CN1552520A - Preparing method for hydrocarbon hydrotreating catalyst - Google Patents

Preparing method for hydrocarbon hydrotreating catalyst Download PDF

Info

Publication number
CN1552520A
CN1552520A CNA031335489A CN03133548A CN1552520A CN 1552520 A CN1552520 A CN 1552520A CN A031335489 A CNA031335489 A CN A031335489A CN 03133548 A CN03133548 A CN 03133548A CN 1552520 A CN1552520 A CN 1552520A
Authority
CN
China
Prior art keywords
catalyzer
accordance
tio
catalyst
add
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
Application number
CNA031335489A
Other languages
Chinese (zh)
Other versions
CN1221312C (en
Inventor
蒋绍洋
王纲
王永林
孙素华
陈金汤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Original Assignee
China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Fushun Research Institute of Petroleum and Petrochemicals filed Critical China Petroleum and Chemical Corp
Priority to CN 03133548 priority Critical patent/CN1221312C/en
Publication of CN1552520A publication Critical patent/CN1552520A/en
Application granted granted Critical
Publication of CN1221312C publication Critical patent/CN1221312C/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Landscapes

  • Catalysts (AREA)

Abstract

A catalyst for hydrodesulfurizing hydrocarbons is composed of the carrier (gamma-Al2O3), active components chosen from the metals in families VIB and VIII, and active assistant (Ti). It is prepared through mixing dried aluminium hydroxide powder with TiO2, adding the alkaline solution containing Mo and/or W, kneading, adding the acidic solution containing Co and/or Ni, kneading, extruding for shaping, drying, and calcining. It has the improved performance.

