CN102728374B - Preparation method of hydrotreatment catalyst - Google Patents
Preparation method of hydrotreatment catalyst Download PDFInfo
- Publication number
- CN102728374B CN102728374B CN201110093573.XA CN201110093573A CN102728374B CN 102728374 B CN102728374 B CN 102728374B CN 201110093573 A CN201110093573 A CN 201110093573A CN 102728374 B CN102728374 B CN 102728374B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- preparation
- active metal
- boron
- weight
- 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.)
- Active
Links
Landscapes
- Catalysts (AREA)
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 hydrotreating catalyst, particularly the preparation method of the hydrotreating catalyst of 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 the content to sulphur, nitrogen and aromatic hydrocarbons.And oil is with the increase of yield, day by day become and heavily become bad, 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 also, becoming bad change weight, also constantly proposes new requirement to hydrogenation catalyst like this.
Hydrogenation catalyst adopts alumina support conventionally, but because pore volume and the aperture of aluminium oxide itself are less, in actual application, conventionally 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 active metal decentralization and active 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, in hydrogenation catalyst, introduce the method for catalyst component of helping, be included in while preparing alumine hydroxide colloid and introduce, in the time preparing the making beating of alumina support process colloid, introduce and introduce during at alumina support supported active metal.Wherein in the time preparing alumine hydroxide colloid, introducing is to adopt coprecipitation, by adding precipitating reagent under aluminium salt and boron-containing compound existence, reacts and obtains through plastic.Be first to prepare alumine hydroxide colloid preparing that alumina support process colloid when making beating introduces, and then boron-containing compound is sneaked in alumine hydroxide colloid and make.In the time of alumina support supported active metal, introducing refers to and first prepares alumina support, then together introduces with active metal component or introduces before or after introducing active metal, is generally to adopt the method for dipping to introduce.Due to boron add mode difference, will produce different impacts to catalyst performance.
US 4,724,226 disclose a kind of B catalyst that contains, the aluminium oxide that its carrier is is 0.1～5.0wt% containing boron oxide, 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 be mainly 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 that regulates alumina surface character.
CN1458232A discloses a kind of hydrotreating catalyst, and the boron-containing alumina carrier wherein adopting is that the precursor of first preparing G-aluminium oxide is aluminium hydroxide, and then making beating, adds 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 by the intensity of heavy losses catalyst and specific area, 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, in the time mixing, need to be heated to 50 ~ 90 ℃ and carry out, and operating process complexity increases production cost.And if adopt boric acid at room temperature to carry out, boric acid is easily separated out, and causes the decentralization of boron in aluminium oxide poor, and exceedes 2% when above when boron content, major part is converted into inactive tetrahedral coordination B.Adopt boric acid as auxiliary agent, although can play reaming effect, but pore volume and the specific area increasing degree of its aluminium oxide that obtains are little, if operating condition control is improper, or the control of boron content is improper, also can affect 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 simultaneously contains group VIB, metal component of group VIII, organic carboxyl acid and polyalcohol mixed twine mixture and auxiliary agent B to make through oxide impregnation alumina supporter.In the method, add organic complexing agent, improved the stability of boron, but owing to flooding with active metal simultaneously, boron and active metal are existing competitive Adsorption with carrier, affect the decentralization of active metal on carrier.Boron certainly will weaken the facilitation of the active phase transformation of the active in opposite directions higher II type of I type activity simultaneously, and then the raising of the type catalyst activity is restricted.In addition,, because boron is in the body formed rear introducing of carrying alumina, the pore structure on alumina support and duct impact are less, do not play the effect of reaming; Before supported active metal, the acid site type to carrier is not adjusted; Interaction stronger between active metal and carrier is not played to abated effect, catalyst activity is reduced.
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, has strengthened the facilitation to active phase transformation, improves activity and the stability of catalyst.
The preparation method of hydrotreating catalyst of the present invention, comprising:
(1) inorganic salt containing aluminium solution reacts with plastic in carrying out with precipitating reagent;
(2) in the system of step (1) gained, add organosilicon source, then aging;
(3) in the system obtaining to step (2), add boracic solution of organic compound, adjusting pH is 7.0～10.0, 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 boracic solution of organic compound;
(4) the aging slurries of step (3) gained are filtered, washed;
(5) step (4) gained filter cake is dried, makes siliceous and aluminum hydroxide solid elastomer boron;
(6) by siliceous and boron aluminum hydroxide solid elastomer, the precursor that contains part active metal component and adhesive kneading, moulding, then at 110 ~ 160 ℃, be dried 1 ~ 20h, 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;
(7) remainder active metal component loads to infusion process in the catalyst intermediate of step (6) gained, then, at 60 ~ 300 ℃ of dry 0.5 ~ 10.0h, obtains hydrotreating catalyst.
