CN100413583C - Method for preparing hydrocarbon hydroprocessing catalyst - Google Patents
Method for preparing hydrocarbon hydroprocessing catalyst Download PDFInfo
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- CN100413583C CN100413583C CNB2005100474649A CN200510047464A CN100413583C CN 100413583 C CN100413583 C CN 100413583C CN B2005100474649 A CNB2005100474649 A CN B2005100474649A CN 200510047464 A CN200510047464 A CN 200510047464A CN 100413583 C CN100413583 C CN 100413583C
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Abstract
The invention relates to a method for preparing hydrocarbon hydrogenation catalyst. Wherein, said catalyst uses gamma-Al2O3 as carrier, uses VIB group and VIII group metal as active components; uses Ti as active agent. The invention adds organic Ti salt into the agglutination process that prepares aluminum hydroxide with carbonization method. And the catalyst preparation uses complete mixing method that adding alkali solution with Mo and/or W into the aluminum hydroxide dry powder, mixing until the aluminum hydroxide powder is wetted by alkali solution; adding the acid solution of Co and/or Ni; mixing and shaping into bars, drying, baking to obtain the catalyst. In said catalyst, the catalyst agent Ti has uniform distribution, and the property of catalyst is improved.
Description
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 hydrodesulfurization, hydrodenitrogeneration, hydrocracking etc., the key of hydrotreatment technology is catalyst, and at present hydrocarbon hydrogenizing treamtent catalyst is many is carrier with the aluminium oxide, is active component with Mo and/or W and Ni and/or Co.In order to obtain bigger economic benefit, 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 " infusion process " or " mix and soak combination " fully, and one-step shaping prepares catalyst, and preparation cost is low.But do not introduce any auxiliary agent in its catalyst, 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 aluminium oxide effect that adds earlier is stronger, make pore volume, the specific surface loss of alumina powder serious, make the performance of final catalyst unsatisfactory.
Improve catalyst activity and usually adopt the method for adding auxiliary agent, as Ti, Zr, P, B, F etc.But this is because introduce the acid of auxiliary agent regulating catalyst and/or improve interaction between active component and carrier.United States Patent (USP) 5,089,453 have introduced auxiliary agent Ti in Hydrobon catalyst, activity of such catalysts is improved, but this catalyst also adopts and add acid earlier, add the method for alkali neutralization again, cause pore volume, the specific surface of final catalyst to reduce greatly, catalyst performance is affected.
EP0339640 discloses the method that a kind of coprecipitation prepares titanium-contained aluminum oxide, mixes with aluminum soluble salts such as aluminium chloride with solubility titanium salts such as titanium trichlorides, regulates pH value with alkaline solution then, and titanium and aluminium are precipitated simultaneously.This method can not be applicable in the carbonizatin method production alumina process, because, the aluminum salt solution that carbonizatin method is produced the aluminium oxide use is the sodium aluminate solution of alkalescence, as if the titaniferous salt solution mix with acidity precipitation reaction takes place at first then, and this course of reaction obtains product titanium skewness.
(as CN 1098433A, US 5,089 in kneading method and " mix and soak combination " method, 453, CN 1289822A etc.), because active component 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 facilitation of catalyst performance, this is to add the deficiency that auxiliary agent titanium or zirconium exist with the solution form, otherwise the performance that obtains catalyst can further improve.
CN 1324687A has announced that a kind of carbonizatin method adds the method for levigate metatitanic acid and silicon-containing compound formulations prepared from solutions titaniferous, silicon aluminium hydroxide, although reduced environmental pollution, but when becoming glue with carbon dioxide reaction, sodium aluminate solution can produce aggregation owing to add solid particle (although its granularity is extremely less than 65 μ m), influence the granularity of aluminium hydroxide, and titanium and the distribution of silicon in aluminium hydroxide also can be uneven, can cause its serviceability to reduce.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of titaniferous preparation method of hydrotreatment catalyst.The present invention introduces the auxiliary agent titanium in the one-tenth glue process of Carbonization Preparation aluminium hydroxide, guaranteeing under the prerequisite that the auxiliary agent titanium is evenly distributed, further improve the performance of titanium-contained aluminum oxide, cooperate suitable catalyst preparation process, can further improve the serviceability of catalyst.
The preparation process of hydrocarbon hydrogenizing treamtent catalyst of the present invention is as follows:
The Preparation of catalysts method is to adopt complete kneading method, in the Ti-contained aluminium hydroxide dry glue powder, add the alkaline solution that is dissolved with the group vib reactive metal, fully mix and pinch, add the acid solution that is dissolved with VIII family metal again, mix and pinch into after the plastic, material is made final catalyst through extrusion, drying and roasting; It is characterized in that the auxiliary agent titanium in the described Ti-contained aluminium hydroxide dry glue powder is to add organic titanium salt solution to introduce in the one-tenth glue process of Carbonization Preparation aluminium hydroxide.
Group vib reactive metal of the present invention is selected from Mo and/or W, and described VIII family metal is selected from Co and/or Ni.Various raw materials are formed definite addition: MoO by following final catalyst weight
3(and/or WO
3) 8.0wt%～24.0wt%, be preferably 16.0wt%～20.0wt%; CoO and/or NiO 1.0wt%～15.0wt% are preferably 4.0wt%～12.0wt%, and preferred two kinds of group VIII metals exist simultaneously; TiO
24.0wt%～12.0wt% is preferably 5.0wt%～10.0wt%; Surplus is γ-Al
2O
3, the catalyst pore volume is 0.30ml/g～0.65ml/g, specific surface is 120m
2/ g～300m
2/ g, average pore size is 6.0nm～15.0nm, bulk density is 0.75g/ml～0.85g/ml.
Add organic titanium salt solution in the process of Ti-contained aluminium hydroxide employing Carbonization Preparation aluminium hydroxide of the present invention and introduce titanium, method is simple; Add with ionic species owing to titanium simultaneously, titanium distributes more even in surface of aluminum hydroxide after becoming glue, with this raw material is the competition that the preparing carriers catalyst will weaken titanium and reactive metal dramatically, improve the utilization rate of reactive metal, thereby catalyst activity is higher.In the Ti-contained aluminium hydroxide dry glue powder, add alkaline solution earlier; adsorb and be covered in surfaces externally and internally formation one deck " diaphragm " of aluminium hydroxide; can slow down the strong interaction of acid and aluminium hydroxide when adding the acid solution peptization more greatly; reduced the loss of aluminium oxide pore volume and specific surface, made final catalyst 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 catalyst reach desirable state simultaneously, and catalyst performance improves greatly.
The specific embodiment
The concrete preparation process of catalyst of the present invention is:
(1) preparation sodium metaaluminate and organic titanium salt solution;
(2) sodium aluminate solution and the carbon dioxide for preparing is reacted into glue on one side under stirring condition, Yi Bian introduce organic titanium salt solution.
(3) solution filtration, washing, drying promptly make final Ti-contained aluminium hydroxide product after the cemented into bundles.
(4) take by weighing a certain amount of above-mentioned Ti-contained aluminium hydroxide dry glue powder, add alkaline solution and (contain NH
34.0wt%～12.0wt%, MoO
3And/or WO
328.0wt%～48.0wt%), fully mix, treat that the aluminum hydroxide solid elastomer powder is all wetted after, add an amount of acid solution again and (contain NiO 3.0wt%～9.0wt%, and/or CoO 3.0wt%～9.0wt%,), mix again and pinch into plastic and (can add nitric acid or acetic acid solution in case of necessity, as containing acetate 12.0wt%～30.0wt%), extruded moulding on banded extruder, drying, roasting promptly obtains catalyst.