Description

A kind of preparation method of hydrocarbon hydrogenizing treamtent catalyst
Technical field
The present invention relates to a kind of preparation method's of hydrocarbon hydrogenizing treamtent catalyst, particularly Hydrodevulcanizing catalyst for hydro-carbons preparation method.
Background technology
Hydrotreatment is the important process technology in the hydro carbons processing, mainly comprise hydrogenating desulfurization, hydrodenitrification, hydrocracking etc., the key of hydrotreatment technology is catalyzer, and at present hydrocarbon hydrogenizing treamtent catalyst is many is carrier with the aluminum oxide, is active ingredient with Mo and/or W and Ni and/or Co.In order to reach maximum economic benefits, improving catalyst performance and reducing cost is the target that pursue this area.
Usually, the simplification catalyst preparation process can reduce the Catalyst Production cost greatly, and as United States Patent (USP) 4,443,558, its adopts and mixes the method that the method for pinching substitutes " pickling process " or " mix and soak combination " fully, and one-step moulding prepares catalyzer, and preparation cost is low.But do not introduce any auxiliary agent in its catalyzer, simultaneously, Preparation of catalysts adopts and to add the method that adds alkali after the acid earlier, and this method is because strong acid and the aluminum oxide effect that adds earlier is stronger, make pore volume, the specific surface loss of aluminum oxide powder serious, make the performance of final catalyzer unsatisfactory.Improve catalyst activity and usually adopt the method for adding auxiliary agent, as Ti, Zr, P, B, F is the usual auxiliaries of hydrogenation catalyst, United States Patent (USP) 5,089,453 has introduced auxiliary agent Ti in Hydrobon catalyst, activity of such catalysts is improved, but this catalyzer also adopts and adds acid earlier, add alkali neutral method again, cause the pore volume of final catalyzer, specific surface to reduce greatly, catalyst performance is affected.EP 0339640 has announced a kind of method of prepared by co-precipitation titanium-contained aluminum oxide, but all there is body phase retention problems in coprecipitation method, thereby can not give full play to TiO 2Promoter action to catalyst performance.(as CN1098433A, US 5,089 in kneading method and " mix and soak combination " method, 453, CN1289822A etc.), because active ingredient and auxiliary agent titanium add simultaneously, each material particularly solution metal ion and the aluminium hydroxide competition when interacting is that inevitably this will weaken TiO 2To the promoter action of catalyst performance, this is the deficiency that exists with solution form adding auxiliary agent titanium or zirconium, and the performance that obtains catalyzer can further improve.CN1344586A and CN1316486A etc. disclose the preparation method of titanium-contained aluminum oxide carrier, wherein titanium is raw material with the nano titanium oxide, the former uses sol-gel method to prepare nano titanic oxide sol, splash into again in the pseudo-boehmite with the different solutions making beating, dry then, roasting, the latter will contain materials such as nano titanium oxide and make sol system, make gelling system then, adopt the supercritical technology drying at last, though both claim to improve the performance of catalyzer, but preparation process is loaded down with trivial details, and the Catalyst Production cost is improved.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of active height and the low hydrocarbons hydrogenation of preparation cost is handled the particularly preparation method of Hydrobon catalyst.
The preparation process of hydrocarbon hydrogenizing treamtent catalyst of the present invention is as follows:
With nano level TiO 2Behind powder and the aluminum hydroxide solid elastomer powder thorough mixing, add the basic solution that is dissolved with the group vib reactive metal, fully mix and pinch, the acidic solution that adds a certain amount of VIII of being dissolved with family metal again, mix and pinch into after the plastic, material is made final catalyzer through extrusion, drying and roasting.Various raw materials are formed definite add-on: MoO by following final catalyst weight 3(and/or WO 3) 8.0～24.0%, be preferably 16.0～20.0w%; CoO and/or NiO1.0～15.0w% are preferably 4.0～12.0%, and preferred two kinds of group VIII metals exist simultaneously; TiO 24.0～12.0%, be preferably 5.0～10.0%; Surplus is γ-Al 2O 3The catalyzer pore volume is 0.30～0.65ml/g, and specific surface is 120～300m 2/ g, mean pore size is 6.0～15.0nm.Bulk density is 0.75～0.85g/ml.