In the inventive method, during carrying out with precipitating reagent, the described inorganic salt containing aluminium solution of step (1) reacts with plastic, can adopt the conventional precipitation method to prepare the method for aluminium hydroxide, such as inorganic salt containing aluminium is one or more in aluminium chloride, aluminum nitrate, aluminum sulfate, sodium metaaluminate, precipitating reagent is ammoniacal liquor, sodium metaaluminate or carbon dioxide.Control plastic reaction temperature at 40 ~ 80 ℃, the pH value of plastic reaction is controlled in 7.0～9.5 scope.After step (1) plastic, can carry out agingly, also can not carry out agingly, wherein aging condition is as follows: 30 ~ 80 ℃ of aging temperatures, ageing time 60 ~ 300min.
Described in step (2), adding organosilicon source can be one or more that comprise in organic silicone oil or estersil class etc., wherein organic silicone oil is one or more in methyl-silicone oil, dimethyl-silicon wet goods, and estersil is one or more in silester, ethyl orthosilicate etc.It is 30 ~ 80 ℃ that step (2) is controlled aging temperature, and ageing time is 60 ~ 300min.
In step (3), the addition of silicon and 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 weight content of silica is 1.0% ~ 15.0%, is preferably 1.0%～7.0%.
The method of the boracic solution of organic compound described in step (3) is as follows: boric acid is dissolved in water, then adds Organic Alcohol to make 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.In boracic solution of organic compound, contain B
2o
31 ~ 10 g/100mL.
The described washing of step (4) is to wash by deionized water, controls temperature when washing between 50 ~ 90 ℃, and washing times is 2-5 time, and each wash time is 30～60min.
Described dry of step (5) is to be dried 1 ~ 20h at 100 ~ 150 ℃.
The described active metal of step (6) adopts conventional hydrogenation active metals, is generally that group vib metal is preferably tungsten and/or molybdenum take group vib and group VIII metal as active metal component, and group VIII metal is preferably nickel and/or cobalt.The described precursor containing active metal component can be reactive metal oxides, can, for containing active metallic compound, can also be also the solution containing active metal, preferably adopts the solution containing active metal.Solution containing active metal can adopt soluble in water the making of soluble-salt containing active metal.
Adhesive when adhesive used can adopt conventional Kaolinite Preparation of Catalyst in the present invention, 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 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 group vib metal is preferably tungsten and/or molybdenum take group vib and group VIII metal as active metal component, 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, step (6) is introduced the weight of active metal and is accounted for 1% ~ 95% of active metal weight in final catalyst, and preferably 50% ~ 90%, wherein active metal is in oxide.Remaining active metal is introduced in catalyst by step (7).
In hydrotreating catalyst of the present invention, can also contain as required other auxiliary agent, as one or more in phosphorus, titanium, zirconium, fluorine 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 the aluminium hydroxide preparation process of siliceous and boron, also can be in the time of Kaolinite Preparation of Catalyst intermediate and introduce when siliceous and boron aluminium hydroxide kneading, can also load in catalyst intermediate with infusion process separately, or preparation loads in catalyst intermediate with infusion process containing the solution of active metal and auxiliary agent.
Siliceous and the boron aluminium hydroxide that hydrotreating catalyst of the present invention adopts is after aluminium hydroxide plastic, 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 after adopting boracic organic solution water-soluble by boric acid, to join in Organic Alcohol and make, make like this boric acid react with Organic Alcohol and generate stable material, thereby overcome, boric acid temperature is low easily to be separated out, boron in aluminium hydroxide skewness, can not with the fine shortcoming coordinating of silicon.Part active metal component is introduced catalyst three sections of roastings under given conditions in kneading mode, remainder active metal component is introduced in catalyst and not roasting of drying with infusion process, three sections of roastings under given conditions together with the aluminum hydroxide solid elastomer of the active metal that the method can make first kneading and siliceous and boron, 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 improve specific area and the pore volume of catalyst, after relatively less with the active metal of infusion process load, and high degree of dispersion, make the catalyst of gained there is pore volume large, specific area is large, the feature that pore size distribution is concentrated.Have again, because boron additive has weakened the interaction between active metal and carrier, be conducive to the dispersion of active metal on carrier, strengthened the facilitation of active metal to active phase transformation simultaneously, improved the activity of catalyst, and in catalyst, there is form difference in the active metal component that two kinds of modes are introduced, cooperatively interact and make the loss of activity rate reduction of 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, on existing equipment, just can realize.