The concentration of above-mentioned sodium aluminate solution is with Al
2O
3Count 5g/l～60g/l, Na and Al atomic ratio are 1.2～2.0.Above-mentioned organic titanium salt solution is selected from Ti (OC
4H
9)
4, Ti (OC
3H
7)
4, Ti (OC
2H
5)
4Ethanol or aqueous isopropanol, perhaps wherein several mixed solutions.The organic titanium salt solution concentration is counted 10g/l～100g/l with titanium dioxide weight.The addition of organic titanium salt solution is benchmark with final products, and wherein containing titanium dioxide is 0.1wt%～20wt%, is preferably 5wt%～15wt%.Become the glue temperature to be controlled at 10 ℃～45 ℃ according to the porous of needed Ti-contained aluminium hydroxide, concentration of carbon dioxide is controlled at 10v%～50v%.Be controlled to the glue slurry pH value and be at 9～12 o'clock and stop logical carbon dioxide, the control slurry pH value is higher than the titanium salt solution interpolation in 0～3 o'clock of final one-tenth glue rear slurry pH value and finishes.Stop can to wear out behind the logical carbon dioxide and also can not wear out, if wear out, ageing time is no more than 2 hours at most.The filter cake that obtains behind the dope filtration spends deionised water 1～5 time, contains Na in the aluminium hydroxide of preparation
+By weight＜0.05wt% till, then 80 ℃～180 ℃ of temperature dry 2～12 hours down.Above-mentioned steps (4) alkaline solution addition is Ti-contained aluminium hydroxide dry glue powder 20wt%～80wt%, mixes and pinches 10～50 minutes, and the acid solution addition is the 20wt%～80wt% of Ti-contained aluminium hydroxide dry glue powder, mixes and pinches 30～80 minutes.Catalyst shape can be cylinder or three (four) leaf grass, and baking 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 ℃.
Catalyst of the present invention can be used for the various hydrotreatment processes of various hydro carbons, raw material can be various distillates, secondary operations oil, heavy oil, residual oil and the hydro carbons that derives from coal etc., the hydrotreatment process comprises hydrodesulfurization, hydrodenitrogeneration, hydro-conversion etc., is specially adapted to the hydrodesulfurization of weight, residual oil.For different raw materials and different hydrogenation process, can adjust the component and the content of catalyst 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 catalyst, 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
With concentration is 30gAl
2O
3/ l, Na and Al atomic ratio are that 1.4 sodium aluminate solution 2000mL places reactor, 25 ℃ of temperature, and feeding concentration is the carbon dioxide of 40v%, in logical carbon dioxide, adding concentration under stirring is 50g TiO
2Ti (the OC of/l
4H
9)
4The aqueous isopropanol 140ml of (titanium isobutoxide) is 11 o'clock Ti (OC at slurry pH value
4H
9)
4Aqueous isopropanol add and to finish, be to stop logical carbon dioxide at 10 o'clock to slurry pH value.Aging 1.0 hours of slurries.Filter then, spend deionised water, in carrier, contain Na
+By weight＜during 0.05wt% till, dry (120 ℃) 4 hours are crushed to 180 orders again.Take by weighing this Ti-contained aluminium hydroxide dry glue powder 50g, add molybdenum acid ammonia solution 35g, wherein MoO
3Concentration is 30.0wt%, and solution contains NH
3Be 10wt%, it is wetting with aluminium hydrate powder to be fully mixed to alkaline solution, adds the 36g acid solution then, contains Ni (NO in the acid solution
3)
216.2wt%, Co (NO
3)
216.2wt%, solution contain acetate 17wt%, fully mix and pinch to plastic, and to become diameter be the bunge bedstraw herb bar of 1.1 * 1.2mm to extrusion on preceding crowded formula twin-screw banded extruder, and the gained catalyst was 100 ℃ of dryings 4 hours; 490 ℃ of roastings 3 hours, catalyst A, its character sees Table 1.
Embodiment 2
Compare with embodiment 1, sodium aluminate solution concentration is become 20gAl
2O
3/ l, the titanium salt solution 92ml of adding same concentrations, MoO
3Concentration changes 46.0wt% into, Ni (NO
3)
2Concentration change 24.8wt% into, Co (NO
3)
2Concentration change 24.8wt% into, other implementation conditions are constant, i.e. cost example catalyst B, its character sees Table 1.
Embodiment 3
Ti (OC will be added earlier among the embodiment 1
3H
7)
4The aqueous isopropanol of (isopropyl titanate), other implementation conditions are constant, i.e. cost example catalyst C, its character sees Table 1.
