? | ? | ? |
| 6～18nm | 51 | 63 | 87* | 84 | 82 | 83 | 89 | 87 |
* 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
Present embodiment is activity of such catalysts evaluation test 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 condition sees that table 2 is following:
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 for decompressed wax oil and wax tailings are by weight the miscella that is 9:1 triumphantly, and character is seen 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，mg/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 is seen 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, mg/g | 31.0 | 20.4 | 23.7 | 11.2 | 12.0 | 10.3 | 3.0 | 8.3 |
| Relative denitrification activity | 100 | 110 | 107 | 125 | 123 | 128 | 157 | 132 |
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 handle the oily nitrogen content of generation with other catalyst hydrogenation.
Can find out by table 4, when supporting same metal, compare with reference catalyst and to have higher hydrodenitrogenationactivity activity with the reference agent through the catalyst of the present invention of boron additive modification.
Embodiment 8
Present embodiment is the life test of catalyst C-5 of the present invention and reference agent C-B, and used experimental rig, feedstock oil and evaluation process conditions are with embodiment 7, and the result sees table 5.
Table 5 catalyst stability result of the test of the present invention
| The catalyst numbering | C-5 | C-5 | C-B | C-B | C-C | C-C |
| The feedstock oil nitrogen content, mg/g | 1900 | 1900 | 1900 | 1900 | 1900 | 1900 |
| Sampling time, h | 500 | 2000 | 500 | 2000 | 500 | 2000 |
| Generate oily nitrogen content, mg/g | 3.0 | 3.9 | 20.9 | 41.8 | 22.7 | 65.8 |
Can see by table 5, when 385 ℃ of following 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 this explanation activity of such catalysts stability of the present invention obviously is better than the reference agent.
Claims (18)
1. preparation method of hydrotreatment catalyst comprises:
(1) inorganic salt containing aluminium solution and precipitating reagent are neutralized into the glue reaction;
(2) in the system of step (1) gained, add the organosilicon source, aging then;
(3) in the system that step (2) obtains, add the boracic solution of organic compound, adjustment pH is 7.0～10.0, and temperature is 50 ~ 90 ℃, wears out, and ageing time is 30～200min; The method of described boracic solution of organic compound is following: boric acid is dissolved in the water, adds organic alcohol then and make the boracic solution of organic compound;
(4) the aging slurries of step (3) gained are filtered, wash;
(5) step (4) gained filter cake is carried out drying, make siliceous and aluminum hydroxide solid elastomer boron;
(6) with siliceous and boron aluminum hydroxide solid elastomer, the precursor that contains the part active metal component and adhesive mixedly pinch, moulding; Under 110 ~ 160 ℃, carry out drying 1 ~ 20h then; Again at 180 ~ 240 ℃ of constant temperature calcining 0.5 ~ 3.0 h; 270 ~ 380 ℃ of constant temperature calcinings 1.0 ~ 4.0 hours,, obtain catalyst intermediate 400 ~ 530 ℃ of constant temperature calcinings 2.0 ~ 5.0 hours;
(7) the remainder active metal component loads to infusion process on the catalyst intermediate of step (6) gained, at 60 ~ 300 ℃ of drying 0.5 ~ 10.0h, obtains hydrotreating catalyst then.
2. according to the described method of claim 1, it is characterized in that step (6) introduces the weight of reactive metal and account for 1% ~ 95% of reactive metal weight in the final catalyst, wherein reactive metal is in oxide; Remaining reactive metal is introduced in the catalyst by step (7).
3. according to the described method of claim 1, it is characterized in that step (6) introduces the weight of reactive metal and account for 50% ~ 90% of reactive metal weight in the final catalyst, wherein reactive metal is in oxide; Remaining reactive metal is introduced in the catalyst by step (7).
4. according to the described method of claim 1, it is characterized in that the weight with catalyst is benchmark, boron oxide content is 0.5%～8.0%, and the content of silica is 1.0% ~ 15.0%.
5. according to the described method of claim 1, it is characterized in that the weight with catalyst is benchmark, boron oxide content is 1.0%～7.0%, and the content of silica is 1.0% ~ 7.0%.
6. according to the described method of claim 1; It is characterized in that described inorganic salt containing aluminium solution of step (1) and precipitating reagent are neutralized into the glue reaction; Used inorganic salt containing aluminium is one or more in aluminium chloride, aluminum nitrate, the aluminum sulfate, and precipitating reagent is ammoniacal liquor or sodium metaaluminate; Be controlled to 40 ~ 80 ℃ of glue reaction temperatures, becoming the glue reaction pH value is 4.5～9.5.
7. according to the described preparation method of claim 1, it is characterized in that containing B in the described boracic solution of organic compound of step (2)
2O
31 ~ 10 g/100mL.
8. according to the described preparation method of claim 1, it is characterized in that described organic alcohol is one or more in sweet mellow wine, ethylene glycol and the glycerine, the mol ratio of boric acid and organic alcohol is 2:1 ~ 1:2.