The specific embodiment
In 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 Micromeritics company of U.S. production; Meleic acid amount is to adopt the infrared absorption spectrographic determination of pyridine.
Embodiment 1
Will be containing Al
2o
3the AlCl of 5g/100mL
3solution 2000mL with containing NH
3the ammoniacal liquor of 10g/100mL drip are added in the plastic reaction filling that temperature is 60 ℃ of stirrings, and keeping pH value is 7.6, reaction contact time 40min.Be 70 ℃ in temperature, pH value is to carry out aging 8.0 times.Ageing time is 1h.Product is filtered to the deionized water that is then 1:20 by solid-liquid volume ratio washing, 80 ℃ of wash temperatures, washing times 3 times.To gained filter cake dry 3h at 120 ℃, obtain aluminium hydroxide.
Get above-mentioned aluminium hydroxide 100g, sneak into the SB alumina powder of 110g by nitric acid peptization, after kneading 20min, make 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 of embodiment 1, drip containing SiO
22g/100mL dimethicone 100mL, aging 80min at 70 ℃, then adds containing B
2o
3the solution of organic compound 100mL of 3g/100mL, boracic solution of organic compound is that boric acid is dissolved in water, is prepared by 1:1 by boric acid and sweet mellow wine mol ratio, the other the same as in Example 1 obtains siliceous and aluminium hydroxide boron.
Get the aluminium hydroxide 120g of above-mentioned siliceous and boron, sneak into 126g by the SB alumina powder of nitric acid peptization and containing the aqueous solution of molybdenum and cobalt, after kneading 20min, make plasticity paste, by the clover orifice plate extrusion of φ 1.4mm.Wet bar is dried 3h at 130 ℃, then at 210 ℃ of constant temperature calcining 2h, at 320 ℃ of constant temperature calcining 1.0h, at 530 ℃ of constant temperature calcining 3.0h, obtains catalyst C-2 intermediate, wherein, and MoO
3weight content be 11.1%, CoO weight content is 2.7%.The catalyst C-2 intermediate dipping molybdenum of surplus and the aqueous solution of cobalt, at 210 ℃ of drying condition 3.0h.In this catalyst, MoO
3weight content be 12.2%, CoO weight content is 3.0%.
Embodiment 3
After the plastic of embodiment 1, drip containing SiO
22g/100mL methyl-silicone oil 100mL, aging 80min at 70 ℃, then adds containing B
2o
3the solution of organic compound 100mL of 3g/100mL, boracic solution of organic compound is that boric acid is dissolved in water, is 1.0:1.5 preparation by boric acid and ethylene glycol mol ratio, then carry out aging at 70 ℃, ageing time is 80min, and the other the same as in Example 1 obtains siliceous and aluminium hydroxide boron.
Get above-mentioned siliceous and boron aluminium hydroxide 110g, sneak into 118g by the SB alumina powder of nitric acid peptization and containing the aqueous solution of molybdenum and phosphorus, after kneading 20min, make plasticity paste, by the clover orifice plate extrusion of φ 1.4mm.Wet bar is dried 3h at 140 ℃, then at 190 ℃ of constant temperature calcining 0.5h, at 350 ℃ of constant temperature calcining 2.0h, at 530 ℃ of constant temperature calcining 2.0h, obtains catalyst C-3 intermediate, wherein MoO
3weight content be 23.2%, P weight content 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, obtains catalyst C-3.In this catalyst, MoO
3the weight content weight content that is 24.6%, NiO be 4.02%, P weight content is 1.21%.
Embodiment 4
After the plastic of embodiment 1, drip ethyl orthosilicate 100mL, aging 100min at 80 ℃, then adds containing B
2o
3the solution of organic compound 100mL of 3g/100mL, boracic solution of organic compound is that boric acid is dissolved in water, is 1.5:1.0 preparation by boric acid and glycerine mol ratio, then carry out aging at 80 ℃, ageing time is 80min, and the other the same as in Example 1 obtains siliceous and aluminium hydroxide boron.
