CN1073616C

CN1073616C - Preparation method of hydrogenation catalyst

Info

Publication number: CN1073616C
Application number: CN98114455A
Authority: CN
Inventors: 苏晓波; 方维平; 吴国林; 张皓; 袁胜华; 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: 2001-10-24
Anticipated expiration: 2018-11-13
Also published as: CN1253986A

Abstract

The present invention discloses a preparation method of hydrogenation processing catalysts, which overcomes the defect of low activity of the existing hydrogenation processing catalysts, particularly residual oil hydrogenation denitrification and carbon residue removing catalysts. In the present invention, in the mixing kneading process of aluminium hydroxide monohydrate and metal salt, the addition quantity of exsolution acid is reduced by 20 to 80w% of that of the prior art for reducing the influence of acid on carrier micropore structures. Catalysts prepared by the method of the present invention have more concentrated pore size distribution than that of catalysts prepared by conventional methods and have high activity on the premise of ensured pore volume and large specific surface area and present high activity for residual oil hydrogenation and denitrification and carbon residue removing.

Description

A kind of preparation method of hydrotreatment catalyst

The present invention relates to a kind of preparation method of hydrotreatment catalyst, particularly residual hydrogenation denitrogenation (DHN) and residual hydrogenation take off carbon residue (HDCR) 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 ingredient that is combined as of elements such as W, Mo, Ni and Co.Such catalyst activity metal load method has two kinds usually: kneading method and pickling 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 catalyzer of active metallic content; Its shortcoming is that difficulty accomplishes to make full use of metal component.Pickling process is to make carrier load active component more earlier, its advantage is to help metal component to disperse at carrier micropore internal surface, but complex manufacturing, especially when single-steeping was difficult to satisfy catalyst themselves to the requiring of metal add-on, 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 terms of settlement, i.e. " amalgamation is soaked " bonded production process.Its main points are to sneak into a part of active ingredient in the preparing carriers process earlier, and another part active ingredient is with the pickling 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, every 100g Al in its exemplary embodiments ₂O ₃(264g contains Al about need acetate 15g ₂O ₃A water aluminum oxide powder of 75% ... add 60g1: 1 acetic acid solution), thus bigger to the micropore property effect of aluminum oxide, make the pore distribution disperse of finished catalyst, the aperture is reduced to below 50% between the pore volume integration rate of 6～10nm, and specific surface area descends.And pore distribution concentration is greatly the precondition of good catalyst activity in certain OK range and specific surface area.

The objective of the invention is above-mentioned " amalgamation is soaked " bonded method for preparing catalyst is improved, when guaranteeing that catalyzer contains higher hydrogenation active metals component, weaken the effect of acidic solution to aluminum oxide, make finished catalyst have concentrated more pore size distribution and bigger specific surface area, help material forming simultaneously, guarantee catalyst strength and tap density, and then improve corresponding use properties such as catalyst activity.

The preparation process of hydrotreating catalyst of the present invention is: a Powdered water-aluminum hydroxide and pulverous VIII metallic compound and pulverous VI B metallic compound are mixed, add acidic solution, peptization acid consumption reduces 20～80w%, every 100gAl than ordinary method ₂O ₃Need acetate 3～12g, mix and pinch into plastic, gained plastic extruded moulding on banded extruder, dry then, roasting.With ammonium molybdate one ammonia solution dipping gained strip, carry out drying, roasting again, promptly make finished catalyst.

The detailed process of hydrotreating catalyst of the present invention preparation is: take by weighing a water-aluminum hydroxide powder, pulverous VIII compound is basic nickel carbonate and pulverous VI B compound technical grade ammonium molybdate preferably preferably, mixes, and adds to contain silicon sol and (contain SiO ₂20～50w%) acetic acid solution contains HAc40～70w% in the solution, the acetate consumption is pressed 100gAl ₂O ₃Add acetate 3～12g.Mix and pinched 3～8 hours, the gained plastic is extruded into bar shaped on banded extruder.The gained strip 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 ammonium molybdate one ammonia solution,, take out until saturated, 20～120 ℃ dry 2～6 hours down, 460～580 ℃ of following roastings 2～6 hours, promptly make the catalyzer finished product.

In above-mentioned preparation process, used acetic acid solution can contain 12～17w%TCl ₃, the acetate consumption is pressed 100gAl ₂O ₃Meter is preferably 5～10g.Acetic acid solution also can be salpeter solution or hydrochloric acid soln; Can contain stablizer as 1～5w%H in used ammonium molybdate one ammonia solution ₃BO ₃Deng.

Above-mentioned mixed pinching can be used the conventional mixed method of pinching, and also can strengthen to mix and pinch intensity, as using the mode of " rolling ".Adopt to mix for a long time and pinch or high-intensity " rolling ", it is more even that metal component is disperseed, and can make the material contact tightr, the gained plastic is sticking tough more, reach the necessarily required while in tap density, the intensity that guarantees catalyzer reaches service requirements, and shaping of catalyst can be carried out smoothly.

Adopt the hydrotreating catalyst of the inventive method preparation to have following feature: with final catalyst weight is benchmark, and catalyzer contains MoO ₃20～25w%, NiO7～10w%, the pore volume of catalyzer are 0.38～0.45cm ³/ g, specific surface area is 190-240m ²/ g, tap density is 0.84～0.90g/cm ³, greater than 50～65%, intensity is 4.0～6.0N/mm between the pore volume integration rate of 6～10nm in the aperture.

The present invention about the advantage of method for preparing catalyst is: in the carrier preparation process, reduce peptization acid amount, can reduce acid to alumina pore structural damage effect; Adopt long-time mixing to pinch or high-intensity " rolling " not only can promote abundant dispersion between each component, and can make material more closely knit, and then guaranteed that the intensity of catalyzer and tap density reach service requirements.The mixed time of pinching of increase combines with the acid of reduction peptization, when guaranteeing that catalyzer contains higher hydrogenation active metals component, it is more concentrated than the catalyzer of ordinary method preparation that the catalyzer aperture is distributed, the specific surface area and the intensity of gained catalyzer all increase, and then have improved the use properties of catalyzer greatly.Handle identical isolated island vacuum residuum under the same process condition, the activity that catalyzer of the present invention shows is higher than the CN1098433A catalyzer far away, and its hydrodenitrification rate and removal of ccr by hydrotreating rate all are significantly improved.The inventive method is the consumption of conservation acetate also, has reduced production cost.

Catalyzer of the present invention can be used for the hydrotreatment of distillate and residual oil, especially cooperate with residuum hydrogenating and metal-eliminating, residuum hydrodesulfurization catalyzer, be used for residual hydrogenation and take off carbon residue (HDCR) and hydrodenitrification (HDN) process, demonstrate outstanding hydrogenation and take off impurity activity.

Further specify technical solution of the present invention by the following examples.

Embodiment 1

(1) preparation of support of the catalyst

Take by weighing 298g and contain Al ₂O ₃The water-aluminum hydroxide powder of 67w%, the Powdered basic nickel carbonate of 52.0g (containing NiO 56.3w%) 24.5g technical grade ammonium molybdate (contains MoO ₃81w%) mix, add and contain SiO by 178g water, 42.3g ₂Silicon sol, the 22.0g of 30w% contain 17w%TCl ₃TCl ₃The mixing solutions that solution and 18gHAc (acetate) mix mixes and to pinch 3.5 hours, and the gained plastic is extruded into the strip of φ 0.82mm on banded extruder, this strip 108 ℃ dry 4 hours down, 540 ℃ of following roastings 3 hours.

(2) preparation of molybdenum-ammonia dipping solution

Take by weighing 122.5g and (contain MoO ₃81w%) technical grade ammonium molybdate, adding density is 0.9500g/cm ³Ammonia soln 240cm ³Stirring and dissolving, placement is spent the night stable, obtains containing MoO ₃33.0g/100cm ³Solution.

(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 all identical situation of the charging capacity of each material and other operational condition, increase mixed in the preparing carriers process and pinch time to 6.0 hour, i.e. cost example with embodiment 1.

Embodiment 3

The charging capacity of each material (except that HAc) is all identical with embodiment 1 with other operational condition, and just the HAc amount is reduced to 15g by 18g.

Embodiment 4

The charging capacity of each material (except that HAc) is all identical with embodiment 1 with other operational condition, and just the HAc amount is reduced to 12g by 18g.

Embodiment 5

In embodiment 1, acetate 18g is made into nitric acid 10g, i.e. the cost example

Comparative example (pressing the preparation of CN1098433A method)

The charging capacity of each material (except that HAc) is all identical with embodiment 1 with other operational condition (pinching the time except that mixing), and just the HAc add-on is 30g, mixes and pinches 35 minutes, be i.e. the cost example.

Embodiment 6

This example is the physico-chemical property and the activity rating result of above each routine catalyzer.

The physico-chemical property of each routine catalyzer sees Table 1.

The catalyst activity evaluation sees Table 2 with stock oil character.

During evaluate catalysts, from top to bottom by beds, through identical hydrogenating desulfurization (HDS) catalyzer, pass through above each routine catalyzer more earlier after hydrogen and stock oil mix, take One-through design.The processing condition of estimating each routine catalyzer employing are all identical: reaction pressure, 14.6MPa; Temperature of reaction, 400 ℃; Total liquid hourly space velocity, 0.33h ^-1Hydrogen-oil ratio (v), 1000.Reactor volume is: φ 25mm * 2000mm.Loaded catalyst is: HDS catalyzer, 120cm ³More than each routine catalyzer, 180cm ³Evaluation result sees Table 3.By this example as can be known, the pore distribution of catalyzer of the present invention is more concentrated, and has higher HDN, especially the HDCR activity.