9. according to the described preparation method of claim 1, it is characterized in that the said organosilicon of step (2) source is one or more in organic silicone oil or the estersil.
10. according to the described preparation method of claim 9, it is characterized in that said organic silicone oil is one or more in methyl-silicone oil, the dimethicone, estersil is one or more in silester, the ethyl orthosilicate.
11. according to the described preparation method of claim 1, it is characterized in that step (2) control aging temperature is 30 ~ 80 ℃, ageing time is 60 ~ 300min.
12. according to the described preparation method of claim 1, it is characterized in that the described washing of step (4) is to wash with deionized water, the control temperature is between 50 ~ 90 ℃ during washing, washing times is 2 ~ 5 times, and each wash time is 30～60min; The described drying of step (5) is under 100 ~ 150 ℃, to carry out drying 1 ~ 20h.
13. according to the described preparation method of claim 1; It is characterized in that in the said hydrotreating catalyst; Reactive metal is group vib and group VIII metal; Weight with hydrotreating catalyst is benchmark, and the weight content of group vib metal oxide is 10% ~ 25%, and the weight content of group VIII metal oxide is 1% ~ 10%.
14. according to the described catalyst of claim 12, it is characterized in that the group vib metal is tungsten and/or molybdenum, the group VIII metal is nickel and/or cobalt.
15., it is characterized in that the described precursor that contains active metal component of step (6) is with reactive metal oxides according to the described preparation method of claim 1, perhaps contain active metallic compound, contain perhaps that the form of the solution of reactive metal adds.
16., it is characterized in that in the described hydrotreating catalyst that contain in auxiliary agent phosphorus, titanium, zirconium, the silicon one or more, this auxiliary agent is in oxide according to the described preparation method of claim 1, the weight content in catalyst is 0.2% ~ 15.0%.
17. according to the described preparation method of claim 1, it is characterized in that said adhesive is little porous aluminum oxide, its addition is a benchmark with the weight of the hydrotreating catalyst that finally obtains, is 3% ~ 30% in oxide content.
18., it is characterized in that the described drying condition of step (7) is following: at 110 ~ 270 ℃ of drying 1.0 ~ 10.0h according to the described preparation method of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110093573.XA CN102728374B (en) | 2011-04-14 | 2011-04-14 | Preparation method of hydrotreatment catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110093573.XA CN102728374B (en) | 2011-04-14 | 2011-04-14 | Preparation method of hydrotreatment catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102728374A true CN102728374A (en) | 2012-10-17 |
| CN102728374B CN102728374B (en) | 2014-05-21 |
Family
ID=46985087
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110093573.XA Active CN102728374B (en) | 2011-04-14 | 2011-04-14 | Preparation method of hydrotreatment catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102728374B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105251494A (en) * | 2015-11-13 | 2016-01-20 | 无锡普爱德环保科技有限公司 | Preparing method for hydrogenation catalyst |
| CN105289618A (en) * | 2015-11-13 | 2016-02-03 | 无锡普爱德环保科技有限公司 | Hydrogenation catalyst, and applications thereof |
| CN105709849A (en) * | 2014-12-02 | 2016-06-29 | 中国石油化工股份有限公司 | Preparation method of modified aluminium oxide-based carrier |
| CN106140181A (en) * | 2015-04-23 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of preparation method of siliceous Hydrodemetalation catalyst |
| CN106140208A (en) * | 2015-04-23 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of preparation method of hydrogenation catalyst |
| CN106140183A (en) * | 2015-04-23 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of preparation method containing zirconium Hydrodemetalation catalyst |
| CN106140122A (en) * | 2015-04-23 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of preparation method of boracic Hydrodemetalation catalyst |
| CN106140187A (en) * | 2015-04-23 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of preparation method of Hydrodemetalation catalyst |
| CN106140182A (en) * | 2015-04-23 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of preparation method of heavy oil hydrogenating treatment catalyst |
| CN107442129A (en) * | 2016-05-30 | 2017-12-08 | 中国石油化工股份有限公司 | A kind of hydrotreating catalyst and its preparation method and application |
| CN108295826A (en) * | 2017-01-12 | 2018-07-20 | 中国石油化工股份有限公司 | A kind of modified aluminas dry glue powder and its preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050211603A1 (en) * | 2004-03-23 | 2005-09-29 | Denis Guillaume | Doped spherically-shaped supported catalyst and process for hydrotreating and hydroconverting metal-containing oil fractions |
| 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 |
| 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 |
-
2011
- 2011-04-14 CN CN201110093573.XA patent/CN102728374B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050211603A1 (en) * | 2004-03-23 | 2005-09-29 | Denis Guillaume | Doped spherically-shaped supported catalyst and process for hydrotreating and hydroconverting metal-containing oil fractions |