The inventive method adds nano level TiO earlier in the aluminum hydroxide solid elastomer powder 2Powder can make TiO 2Distribution on alumina supporter is more even, and when having avoided adding titanium and the competitive adsorption of other metal ion with ionic condition, improve various reactive metals and the auxiliary agent distribution situation on carrier, the position, active centre is increased, improved the performance of catalyzer.In the aluminum hydroxide solid elastomer powder mixture, add basic solution earlier; adsorb and be covered in surfaces externally and internally formation one deck " protective membrane " of aluminium hydroxide; can slow down the strong interaction of acid and aluminium hydroxide when adding the acidic solution peptization more greatly; reduced the loss of aluminum oxide pore volume and specific surface, made final catalyzer have higher pore volume and specific surface.The inventive method has been taken all factors into consideration influence and the protection carrier hole structure two aspect factors of the adding mode of metal and auxiliary agent to catalyst performance, makes the metal dispersion and the pore structure of catalyzer reach the ideal state simultaneously, and catalyst performance improves greatly.The inventive method step is simple, and the three wastes produce and lack in the production process, and the Catalyst Production cost is low.
Embodiment
The concrete preparation process of catalyzer of the present invention is: take by weighing a certain amount of commercially available aluminum hydroxide solid elastomer powder and (when 450-700 ℃ of roasting, can be converted into γ-Al 2O 3, when below mentioning aluminum hydroxide solid elastomer, all be meant this type), adding 7～14wtw% median size is the TiO that 20～500nm is preferably 30～80nm 2Behind the thorough mixing, add basic solution and (contain NH 34.0～12.0wt%, MoO 3And/or WO 328.0～48.0wt%), thorough mixing, treat that the aluminum hydroxide solid elastomer powder is all wetted after, add an amount of acidic solution again and (contain NiO3.0～9.0wt%, and/or CoO3.0～9.0wt%), mix again and pinch into plastic, (can add nitric acid or acetic acid solution in case of necessity, as containing acetate 12.0～30.0wt%), extruded moulding on banded extruder, drying, roasting promptly obtains catalyzer.The basic solution add-on is aluminum hydroxide solid elastomer powder and nano-TiO 220～80wt% of mixture mixes and pinched 10～50 minutes, and the acidic solution add-on is aluminum hydroxide solid elastomer powder and nano-TiO 220～80w% of mixture mixes and pinched 30～80 minutes.The adding method of above-mentioned auxiliary agent Ti also is applicable to auxiliary agent Zr, as adopting nanometer ZrO 2, can prepare the catalyzer that contains Zr, or preparation contains the catalyzer of Ti and Zr simultaneously.
In above preparation process, if get the aluminum hydroxide solid elastomer powder that 500g contains butt 75%, the then above-mentioned nano-TiO of Jia Ruing 2Be 35-70g, basic solution is 100-400g, and acidic solution is 100-400g.Catalyst shape can be cylinder or three (four) leaf grass, and drying temperature is 80～140 ℃, and the time is 3～6 hours.During roasting, the heating-up time is 4～6 hours, and constant temperature 2～4 hours, thermostat temperature are 450 ℃～700 ℃.
Catalyzer of the present invention can be used for the various hydrotreatment processes of various hydro carbons, raw material can be various distillates, secondary processing oil, heavy oil, residual oil and the hydro carbons that derives from coal etc., the hydrotreatment process comprises hydrogenating desulfurization, hydrodenitrification, hydrocracking etc., is specially adapted to the hydrodesulfurization process of weight, residual oil.For different raw materials and different hydrogenation process, can adjust the component and the content of catalyzer according to this area general knowledge, can substitute with W as Mo, or Mo and W use simultaneously, as adding auxiliary agents such as other Si, P, B, F in the catalyzer, handling light hydrocarbons activity of such catalysts metal and auxiliary dosage can suitably reduce, and treatment of heavy hydrocarbon class activity of such catalysts metal and auxiliary dosage can suitably increase, and adopt the inventive method to prepare corresponding catalyst then.
Further describe technical characterictic of the present invention below by comparative example and embodiment, but be not limited to embodiment.
Embodiment 1
Take by weighing commercially available aluminum hydroxide solid elastomer powder 500g (butt 75%), adding the 40g median size is the TiO of 50nm 2Behind the powder thorough mixing, add molybdenum acid ammonia solution 350g, wherein MoO 3Concentration is 30.0wt%, and solution contains NH 3Be 10wt%, it is wetting with aluminium hydrate powder to be fully mixed to alkali lye, adds the 360g acidic solution then, contains Ni (NO in the acid liquid 3) 216.2wt%, Co (NO 3) 216.2wt%, solution contain acetate 17wt%, fully mix and pinch to plastic, and to become diameter be the Herba Galii Bungei bar of 1.1 * 1.2mm to extrusion on preceding crowded formula twin screw banded extruder, and the gained catalyzer was 100 ℃ of dryings 4 hours; 490 ℃ of roastings 3 hours, catalyst A, its character sees Table 1.
Embodiment 2
With TiO among the embodiment 1 2It is 70g that powder becomes median size 150nm consumption, MoO 3Concentration changes 46.0% into, Ni (NO 3) 2Concentration change 24.8% into, Co (NO 3) 2Concentration change 24.8% into, other implementation conditions are constant, catalyst B, its character sees Table 1, i.e. the cost example.