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, after kneading 20min, make plasticity paste, by the clover orifice plate extrusion of φ 1.4mm.Wet bar is dried 2.0h at 120 ℃, then at 210 ℃ of constant temperature calcining 2.0h, at 310 ℃ of constant temperature calcining 2.0h, at 520 ℃ of constant temperature calcining 2.0h, obtains catalyst C-4 intermediate, wherein WO
3weight content be 20.1%, MoO
3weight content be 2.1%, NiO weight content is 2.2%.The catalyst C-4 intermediate dipping tungsten of surplus and the aqueous solution of nickel, at 240 ℃ of drying condition 2.0h, obtain catalyst C-4.In this catalyst, WO
3weight content be 21.3%, MoO
3weight content be 2.1%, NiO weight content is 2.6%.
Embodiment 5
The plastic of embodiment 1, aging after, drip containing SiO
28g/100mL dimethicone 100mL, aging 80min at 70 ℃, then adds containing B
2o
3the solution of organic compound 100mL of 6g/100mL, boracic solution of organic compound is that boric acid is dissolved in water, is 1.0:1.5 preparation by boric acid and ethylene glycol mol ratio, then carry out aging at 70 ℃, ageing time is 80min, and the other the same as in Example 1 obtains siliceous and aluminium hydroxide boron.
Get above-mentioned siliceous and boron aluminium hydroxide 100g, sneak into 105g by the SB alumina powder of nitric acid peptization and containing the aqueous solution of molybdenum and phosphorus, after kneading 20min, make plasticity paste, by the clover orifice plate extrusion of φ 1.4mm.Wet bar is dried 1.0h at 130 ℃, then at 200 ℃ of constant temperature calcining 2.0h, at 320 ℃ of constant temperature calcining 2.0h, at 540 ℃ of constant temperature calcining 2.0h, obtains catalyst C-5 intermediate, wherein MoO
3weight content be 14.6%, P weight content is 1.4%.Catalyst C-5 intermediate floods the nickeliferous aqueous solution, at 240 ℃ of drying condition 3.0h, obtains catalyst C-5.In this catalyst, MoO
3the weight content weight content that is 14.6%, NiO be 6.5%, P weight content is 1.4%.
Embodiment 6
Will be containing Al
2o
3the Al of 5g/100mL
2(SO
4)
3solution 1000mL with containing Al
2o
3the sodium aluminate solution of 6.0g/100mL drip are added in the plastic reaction filling that temperature is 65 ℃ of stirrings, and keeping pH value is 8.2, reaction contact time 50min.After cemented into bundles, drip 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 2:1 preparation by boric acid and sweet mellow wine mol ratio.Be 8.5 by slurries in pH value, carry out agingly under the condition of temperature 60 C, ageing time is 1.5h.Product is filtered to the deionized water that is then 1:20 by solid-liquid volume ratio washing, 70 ℃ of wash temperatures, washing times 3 times.To gained filter cake dry 3h at 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, after kneading 20min, make plasticity paste, by the clover orifice plate extrusion of φ 1.4mm.Wet bar is dried 2.0h at 110 ℃, then at 240 ℃ of constant temperature calcining 1.0h, at 340 ℃ of constant temperature calcining 2.0h, at 510 ℃ of constant temperature calcining 3.0h, obtains catalyst C-6 intermediate, wherein WO
3weight content be 18.4%, MoO
3weight content be 4.1%, NiO weight content is 5.6%.The catalyst C-6 intermediate dipping tungsten of surplus and the aqueous solution of molybdenum, at 260 ℃ of drying condition 2.0h, obtain catalyst C-6.In this catalyst, WO
3weight content be 19.8%, MoO
3weight content be 5.1%, NiO weight content is 5.6%.
Comparative example 1
After the plastic reaction of embodiment 1, add the solution 245mL that contains 15g sodium metasilicate, add boric acid 10g, the other the same as in Example 1 after aging.
With embodiment 2, obtain catalyst C-A by the process of boracic aluminium hydroxide Kaolinite Preparation of Catalyst.
Comparative example 2
After the plastic reaction of embodiment 1, add the solution 1000mL that contains 15.3g sodium metasilicate, add boric acid aqueous solution, the other the same as in Example 1 after aging.