| 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 |
| 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 |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105709849A (en) * | 2014-12-02 | 2016-06-29 | 中国石油化工股份有限公司 | Preparation method of modified aluminium oxide-based carrier |
| CN105709849B (en) * | 2014-12-02 | 2018-04-10 | 中国石油化工股份有限公司 | The preparation method of modified oxidized alumina-based support |
| CN106140183A (en) * | 2015-04-23 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of preparation method containing zirconium Hydrodemetalation catalyst |
| CN106140182B (en) * | 2015-04-23 | 2018-07-03 | 中国石油化工股份有限公司 | A kind of preparation method of heavy oil hydrogenating treatment catalyst |
| CN106140208A (en) * | 2015-04-23 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of preparation method of hydrogenation catalyst |
| CN106140183B (en) * | 2015-04-23 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of preparation method of the Hydrodemetalation catalyst containing zirconium |
| CN106140122A (en) * | 2015-04-23 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of preparation method of boracic Hydrodemetalation catalyst |
| CN106140187A (en) * | 2015-04-23 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of preparation method of Hydrodemetalation catalyst |
| CN106140182A (en) * | 2015-04-23 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of preparation method of heavy oil hydrogenating treatment catalyst |
| CN106140181B (en) * | 2015-04-23 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of preparation method of siliceous Hydrodemetalation catalyst |
| CN106140122B (en) * | 2015-04-23 | 2018-08-14 | 中国石油化工股份有限公司 | A kind of preparation method of boracic Hydrodemetalation catalyst |
| CN106140181A (en) * | 2015-04-23 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of preparation method of siliceous Hydrodemetalation catalyst |
| CN106140208B (en) * | 2015-04-23 | 2018-08-14 | 中国石油化工股份有限公司 | A kind of preparation method of hydrogenation catalyst |
| CN106140187B (en) * | 2015-04-23 | 2018-08-14 | 中国石油化工股份有限公司 | A kind of preparation method of Hydrodemetalation catalyst |
| CN105289618A (en) * | 2015-11-13 | 2016-02-03 | 无锡普爱德环保科技有限公司 | Hydrogenation catalyst, and applications thereof |
| CN105251494A (en) * | 2015-11-13 | 2016-01-20 | 无锡普爱德环保科技有限公司 | Preparing method for hydrogenation catalyst |
| CN107442129A (en) * | 2016-05-30 | 2017-12-08 | 中国石油化工股份有限公司 | A kind of hydrotreating catalyst and its preparation method and application |
| CN107442129B (en) * | 2016-05-30 | 2020-04-14 | 中国石油化工股份有限公司 | Hydrotreating catalyst and preparation method and application thereof |
| CN108295826A (en) * | 2017-01-12 | 2018-07-20 | 中国石油化工股份有限公司 | A kind of modified aluminas dry glue powder and its preparation method and application |
| CN108295826B (en) * | 2017-01-12 | 2020-02-14 | 中国石油化工股份有限公司 | Modified alumina dry glue powder and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102728374B (en) | 2014-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102728374B (en) | Preparation method of hydrotreatment catalyst | |
| CN102728373B (en) | Preparation method of hydrotreating catalyst | |
| CN102039203B (en) | Hydrotreating catalyst and preparation method thereof | |
| CN100400165C (en) | Silicon and boron contained alumina carrier and production thereof | |
| CN100496719C (en) | Heavy fractional oil hydrogenation catalyst and production thereof | |
| CN102451765A (en) | Preparation method for composite oxide carrier | |
| CN102310003A (en) | Hydrocracking catalyst and preparation method thereof | |
| CN101491768B (en) | Preparation method of hydrogenation catalyst containing silicon and zirconium | |
| CN103191773B (en) | Method for preparing hydrocracking catalyst | |
| CN102259900B (en) | Hydrated alumina and preparation method thereof | |
| CN102861590A (en) | Hydrodemetallization catalyst and preparation method thereof | |
| CN102553638B (en) | Double-microporous-mesoporous composite molecular sieve hydrocracking catalyst | |
| CN103666548B (en) | A kind of process for selective hydrogenation of gasoline | |
| CN102451699B (en) | Method for preparing catalyst by hydrotreatment | |
| CN102309999B (en) | Hydrogenation catalyst carrier and preparation method thereof | |
| CN102451764A (en) | Method for preparing zirconia-alumina composite oxide carrier | |
| CN105771970B (en) | The method of hydroisomerization catalyst and preparation method thereof and hydrocarbon ils or Fischer-Tropsch synthesis oil production lube base oil | |
| CN100421784C (en) | Alumina dry glue containing silicon and boron and production thereof | |
| CN102451768A (en) | Method for preparing zirconia-alumina composite oxide xerogel | |
| CN102309970B (en) | Hydro-treating catalyst and preparation method thereof | |
| CN106179382B (en) | A kind of preparation method of body phase hydrotreating catalyst | |
| CN102451700B (en) | Preparation method of hydrotreatment catalyst | |
| CN103769186A (en) | Catalyst for anthraquinone hydrogenation and preparation method thereof | |
| CN102451769A (en) | Preparation method of composite oxide adhesive | |
| CN1331605C (en) | Alumina support containing silicon and titanium and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |