CN1253861A - Preparation method of hydrogenation catlayst - Google Patents
Preparation method of hydrogenation catlayst Download PDFInfo
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- CN1253861A CN1253861A CN 98114457 CN98114457A CN1253861A CN 1253861 A CN1253861 A CN 1253861A CN 98114457 CN98114457 CN 98114457 CN 98114457 A CN98114457 A CN 98114457A CN 1253861 A CN1253861 A CN 1253861A
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Abstract
The present invention discloses a preparation method of hydrotreatment catalyst, in particular it is a preparation method of catalyst for residual hydrodenitrification and hydrogenation to remove carbon residue. Said invention is characterized by adding a neutral solution to prewet powdered material in the course of mix-kneading aluminium hydroxide monohydrate and metallic salt material, then adding acid solution and mix-kneading them into plastic body. On the premise of ensuring that said catalyst possesses high strength and stacking density its pore volume, specially its specific surface area are greater than that of catalyst prepared by using one-step solution addition process, and when it is used for treating residuum, its activity is obviously higher than that of existent catalyst.
Description
The present invention relates to a kind of preparation method of hydrotreatment catalyst, particularly residual hydrogenation and take off carbon residue (HDCR) and residual hydrogenation denitrogenation (HDN) Preparation of catalysts method.
Usually, the hydrotreating catalyst of hydrocarbon feed is all with γ～Al
2O
3Or contain the γ～Al of a small amount of one or more other elements (as Si, P, Ti, B, Mg, F etc.)
2O
3Be carrier, with a certain active component that is combined as of elements such as W, Mo, Ni and Co.Such catalyst activity metal carrying method has two kinds usually: kneading method and infusion process.Kneading method refers to and mix active metallic compound simultaneously in the preparing carriers process, and its advantage is that preparation technology is easy, and is with short production cycle, the efficient height, and cost is low, can obtain the higher catalyst of active metallic content; Its shortcoming is that difficulty accomplishes to make full use of metal component.Infusion process refers to and makes carrier load active component more earlier, its advantage is to help metal component to disperse at carrier micropore inner surface, but complex manufacturing, especially when single-steeping was difficult to satisfy catalyst itself to the requiring of metal addition, the complex operations of bringing by repeatedly flooding was to mention in the same breath with the easy of kneading method.For solving this class contradiction, Chinese invention patent CN1098433A has proposed a kind of solution, promptly " mix-soaks " production process of combination.Its main points are to sneak into a part of active component in the preparing carriers process earlier, and another part active component is with the infusion process load.Owing to added metallic salt in the kneading process, for guaranteeing that shaping of catalyst is smooth and intensity good, its peptization acid amount needs corresponding raising, acid has destruction to the aluminium oxide microcellular structure, thereby it is bigger to the influence of the pore volume of aluminium oxide especially specific area, the specific area of finished catalyst is descended, and in its exemplary embodiments, peptization acid consumption is pressed 100g Al
2O
3Meter adds about acetate 15g, and specific area is at 230m
2Below/the g, pore volume is below 0.4ml/g.And the surface of catalyst promptly is the reacting environment of reactant, also is the place that reactive metal is rely and disperseed, and for for the aluminium oxide of class methods preparation, calculation and its specific area are approximated to direct ratio in its effective active.Therefore, the loss of specific area brings adverse effect for the most at last the serviceability of catalyst.
The objective of the invention is the method for preparing catalyst of above-mentioned " mix-soaking " combination is improved, weaken the effect of acid solution to aluminium oxide, when guaranteeing that catalyst contains the high level hydrogenation active metals, make finished catalyst have bigger specific area, simultaneously can help material forming, guarantee catalyst strength and then improve corresponding serviceability such as catalyst activity.
The preparation process of hydrotreating catalyst of the present invention is: even a Powdered water-aluminum hydroxide and Powdered VIII compound and Powdered VIB compound, add neutral solution, and uniform mixing is also placed certain hour; Add acid solution again, mix and pinch into plastic, moulding on banded extruder, dry then, roasting.With ammonium molybdate-ammonia solution dipping gained strip, carry out drying, roasting again, promptly make finished catalyst.
The detailed process of hydrotreating catalyst preparation of the present invention is: take by weighing a water-aluminum hydroxide powder, Powdered VIII compound is preferably technical grade ammonium molybdate or molybdenum oxide of basic nickel carbonate and Powdered VIB compound preferably, mix, add and contain the uniform mixing of Si element neutral aqueous solution, until no Al
2O
3Dust floats, and it is evenly approximate to show that promptly solid, liquid mixes and stirs mutually, mixes and stirs and places 10～60 minutes.Add acetic acid solution again, mix and pinch into plastic, on banded extruder, be extruded into bar shaped.The strip that obtains under 100～150C dry 2～6 hours, 470～600 ℃ of following roastings 2～6 hours.Get strip after the above-mentioned roasting and place and rotate vessel, spray into molybdenum-ammonia solution,, take out until saturated, 20～120 ℃ dry 2～6 hours down, 460～580 ℃ of following roastings 2～6 hours, promptly make the catalyst finished product.
Above-mentioned acetic acid solution also can wherein can contain the TiCl of 12～17w% with dilute hydrochloric acid solution or/and dilute nitric acid solution replaces
3Can contain stabilizing agent such as H in used molybdenum-ammonia solution
3BO
3Deng, its concentration in molybdenum-ammonia solution is 2～5w%.The neutral aqueous solution of the above-mentioned Si of containing element preferably contains the aqueous solution of Ludox, and described Ludox is for containing SiO
2The Ludox of 20～50w%.
Adopt the hydrotreating catalyst of the inventive method preparation to have following feature: with final catalyst weight is benchmark, and catalyst contains MoO
320～25w%, NiO 7～10w%, the pore volume of catalyst are 0.38～0.45cm
3/ g, specific area is 220-270m
2/ g, bulk density is 0.84～0.90g/cm
3, intensity is 4.0～5.5N/mm.
Catalyst of the present invention can be used for the hydrotreatment of distillate and residual oil, especially cooperates with residuum hydrogenating and metal-eliminating, residuum hydrodesulfurization catalyst, is used for residual hydrogenation and takes off carbon residue and hydrodenitrogeneration process.
The inventive method adopts substep to add different solutions in kneading process; at first add the neutral solution uniform mixing and place certain hour; make aluminium oxide wetting in advance; make in the partial oxidation aluminium micropore and be filled with neutral solution; aluminium oxide is when next step contacts with acid solution, and the acid solution that enters in these micropores is less, thereby has reduced the destruction of acid to the aluminium oxide microcellular structure; these microcellular structures are protected, keep the original character of aluminium oxide not to be damaged.Finally when guaranteeing that catalyst hydrogenation activity metal component content is higher, the specific area of catalyst is improved, and the pore volume of catalyst, heap are than also increasing to some extent.Under the same process condition, handle identical isolated island decompression residuum, the catalyst that uses the inventive method to obtain shows the very high impurity activity of taking off, and its hydrodenitrogeneration rate is compared all with CN1098433A with the removal of ccr by hydrotreating rate and is significantly improved.
Following examples further specify the present invention.
Embodiment 1
(1) catalyst carrier preparation
Take by weighing 300g and contain Al
2O
3The water-aluminum hydroxide powder of 67w%, the Powdered basic nickel carbonate of 52.5g (containing NiO 56.3w%) 46.5g technical grade ammonium molybdate (contains MoO
381w%) mix, add 42.6g and (contain SiO
230w%) the mixed solution of Ludox and 120g water mixes and stirs and placed 30 minutes, adds 22.5g again and (contains TCl
317w%) TCl
3The mixed solution of solution and 30g HAc and 50g water mixes and pinches into plastic, is extruded into the strip of Φ 0.82mm on banded extruder, and this strip was descended dry 4 hours at 108 ℃, 540 ℃ of following roastings 3 hours.