Above-mentioned Hydrobon catalyst is that the trade mark that first fertilizer plant of Qilu Petrochemical company produces is the Hydrobon catalyst of ZTS-01.

The physico-chemical property of each catalyzer of table 1

Physico-chemical property	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Comparative example
Physico-chemical property	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Comparative example	Particle size, φ mm * mm	0.82× 3～6	0.82× 3～6	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	0.420	0.422	0.386	0.395	Particle size, φ mm * mm	0.82× 3～6	0.82× 3～6	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	0.420	0.422	0.386	0.395	Specific surface area, m ²/g	218	228	220	225	195	190
Mean pore size, nm	7.0	7.1	7.1	7.2	7.5	7.2	Specific surface area, m ²/g	218	228	220	225	195	190
Mean pore size, nm	7.0	7.1	7.1	7.2	7.5	7.2	6～10nm pore volume integration rate, %	57	59	55	50	51	48
Tap density, g/cm ³	0.870	0.865	0.865	0.850	0.88	0.875	6～10nm pore volume integration rate, %	57	59	55	50	51	48
Tap density, g/cm ³	0.870	0.865	0.865	0.850	0.88	0.875	Intensity, N/mm	5.2	5.5	5.0	4.5	4.1	4.0
MoO ₃Content, w%	22.9	23.41	23.4	24.1	22.8	24.19	Intensity, N/mm	5.2	5.5	5.0	4.5	4.1	4.0
MoO ₃Content, w%	22.9	23.41	23.4	24.1	22.8	24.19	NiO content, w%	8.68	8.59	8.75	8.90	8.0	9.46

Table 2 stock oil character

Character	Isolated island residual oil
Character	Isolated island residual oil	Density (20 ℃), g/cm ³	1.02
S,w％	2.6	Density (20 ℃), g/cm ³	1.02
S,w％	2.6	N,w％	0.8
CCR,w％	16	N,w％	0.8

Table 3 evaluation result

Embodiment	HDCR,％	HDN,％
Embodiment	HDCR,％	HDN,％	Embodiment 1	62.6	58.3
Embodiment 2	63.2	58.9	Embodiment 1	62.6	58.3
Embodiment 2	63.2	58.9	Embodiment 3	62.5	58.0
Embodiment 4	62.3	58.1	Embodiment 3	62.5	58.0
Embodiment 4	62.3	58.1	Comparative example	59.7	55.9

Claims

1, a kind of preparation method of hydrotreatment catalyst may further comprise the steps:

(1) water-aluminum hydroxide and powdery nickel compound and powdery molybdenum compound are mixed;

(2) a kind of peptization acid solution of adding is mixed in the said mixture material pinches, until becoming 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 obtains the finished product catalyzer by the strip of (5) gained; It is characterized in that: peptization acid add-on is pressed 100g Al in (2) step ₂O ₃Meter, peptization acid consumption is 3～12g.

2,, it is characterized in that the used peptization acid solution in the step (2) is selected from acetic acid solution, the salpeter solution that contains silicon sol that contains silicon sol, the hydrochloric acid soln that contains silicon sol according to the described preparation method of claim 1.

3, in accordance with the method for claim 2, it is characterized in that described silicon sol contains SiO ₂20～50w%.

4, in accordance with the method for claim 1, it is characterized in that the described mixed time of pinching is 3～8 hours.

5, according to the described preparation method of claim 1, it is characterized in that the drying temperature in the step (4) is 100～150 ℃, 2～6 hours time of drying, maturing temperature is 470～600 ℃, roasting time is 2～6 hours; Drying temperature in the step (6) is 20～120 ℃, and 2～6 hours time of drying, maturing temperature is 460～580 ℃, and roasting time is 2～6 hours.

6, according to the described preparation method of claim 1, it is characterized in that described Powdered nickel compound is a basic nickel carbonate, described Powdered molybdenum compound is the technical grade ammonium molybdate.

7,, it is characterized in that containing in the described acetic acid solution titanous chloride of 12～17w% according to claim 1 or 2 described preparation methods.

8, in accordance with the method for claim 1, it is characterized in that described peptization acid consumption is every 100gAl ₂O ₃With 5～10g.

9, in accordance with the method for claim 1, it is characterized in that with final catalyst weight be benchmark, catalyzer contains MoO ₃20～25w%, NiO7～10w%, the pore volume of catalyzer are 0.38～0.44cm ³/ g, specific surface area is 190～240m ²/ g, tap density is 0.84～0.90g/cm ³, the aperture is between the pore volume integration rate 50～65% of 6～10mm, and intensity is 4.0～6.0N/mm.