CN1102447C

CN1102447C - Preparation method of hydrogenation catlayst

Info

Publication number: CN1102447C
Application number: CN98114457A
Authority: CN
Inventors: 苏晓波; 方维平; 张皓; 袁胜华; 吴国林; 付泽民
Original assignee: Sinopec Fushun Research Institute of Petroleum and Petrochemicals; China Petrochemical Corp
Current assignee: Sinopec Fushun Research Institute of Petroleum and Petrochemicals; China Petrochemical Corp
Priority date: 1998-11-13
Filing date: 1998-11-13
Publication date: 2003-03-05
Anticipated expiration: 2018-11-13
Also published as: CN1253861A

Abstract

The present invention discloses a preparation method of hydroprocessing catalysts, particularly a preparation method of residual oil hydrogenation denitrification and hydrogenation carbon residue removing catalysts. The method overcomes the defect that in the conventional technique, peptization acid destroys the micropore structure of alumina. In the present invention, in the mixing kneading process of aluminium hydroxide monohydrate, metal salt, etc., firstly, neutral solutions are added for pre-wetting powder materials; then, acidic solutions are added for causing powder materials to be mixed and kneaded into plastic bodies. The catalysts prepared by the method of the present invention have pore volume and especially specific surface area which are larger than that of catalysts prepared by a once solution adding method on the premise of ensured strength and high bulk density; when the catalysts of the present invention are used for processing residual oil, the activity of the catalysts of the present invention are obviously higher than that of the existing catalysts.

Description

A kind of preparation method of hydrotreatment catalyst

1, technical field

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.

2, background technology

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.

3, summary of the invention

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 100～150 ℃ dry 2～6 hours down, 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.

4, the specific embodiment

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
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	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	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	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	MoO ₃Content, w%	22.9	23.41	23.56	24.19

Table 2 feedstock oil property list 3 evaluation results

Character	Isolated island residual oil
Character	Isolated island residual oil	Density (20 ℃), g/cm ³	1.04
S，w％	2.6	Density (20 ℃), g/cm ³	1.04
S，w％	2.6	N，w％	0.8
CCR，w％	16	N，w％	0.8

Catalyst	HDCR，％	HDN，％
Catalyst	HDCR，％	HDN，％	Embodiment 1	62.8	58.0
Embodiment 2	62.5	58.1	Embodiment 1	62.8	58.0
Embodiment 2	62.5	58.1	Embodiment 3	63.3	58.8
Comparative example	59.7	55.9	Embodiment 3	63.3	58.8

Claims

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 said neutral solution is the neutral solution that contains the Si element in the above-mentioned steps (2), add earlier this neutral solution and mix and stir and placed 10～60 minutes, and then add peptization acid and mix and pinch.

2, 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.

3, 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.

4, 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.

5,, it is characterized in that containing in the described peptization acid solution titanium trichloride of 12～17w% according to claim 1 or 4 described methods.

6, 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.