Embodiment 4
Catalyst sintering temperature among the embodiment 1 is become 550 ℃, and other implementation conditions are constant, i.e. cost example catalyst D, and its character sees Table 1.
Comparative example 1
This comparison example is to prepare the dried glue of Ti-contained aluminium hydroxide by the method that CN 1324687A describes.
With concentration is 30gAl
2O
3The sodium aluminate solution 500mL of/l places reactor, 25 ℃ of temperature, and feeding concentration is the carbon dioxide of 40v%, the concentration that adds pulp under continuous stirring is 20gTiO
2/ l metatitanic acid slurries (the pH value is 8.0, and granularity is less than 40 μ m) make carrier contain the TiO of 10wt%
2The unclassified stores consumption is identical with embodiment 1 with operating condition and method for preparing catalyst, gets catalyst E.
Embodiment 5
Under the same process condition, desulfurization, the denitrogenation that comparative catalyst A, B, C, D, E show when handling Middle East residual oil and take off the carbon residue performance.Estimate feedstock oil character and estimate process conditions and see Table 2 and table 3 respectively, wherein Hydrobon catalyst is the catalyst that various embodiments of the present invention make, hydrodenitrogenation catalyst is the same industry catalyst, is the FZC-41 residual hydrogenation denitrification catalyst of Qilu Petrochemical company catalyst plant production.Evaluation result sees Table 4.
Table 1 catalyst physico-chemical property
* annotate: the dispersivity test method is an X-ray photoelectron spectroscopy, and the decentralization value is big more, illustrates that the dispersion of metal in aluminium oxide is even more.
Table 2 feedstock oil property list 3 is estimated process conditions
Table 4 activity rating result
*
* sample analysis result after turning round 300 hours
From table 1 catalyst physico-chemical property as seen, in the process of Carbonization Preparation aluminium hydroxide, add organic titanium salt solution and introduce titanium, prepared catalyst metals decentralization I
Ti/ I
AlBe better than the comparative catalyst with specific surface, pore volume; And as seen from Table 4, the serviceability of catalyst of the present invention is better than the comparative catalyst.
Claims (9)
1. the preparation method of a hydrocarbon hydrogenizing treamtent catalyst comprises the steps:
(1) preparation sodium aluminate solution and organic titanium salt solution, then sodium aluminate solution and carbon dioxide are reacted into glue under stirring condition, introduce organic titanium salt solution when becoming glue, solution filtration, washing, drying promptly make the Ti-contained aluminium hydroxide dry glue powder after the cemented into bundles; Wherein becoming the glue temperature is 10 ℃～45 ℃, and the concentration of carbon dioxide is 10v%～50v%, is controlled to the glue slurry pH value and is at 9～12 o'clock and stop logical carbon dioxide, and pH value 0～3 an o'clock titanium salt solution adding finished after the control slurry pH value was higher than into glue; Described organic titanium salt solution is selected from Ti (OC
4H
9)
4, Ti (OC
3H
7)
4Or Ti (OC
2H
5)
4Ethanol or aqueous isopropanol or the wherein ethanol or the isopropyl alcohol mixture of several titanium salts;
(2) get the Ti-contained aluminium hydroxide dry glue powder that step (1) makes, add the alkaline solution that is dissolved with the group vib reactive metal, fully mix and pinch, add the acid solution that is dissolved with VIII family metal again, mix and pinch into after the plastic, material is made final catalyst through extrusion, drying and roasting; Described alkaline solution contains MoO
3And/or WO
328.0wt%～48.0wt%, and NH
34.0wt%～12.0wt%; Described acid solution contains NiO 3.0wt%～9.0wt% and/or CoO 3.0wt%～9.0wt% and acetate 12.0wt%～30.0wt%.
2. in accordance with the method for claim 1, it is characterized in that the various raw materials of catalyst are by definite addition: the MoO of following final catalyst weight composition
3And/or WO
38.0wt%～24.0wt%, CoO and/or NiO1.0wt%～15.0wt%, TiO
24.0wt%～12.0wt%, surplus is γ-Al
2O
3
3. in accordance with the method for claim 2, it is characterized in that the various raw materials of catalyst are by definite addition: the MoO of following final catalyst weight composition
3And/or WO
316.0wt%～20.0wt%, CoO and/or NiO4.0wt%～12.0wt%, TiO
25.0wt%～10.0wt%.