With embodiment 5, obtain catalyst C-B by the process of siliceous and boron 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 active 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%.
By 1 ~ 3 preparation of embodiment 1 ~ 6 and comparative example in table 1.
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 |
| 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
The present embodiment is the active evaluation test of catalyst of the present invention, and carries out activity contrast with the hydrotreating catalyst that adopts distinct methods to prepare, and mainly investigates the hydrodenitrogeneration performance of catalyst.
Catalyst activity evaluation is carried out on 200mL small hydrogenation device, and condition is as follows in table 2:
The hydroprocessing condition that table 2 embodiment and comparative example are used
| 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 is in 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 in table 4.
Table 4 catalyst of the present invention and the contrast of reference agent nitrogen removal performance
| Catalyst numbering | C-A | C-B | C-C | C-2 | C-3 | C-4 | C-5 | C-6 |
| Type | Reference agent | Reference agent | 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 |
| Denitrification activity relatively | 100 | 110 | 107 | 125 | 123 | 128 | 157 | 132 |
Note: the hydrodenitrogenationactivity activity of regulation reference agent C-A is 100, and all the other are pressed
Denitrification activity=[ln (Nf/Np)]/ln (Nf/Npr) relatively] * 100
Wherein: Nf is raw material nitrogen content, Npr and Np are respectively catalyst C-A and the oily nitrogen content of other catalyst hydrogenation processing generation.
As seen from Table 4, the catalyst of the present invention of process boron additive modification, in the time supporting same metal with reference agent, has higher hydrodenitrogenationactivity activity compared with reference catalyst.
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, with embodiment 7, the results are shown in Table 5.
Table 5 catalyst stability result of the test of the present invention
| Catalyst numbering | C-5 | C-5 | C-B | C-B | C-C | C-C |
| 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 be seen by table 5, at 385 ℃ when steady running 2000h, while adopting catalyst of the present invention, generating oily nitrogen content slightly raises, and while adopting reference agent, generate oily nitrogen content obviously to raise, activity stability of this explanation catalyst of the present invention is significantly better than reference agent.
Claims (18)
1. a preparation method for hydrotreating catalyst, comprising:
(1) inorganic salt containing aluminium solution reacts with plastic in carrying out with precipitating reagent;
(2) in the system of step (1) gained, add organosilicon source, then aging;
(3) in the system obtaining to step (2), add boracic solution of organic compound, adjusting pH is 7.0～10.0, 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 boracic solution of organic compound;
(4) the aging slurries of step (3) gained are filtered, washed;
(5) step (4) gained filter cake is dried, makes siliceous and aluminum hydroxide solid elastomer boron;
(6) by siliceous and boron aluminum hydroxide solid elastomer, the precursor that contains part active metal component and adhesive kneading, moulding, then at 110～160 ℃, be dried 1～20h, again at 180～240 ℃ of constant temperature calcining 0.5～3.0h, 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;
(7) remainder active metal component loads to infusion process in the catalyst intermediate of step (6) gained, then, at 60～300 ℃ of dry 0.5～10.0h, obtains hydrotreating catalyst.
2. according to preparation method claimed in claim 1, it is characterized in that step (6) introduces the weight of active metal and account for 1%～95% of active metal weight in final catalyst, wherein active metal is in oxide; Remaining active metal is introduced in catalyst by step (7).
3. according to preparation method claimed in claim 1, it is characterized in that step (6) introduces the weight of active metal and account for 50%～90% of active metal weight in final catalyst, wherein active metal is in oxide; Remaining active metal is introduced in catalyst by step (7).
4. according to preparation method claimed in claim 1, it is characterized in that weight take catalyst is as benchmark, boron oxide content is 0.5%～8.0%, the content of silica is 1.0%～15.0%.
5. according to preparation method claimed in claim 1, it is characterized in that weight take catalyst is as benchmark, boron oxide content is 1.0%～7.0%, the content of silica is 1.0%～7.0%.
6. according to preparation method claimed in claim 1, it is characterized in that the described inorganic salt containing aluminium solution of step (1) reacts with plastic in carrying out with precipitating reagent, 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 7.0～9.5.
7. according to preparation method claimed in claim 1, it is characterized in that in the described boracic solution of organic compound of step (3) that boracic is with B
2o
3meter 1～10g/100mL.
8. 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.
9. according to preparation method claimed in claim 1, it is characterized in that the described organosilicon of step (2) source is one or more in organic silicone oil or estersil.