Embodiment 3
Change maturing temperature among the embodiment 1 into 550 ℃, both cost examples, catalyzer numbering C, its character sees Table 1.
Comparative example 1
This comparison example is to prepare catalyzer by the method that CN1289822A describes.
Take by weighing commercially available aluminum hydroxide solid elastomer powder 500g (butt 75%), add molybdenum acid ammonia solution 350g, wherein MoO 3Concentration is 30.0%, and it is wetting with aluminium hydrate powder to be fully mixed to alkali lye, adds the 360g acidic solution then, contains Ni (NO in the acid liquid 3) 216.2%, Co (NO 3) 216.2%, TiCl 329.2%, fully mix and pinch to plastic, to become diameter be the Herba Galii Bungei bar of 1.1 * 1.2mm to extrusion on preceding crowded formula twin screw banded extruder, the gained catalyzer was 100 ℃ of dryings 4 hours; 490 ℃ of roastings 3 hours, catalyzer D, its character sees Table 1.
Comparative example 2
This comparison example is by US4, and 443,558 methods of describing prepare catalyzer.
With 100g nickel acetate and 100g Cobaltous diacetate and 177.6g TiCl 3Add in the 475ml water, mix with the solution that 25g concentrated nitric acid and 50ml water are made into again, acidic solution, join in the identical commercially available aluminium hydrate powder of 1000g and embodiment 1 with 50ml/min speed, mix after 20 minutes, speed with 50ml/min adds the 480ml basic solution again, and basic solution is by 59.0g MoO 3Be dissolved in the NH of 67.72ml 30% 4OH and 10 prepares in the 172ml distilled water, mix pinched 20 minutes after, with the plastic extrusion, 250 dryings 2 hours, 400 dryings 2 hours, 1200 °F, roasting is 1 hour under the dry and comfortable air conditions, catalyzer called after E, its character sees Table 1.
Comparative example 3
This Comparative Examples is by US5, and 089,453 described method and adding assistant titanium prepare catalyzer.
With 196gTiCl 3Slowly add in the 600g water, stir, add 165gNi (C then respectively until limpid 2H 3O 2) 24H 2O and 165gCo (C 2H 3O 2) 24H 2O, this solution pH value is 1.5, label is 2A;
Solution 2B is by containing MoO 330.9%, NH 4The solution 753ml of OH 26.5% and the dense NH of 100g 4OH solution mixes.
Take by weighing the identical aluminium hydroxide of 1013g and embodiment 1, add 2A solution earlier, after mixing 20 minutes, mixed pinching do not stop adding 2B solution, remix 20 minutes is extrusion then, at 1150 °F, and under the airflow condition, drying, roasting 2 hours, catalyzer is numbered F, and its character sees Table 1.
Embodiment 4
Under the same process condition, desulfurization, the denitrogenation that comparative catalyst A, B, C, D, E, F show when handling isolated island vacuum residuum and take off the carbon residue performance.Estimate stock oil character and estimate processing condition and see Table 2 and table 3 respectively, wherein Hydrobon catalyst is the catalyzer that various embodiments of the present invention make, hydrodenitrogenation catalyst is the same industry catalyzer, is the FZC-41 residual hydrogenation denitrification catalyst of Qilu Petrochemical company catalyst plant production.Evaluation result sees Table 4.
Table 1 catalyst property
Catalyzer ??A ??B ??C ??D ??E ??F
Dispersity *I Ti/I AlPore volume, ml/g specific surface, m 2/ g can several apertures, and nm piles ratio, g/ml MoO 3，wt％ NiO，wt％ CoO，wt％ TiO 2，wt％ ??0.23 ??0.48 ??279 ??6.5 ??0.82 ??18.5 ??4.2 ??4.2 ??7.0 ??0.22 ??0.45 ??269 ??6.2 ??0.83 ??23.7 ??5.4 ??5.4 ??10.3 ??0.23 ??0.50 ??259 ??7.0 ??0.80 ??18.4 ??4.18 ??4.15 ??7.0 ??0.19 ??0.42 ??245 ??6.5 ??0.82 ??18.2 ??4.1 ??4.1 ??7.2 ??0.18 ??0.36 ??233 ??6.5 ??0.84 ??18.2 ??4.0 ??4.0 ??7.18 ??0.18 ??0.37 ??228 ??7.2 ??0.86 ??24.0 ??4.2 ??4.18 ??7.3
*Annotate: the dispersivity test method is an X-ray photoelectron spectroscopy, and the dispersity value is big more, illustrates that the dispersion of metal in aluminum oxide is even more.
Table 2 stock oil property list 3 is estimated processing condition
Density (20 ℃) g/cm 3????S，wt％ ????N，wt％ ????CCR，wt％ ????1.018 ????2.56 ????0.76 ????15.6
Catalyst loading ml One anti-two is anti- ??HDS ??HDN ??120 ??180
Pressure, MPa air speed, h -1Temperature, ℃ hydrogen-oil ratio, (v) ??????????14.7 ??????????0.33 ??????????400 ??????????1000
Table 4 activity rating result *
Catalyst A B C D E F
Desulfurization degree, wt% 91.2 90.6 90.0 89.2 85.5 84.6
Denitrification percent, wt% 61.5 64.3 61.0 60.6 56.6 57.8
Take off carbon yield, wt% 59.5 62.4 59.8 58.7 55.8 56.4
*Sampling analysis result after turning round 300 hours
From table 1 catalyzer physico-chemical property as seen, catalyst metal dispersity I of the present invention Ti/ I AlBe better than the comparative catalyst with specific surface; And as seen from Table 4, the use properties of catalyzer of the present invention is better than the comparative catalyst, and particularly the desulfurization performance of catalyzer of the present invention is significantly better than the comparative catalyst.