4. in accordance with the method for claim 1, it is characterized in that the concentration of described sodium aluminate solution is counted 5g/l～60g/l with aluminium oxide, Na and Al atomic ratio are 1.2～2.0.
5. in accordance with the method for claim 1, it is characterized in that the concentration of described organic titanium salt solution is counted 10g/l～100g/l with titanium dioxide, the addition of titanium salt solution is benchmark with final products, and wherein containing titanium dioxide is 0.1wt%～20wt%.
6. in accordance with the method for claim 1, it is characterized in that described washing for spending deionised water 1～5 time, contains Na in the aluminium hydroxide of preparation
+By weight＜0.05wt% till, drying be 80 ℃～180 ℃ dry 2～12 hours down.
7. in accordance with the method for claim 1, it is characterized in that described alkaline solution addition is the 20wt%～80wt% of Ti-contained aluminium hydroxide dry glue powder, mix and pinched 10～50 minutes, the acid solution addition is the 20wt%～80wt% of Ti-contained aluminium hydroxide dry glue powder, mixes and pinches 30～80 minutes.
8. in accordance with the method for claim 1, it is characterized in that described baking temperature is 80 ℃～140 ℃, be 3～6 hours drying time, and sintering temperature is 450 ℃～700 ℃, and roasting time is 2～4 hours.
9. in accordance with the method for claim 1, the pore volume that it is characterized in that described hydrotreating catalyst is 0.30ml/g～0.65ml/g, and specific surface is 120m
2/ g～300m
2/ g.
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|---|---|---|---|
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|---|---|---|---|
| CNB2005100474649A CN100413583C (en) | 2005-10-19 | 2005-10-19 | Method for preparing hydrocarbon hydroprocessing catalyst |
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| CN100413583C true CN100413583C (en) | 2008-08-27 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5089453A (en) * | 1990-06-25 | 1992-02-18 | Chevron Research And Technology Company | Hydroconversion catalyst and method for making the catalyst |
| CN1324687A (en) * | 2000-05-19 | 2001-12-05 | 中国石油化工集团公司 | Prepn. of titanium-containing aluminium bydroxide |
| US6383975B1 (en) * | 1998-07-07 | 2002-05-07 | Instituto Mexicano Del Petroleo | Procedure to obtain a catalyst for the hydrodenitrogenation and hydrodesulfurization of middle and heavy oil fraction and the resulting product |
| CN1552813A (en) * | 2003-05-31 | 2004-12-08 | 中国石油化工股份有限公司 | Heavy, residual oil hydrogenating catalyst and its preparation |
-
2005
- 2005-10-19 CN CNB2005100474649A patent/CN100413583C/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5089453A (en) * | 1990-06-25 | 1992-02-18 | Chevron Research And Technology Company | Hydroconversion catalyst and method for making the catalyst |
| US6383975B1 (en) * | 1998-07-07 | 2002-05-07 | Instituto Mexicano Del Petroleo | Procedure to obtain a catalyst for the hydrodenitrogenation and hydrodesulfurization of middle and heavy oil fraction and the resulting product |
| CN1324687A (en) * | 2000-05-19 | 2001-12-05 | 中国石油化工集团公司 | Prepn. of titanium-containing aluminium bydroxide |
| CN1552813A (en) * | 2003-05-31 | 2004-12-08 | 中国石油化工股份有限公司 | Heavy, residual oil hydrogenating catalyst and its preparation |
Non-Patent Citations (2)
| Title |
|---|
| TiO2-Al2O3 复合氧化物负载N iMo 加氢脱硫催化剂的研究. 刘百军等.分子催化，第18卷第6期. 2004 |
| TiO2-Al2O3 复合氧化物负载N iMo 加氢脱硫催化剂的研究. 刘百军等.分子催化，第18卷第6期. 2004 * |
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