10. according to preparation method claimed in claim 9, it is characterized in that described organic silicone oil is dimethicone, estersil is ethyl orthosilicate.
11. according to preparation method claimed in claim 1, it is characterized in that it is 30～80 ℃ that step (2) is controlled aging temperature, and ageing time is 60～300min.
12. according to preparation method claimed in claim 1, it is characterized in that the described washing of step (4) is to wash by deionized water, when washing, control temperature between 50～90 ℃, washing times is 2～5 times, each wash time is 30～60min; Described dry of step (5) is to be dried 1～20h at 100～150 ℃.
13. according to preparation method claimed in claim 1, it is characterized in that in described hydrotreating catalyst, active 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%.
14. according to the preparation method described in claim 13, it is characterized in that: group vib metal is tungsten and/or molybdenum, and group VIII metal is nickel and/or cobalt.
15. according to preparation method claimed in claim 1, it is characterized in that the described precursor containing part active metal component of step (6) is with containing active metallic compound, or add containing the form of the solution of active metal.
16. according to preparation method claimed in claim 1, it is characterized in that in described hydrotreating catalyst, contains one or more in auxiliary agent phosphorus, titanium, zirconium, silicon, and this auxiliary agent is in oxide, and the weight content in catalyst is 0.2%～15.0%.
17. according to preparation method claimed in claim 1, it is characterized in that described adhesive is little porous aluminum oxide, and its addition is take the weight of the hydrotreating catalyst that finally obtains as benchmark, take oxide content as 3%～30%.
18. according to preparation method claimed in claim 1, it is characterized in that the described drying condition of step (7) is as follows: at 110～270 ℃ of dry 1.0～10.0h.
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 CN102728374A (en) | 2012-10-17 |
| CN102728374B true 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 | A boron-containing hydrodesulfurization 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2867988B1 (en) * | 2004-03-23 | 2007-06-22 | Inst Francais Du Petrole | DOPE SUPPORTED CATALYST OF SPHERICAL FORM AND METHOD FOR HYDROPROCESSING AND HYDROCONVERSION OF PETROLEUM FRACTIONS CONTAINING METALS |
-
2011
- 2011-04-14 CN CN201110093573.XA patent/CN102728374B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 | A boron-containing hydrodesulfurization 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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102728374A (en) | 2012-10-17 |
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 | |
| CN106179382B (en) | A kind of preparation method of body phase hydrotreating catalyst | |
| CN102309975B (en) | Method for preparing hydrocracking catalyst | |
| CN103191773B (en) | Method for preparing hydrocracking catalyst | |
| CN101491768B (en) | Preparation method of hydrogenation catalyst containing silicon and zirconium | |
| CN102451764B (en) | Method for preparing zirconia-alumina composite oxide carrier | |
| CN102451699B (en) | Method for preparing catalyst by hydrotreatment | |
| CN102641739A (en) | Hydrogenation catalyst with gradient distribution of alkaline metal and active metal component concentration and preparation method thereof | |
| CN107303484A (en) | The preparation method and hydrotreating catalyst of a kind of siliceous macropore alumina supporter | |
| CN104437578B (en) | Hydrodesulfurization catalyst, preparation method and applications thereof | |
| CN103666548B (en) | Selective hydrogenation method for gasoline | |
| CN103801346B (en) | A kind of method preparing hydrotreating catalyst | |
| CN103801312A (en) | Preparation method for hydrotreatment catalyst | |
| CN103372440A (en) | Preparation method of methanol synthesis catalyst | |
| JP2019171288A (en) | Hydrogenation catalyst of hydrocarbon oil, production method therefor, and hydrogenation method | |
| CN102451768A (en) | Preparation method of zirconia-alumina composite oxide dry glue | |
| CN102451766A (en) | Preparation method of composite oxide carrier | |
| CN102451769B (en) | Preparation method of composite oxide adhesive | |
| CN102451700B (en) | Preparation method of hydrotreatment catalyst | |
| CN102309970B (en) | Hydro-treating catalyst and preparation method thereof | |
| CN104014328B (en) | A carrier, a residue hydrogenation catalyst based on the carrier and a preparation method thereof | |
| CN108067210B (en) | A kind of zirconium-containing alumina dry glue powder and its preparation method and application | |
| CN106179388A (en) | A kind of preparation method of hydrotreating catalyst |
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 |