Claims (10)

1, a kind of preparation method of hydrocarbon hydrogenizing treamtent catalyst is characterized in that nano level TiO 2Behind powder and the aluminum hydroxide solid elastomer powder thorough mixing, add the basic solution that is dissolved with the group vib reactive metal, fully mix and pinch, add the acidic solution that is dissolved with VIII family metal again, mix and pinch into after the plastic, material is made final catalyzer through extrusion, drying and roasting.
2, in accordance with the method for claim 1, it is characterized in that the various raw materials of catalyzer are by definite add-on: the MoO of following final catalyst weight composition 3And/or WO 38.0～24.0%, CoO and/or NiO1.0～15.0w%, TiO 24.0～12.0w%, surplus is γ-Al 2O 3Carrier.
3, in accordance with the method for claim 2, it is characterized in that the various raw materials of catalyzer are by definite add-on: the MoO of following final catalyst weight composition 3And/or WO 316.0～20.0w%, CoO and/or NiO4.0～12.0w%, TiO 25.0～10.0w%.
4, in accordance with the method for claim 1, it is characterized in that described nano level TiO 2The median size of powder is 20～500nm, and described aluminum hydroxide solid elastomer powder is for can be converted into γ-Al 450-700 ℃ of roasting 2O 3The aluminum hydroxide solid elastomer powder, the described basic solution that is dissolved with the group vib reactive metal contains NH 34.0～12.0wt%, MoO 3And/or WO 328.0～48.0wt%, the acidic solution of the described VIII of being dissolved with family metal contains NiO3.0～9.8wt% and/or CoO3.0～9.0wt%, acetate 12.0～30.0wt%.
5, in accordance with the method for claim 4, it is characterized in that described nano level TiO 2The median size of powder is 30～80nm.
6, in accordance with the method for claim 1, it is characterized in that described basic solution add-on is aluminum hydroxide solid elastomer powder and nano-TiO 220～80wt% of mixture mixes and pinched 10～50 minutes, and the acidic solution add-on is aluminum hydroxide solid elastomer powder and nano-TiO 220～80w% of mixture mixes and pinched 30～80 minutes.
7, in accordance with the method for claim 1, it is characterized in that described drying temperature is 80～140 ℃, the time is 3～6 hours, and maturing temperature is 450 ℃～700 ℃, and roasting time is 2～4 hours.
8, in accordance with the method for claim 1, it is characterized in that described hydrocarbon hydrogenizing treamtent catalyst is heavy, residuum hydrodesulfurization catalyzer.
9, in accordance with the method for claim 1, it is characterized in that with nanometer ZrO 2Be raw material, preparation contains the catalyzer of auxiliary agent Zr, or preparation contains the catalyzer of auxiliary agent Ti and Zr simultaneously.
10, in accordance with the method for claim 1, the pore volume that it is characterized in that described hydrotreating catalyst is 0.30～0.65ml/g, and specific surface is 120～300m 2/ g.
CN 03133548 2003-05-31 2003-05-31 Preparing method for hydrocarbon hydrotreating catalyst Expired - Lifetime CN1221312C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 03133548 CN1221312C (en) 2003-05-31 2003-05-31 Preparing method for hydrocarbon hydrotreating catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 03133548 CN1221312C (en) 2003-05-31 2003-05-31 Preparing method for hydrocarbon hydrotreating catalyst