(2) molybdenum-ammonia solution preparation
Take by weighing 70.5g and (contain MoO
381w%) technical grade ammonium molybdate, adding density is 0.9700g/cm
3Ammonia spirit 260cm
3Stirring and dissolving, placement is spent the night stable, contains MoO
319.0g/100cm
3
(3) Preparation of catalysts
Strip by (1) gained is placed the rotation vessel, spray into the solution by (2) preparation, until saturated, take out, drying is 3 hours under 120 ℃, again 490 ℃ of following roastings 3 hours.
Embodiment 2
Under the inventory of each material and all identical situation of other operating condition, reduce and mix and stir standing time to 15 minute, be i.e. the cost example with embodiment (1).
Embodiment 3
Under the inventory of each material and all identical situation of other operating condition, increase and mix and stir standing time to 50 minute, be i.e. the cost example with embodiment (1).
Comparative example (pressing the preparation of CN1098433A method)
The inventory of each material is all identical with embodiment (1) with other operating condition, just mixes when pinching, and each liquid once adds, i.e. the cost example.
Embodiment 4
This example is the physicochemical property and the activity rating result of above each routine catalyst.The physicochemical property of each routine catalyst sees Table 1.Estimate and see Table 2 with feedstock oil character.
During evaluate catalysts, from top to bottom by beds, through hydrodesulfurization (HDS) catalyst, pass through above each routine catalyst more earlier after hydrogen and feedstock oil mix, take One-through design, the HDS catalyst is with batch industrial products.The process conditions of estimating each routine catalyst employing are all identical, are respectively: reaction pressure, 14.6MPa; Reaction temperature, 400 ℃; Total liquid hourly space velocity (LHSV), 0.33h
-1Hydrogen-oil ratio (v), 1000.Reactor volume is: φ 25mm * 2000mm.Loaded catalyst is respectively: HDS catalyst, 120cm
3More than each routine catalyst, 180cm
3Evaluation result sees Table 3.Above-mentioned Hydrobon catalyst is that the trade mark that first chemical fertilizer factory of Qilu Petrochemical company produces is the Hydrobon catalyst of ZTS-01.
By this example as can be known, catalyst of the present invention has higher HDN, especially the HDCR activity.
The physicochemical property of each catalyst of table 1
| Physicochemical property | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example |
| Particle size, φ mm * mm | ??0.82×3～6 | ??0.82×3～6 | ??0.82×3～6 | ??0.82×3～6 |
| Pore volume, cm 3/g | ????0.416 | ????0.418 | ????0.421 | ????0.395 |
| Specific area, m 2/g | ?????239 | ?????232 | ?????243 | ?????203 |
| Average pore size, nm | ?????7.0 | ?????7.1 | ?????6.9 | ?????7.2 |
| Bulk density, g/cm 3 | ????0.870 | ????0.855 | ????0.864 | ????0.875 |
| Intensity, N/mm | ?????4.5 | ?????4.2 | ?????5.0 | ?????4.0 |
| ?MoO 3Content, w% | ?????22.9 | ?????23.41 | ?????23.56 | ?????24.19 |
| NiO content, w% | ?????8.68 | ?????8.59 | ?????9.58 | ?????9.46 |
Table 2 feedstock oil property list 3 evaluation results
| Character | Isolated island residual oil |
| Density (20 ℃), g/cm 3 | ????1.04 |
| ?S，w％ | ????2.6 |
| ?N，w％ | ????0.8 |
| ?CCR，w％ | ????16 |
| Catalyst | ?HDCR，％ | ?HDN，％ |
| Embodiment 1 | ???62.8 | ???58.0 |
| Embodiment 2 | ???62.5 | ???58.1 |
| Embodiment 3 | ???63.3 | ???58.8 |
| Comparative example | ???59.7 | ???55.9 |
Claims (8)
1, a kind of preparation method of hydrotreatment catalyst may further comprise the steps: (1) mixes a water-aluminum hydroxide and powdery nickel compound and powdery molybdenum compound; (2) in the said mixture material, add a kind of neutral solution and peptization acid, mix and pinch into plastic; (3) (2) gained plastic is carried out extruded moulding; (4) drying, roasting is by (3) gained strip; (5) with containing the strip of molybdenum solution dipping by (4) gained; (6) drying, roasting is by the strip of (5) gained;
It is characterized in that adding neutral solution earlier in the above-mentioned steps (2) mixes and stirs placement, and then add peptization acid and mix and pinch.
2,, it is characterized in that be 10～60 minutes the standing time of mixing and stirring of solid material and neutral solution according to the method for claim 1.
3, in accordance with the method for claim 1, it is characterized in that the neutral solution in the step (2) is the neutral solution that contains the Si element.
4, in accordance with the method for claim 1, it is characterized in that the baking temperature in the step (4) is 100～150 ℃, 2～6 hours time, sintering temperature is 470～600 ℃, 2～6 hours time; Baking temperature in the step (6) is 20～120 ℃, and 2～6 hours time, sintering temperature is 460～580 ℃, 2～6 hours time.
5, in accordance with the method for claim 1, it is characterized in that described Powdered nickel compound is a basic nickel carbonate, Powdered molybdenum compound is the technical grade ammonium molybdate.
6, in accordance with the method for claim 1, it is characterized in that described peptization acid is selected from acetic acid solution, salpeter solution, hydrochloric acid solution.
7,, it is characterized in that containing in the described peptization acid solution titanium trichloride of 12～17w% according to claim 1 or 6 described methods.
8, in accordance with the method for claim 1, it is characterized in that being characterized as of resultant catalyst: with final catalyst weight is benchmark, contains MoO
320～25w%, NiO 7～10w%, the pore volume of catalyst are 0.38～0.45cm
3/ g, specific area is 220～270m
2/ g, bulk density is 0.84～0.90g/cm
3, intensity is 4.0～5.5N/mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98114457A CN1102447C (en) | 1998-11-13 | 1998-11-13 | Preparation method of hydrogenation catlayst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98114457A CN1102447C (en) | 1998-11-13 | 1998-11-13 | Preparation method of hydrogenation catlayst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1253861A true CN1253861A (en) | 2000-05-24 |
| CN1102447C CN1102447C (en) | 2003-03-05 |
Family
ID=5224118
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98114457A Expired - Lifetime CN1102447C (en) | 1998-11-13 | 1998-11-13 | Preparation method of hydrogenation catlayst |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103785397A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Catalyst for removal of carbon residue through hydrogenation and preparation method thereof |
| CN105983415A (en) * | 2015-02-05 | 2016-10-05 | 中国石油天然气股份有限公司 | Preparation method of hydrotreating catalyst |
| CN116408112A (en) * | 2021-12-29 | 2023-07-11 | 中国石油天然气股份有限公司 | Heavy distillate oil hydrotreating catalyst and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042138C (en) * | 1993-08-04 | 1999-02-17 | 中国石油化工总公司 | Method for preparation of hydrofining catalyst |
| US5510306A (en) * | 1993-12-29 | 1996-04-23 | Shell Oil Company | Process for isomerizing linear olefins to isoolefins |
| RU2067497C1 (en) * | 1994-01-06 | 1996-10-10 | Товарищество с ограниченной ответственностью Научно-производственное объединение "Ленар" | Method of preparing zeolite-containing catalyst for hydrocarbon aromatization |
-
1998
- 1998-11-13 CN CN98114457A patent/CN1102447C/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103785397A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Catalyst for removal of carbon residue through hydrogenation and preparation method thereof |
| CN103785397B (en) * | 2012-11-01 | 2016-04-13 | 中国石油化工股份有限公司 | A kind of removal of ccr by hydrotreating Catalysts and its preparation method |
| CN105983415A (en) * | 2015-02-05 | 2016-10-05 | 中国石油天然气股份有限公司 | Preparation method of hydrotreating catalyst |
| CN105983415B (en) * | 2015-02-05 | 2018-11-16 | 中国石油天然气股份有限公司 | Preparation method of hydrotreating catalyst |
| CN116408112A (en) * | 2021-12-29 | 2023-07-11 | 中国石油天然气股份有限公司 | Heavy distillate oil hydrotreating catalyst and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1102447C (en) | 2003-03-05 |
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