Publications (2)

Publication Number Publication Date
CN1552520A true CN1552520A (en) 2004-12-08
CN1221312C CN1221312C (en) 2005-10-05

Family

ID=34323086

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 03133548 Expired - Lifetime CN1221312C (en) 2003-05-31 2003-05-31 Preparing method for hydrocarbon hydrotreating catalyst

Country Status (1)

Country Link
CN (1) CN1221312C (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7968069B2 (en) 2005-11-29 2011-06-28 Instituto Mexicano Del Petroleo Catalyst, its preparation and use for hydrodesulfurization of residua and heavy crudes

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7968069B2 (en) 2005-11-29 2011-06-28 Instituto Mexicano Del Petroleo Catalyst, its preparation and use for hydrodesulfurization of residua and heavy crudes

Also Published As

Publication number Publication date
CN1221312C (en) 2005-10-05

Similar Documents

Publication Publication Date Title
TWI641554B (en) Silica containing alumina supports, catalysts made therefrom and processes using the same
CN101376830A (en) Hydrotreating catalyst carrier and preparation thereof
CN100537028C (en) Preparation process of hydroprocessing catalyst
CN1123628C (en) Heavy oil hydrogenating treatment catalyst and its preparing method
CN1123626C (en) Heavy and residual oil hydrogenating treatment catalyst and its preparing method
CN1221312C (en) Preparing method for hydrocarbon hydrotreating catalyst
CN1112240C (en) Macroreticular alumina carrier containing Si and Ti and its preparing process
CN1107102C (en) Demetalating and desulfurizing hydrocatalyst and its preparing process
CN110038620A (en) The method for preparing hydrocracking catalyst
CN100340638C (en) Preparation method of hydrocarbon hydrotreatment catalyst
CN107670699A (en) A kind of heavy oil floating bed hydrogenation catalyst using complex carrier
CN101376829A (en) Bubbling bed hydrotreating catalyst and preparation thereof
CN114471593B (en) Preparation method of hydrofining catalyst
CN1091135C (en) Hydrogenating catalyst for heavy oil and its preparing process
CN1088093C (en) Process for preparing hydrorefining catalyst
CN1091134C (en) Hydrotransforming catalyst for residual oil and its preparing process
CN1227332C (en) Heavy, residual oil hydrogenating catalyst and its preparation
CN110038633A (en) A kind of hydrocracking catalyst and its production method
CN1053458C (en) Catalyzer for hydrotreating residuum and its prepn. method
CN100413583C (en) Method for preparing hydrocarbon hydroprocessing catalyst
CN1073616C (en) Preparation method of hydrogenation catalyst
CN1102639C (en) Residuum hydrotreatment catalyst and its preparation method
CN109794298B (en) Hydrofining catalyst and preparation method thereof, and distillate oil hydrofining method
CN110038619A (en) A kind of production method of hydrocracking catalyst
CN1102432C (en) Ti-contained aluminium hydroxide and its preparing process and application

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
CX01 Expiry of patent term

Granted publication date: 20051005

CX01 Expiry of patent term