CN103769118B - Heavy oil hydrogenation catalyst and preparation method thereof - Google Patents
Heavy oil hydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN103769118B CN103769118B CN201210408208.8A CN201210408208A CN103769118B CN 103769118 B CN103769118 B CN 103769118B CN 201210408208 A CN201210408208 A CN 201210408208A CN 103769118 B CN103769118 B CN 103769118B
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Abstract
The invention discloses a heavy oil hydrogenation catalyst and a preparation method thereof. The heavy oil hydrogenation catalyst comprises a carrier and an active ingredient; the carrier is aluminum oxide, and is prepared from pseudo-boehmite with dry basis content below 50% via moulding; the active ingredient are metals selected form family VIII, Co or Ni, and/or family VI B, Mo or W. The preparation method comprises following steps: preparation of pseudo-boehmite, preparation of the carrier, and loading of the active ingredient. The heavy oil hydrogenation catalyst is capable of maintaining high demetalization, desulphurization, and carbon residue removing activities, simplifying drying process of pseudo-boehmite preparation, avoiding dust pollution caused by moulding process, increasing production efficiency, reducing production energy consumption, and reducing catalyst cost further.
Description
Technical field
The present invention relates to a kind of heavy-oil hydrogenation catalyst and preparation method thereof.
Background technology
Deteriorate again as world's crude oil gradually becomes, while market is particularly high-quality cleaning light-end products to light-end products
Demand increase very fast, hydrogen addition technology is worldwide especially paid attention to.The hydrogenation of such as various light ends oil
Refined, hydrotreating of mink cell focus etc..
Mink cell focus is the most complicated part of component in crude oil, wherein including more metal（Fe, Ca, Na, Ni, V etc.）、
Sulfur, nitrogen and other undesirable components（Colloid, asphalitine）.In heavy-oil hydrogenation processing procedure, these impurity are deposited on catalyst
On, cause the permanent poisoning of catalyst, more seriously blocking catalyst bed, cause to be replaced as frequently as catalyst.Heavy oil adds
One of key of hydrogen treatment technology is to develop the catalyst of excellent performance.Its performance depend not only on active metal species,
The chemical state of content and active specy, and it is closely related with catalyst carrier.
For heavy oil hydrogenating treatment catalyst, not only to improve the pore structure of catalyst, improve its performance, prolongation is urged
Agent service cycle, but also catalyst cost should be reduced.Reducing the method for catalyst cost includes cost of material and produces into
This, therefore it is one of effective way of reduction catalyst cost to reduce production cost.The production cost for reducing catalyst will be
Make an effort in catalyst preparation flow process.
Woelm Alumina is the wide variety of carrier material in heavy-oil hydrogenation field, prepares the preparation process master of hydrogenation catalyst
Including：Aluminum salt solution carries out plastic reaction with precipitant, then filters, is dried to obtain the aluminum hydroxide solid elastomer of suitable morphology
Powder, adds peptizer or binding agent molding, again drying and roasting to obtain porous activated alumina carrier, then impregnates activity gold
Category component makes catalyst.
A kind of preparation method of alumina support is disclosed in CN2004100500726.2, CN200610046922.1, i.e.,
Neutralized under suitable temperature, pH value, time with acid aluminium salt aqueous solution and alkali metal aluminate aqueous solution.Neutralization terminate after
It is higher than neutral temperature and aging higher than carrying out under neutralization pH value condition.Then, filter, wash, aluminum oxide dry glue powder is obtained.Most
Afterwards, molding, roasting obtains alumina support.
CN201010509363.X discloses a kind of preparation method of catalyst for heavy oil hydrogenation demetal, and its process is to intend
Boehmite dry glue powder and extrusion aid mix homogeneously, are subsequently adding the aqueous solution for having dissolved physics expanding agent and chemical enlargement agent,
It is kneaded into plastic；Plastic is extruded into into bar on banded extruder, the bar of gained is dried and high temperature roasting
Fire to obtain alumina support；Then infusion process supported active metals component is adopted, final hydrogenation is obtained through dry and roasting de-
Metallic catalyst.
CN201010276687.3, CN97115112.1 etc. are also by boehmite dry glue powder and water or aqueous solution（With
Extrusion aid）After being mixed and made into carrier, then impregnate active metal component and make catalyst.Powder can be produced unavoidably in mixed process
Dirt.
In above-mentioned prior art, the boehmite for using（A kind of aluminium hydroxide of concrete form）It is powder-product,
70% or so, the water for containing typically is water of crystallization to aluminium oxide contents on dry basis in boehmite（Contents on dry basis is the thin water aluminum of plan
The alumina solid that stone is heated to being obtained during anhydrous state accounts for the mass percent of boehmite, same as below）, not only in system
Longer drying time, low production efficiency, high energy consumption are needed during standby；And it is dirty that dust is easily caused during molding
Dye, affects environment, endangers the health of people.
The content of the invention
For the deficiencies in the prior art, the present invention provides a kind of heavy-oil hydrogenation catalyst and preparation method thereof.Party's legal system
Standby catalyst while high demetalization, desulfurization, de- carbon residue activity is kept, in simplifying boehmite preparation process
Dry run, it is to avoid the dust pollution caused in forming process, improve production efficiency reduces energy consumption, and then reduces urging
The cost of agent.
A kind of heavy-oil hydrogenation catalyst, including carrier and active component, the carrier is aluminium oxide, is with contents on dry basis
Prepared by less than 50% boehmite molding, preferred contents on dry basis is prepared by 30%~50% boehmite molding；Activearm
It is divided into the metal of the VIIIth race and/or VI B races, wherein VIII race's metal is Co or Ni, VI B races metal is Mo or W.
A kind of preparation method of heavy-oil hydrogenation catalyst, including boehmite preparation process；The preparation process of carrier and
Active component loading process.
Boehmite preparation process described in the inventive method, comprises the steps：（1）Aluminum salt solution and precipitant
It is neutralized plastic reaction；（2）The solid product of plastic reaction is recovered by filtration；（3）Solid product obtains after drying butt and contains
Measure as less than 50%, preferably 35%~50% boehmite.
In above-mentioned preparation method, step（1）Plastic reaction can adopt the conventional method in this area, it is concrete such as acidic aluminum
React with plastic in saline solution and alkaline precipitating agent, basic aluminium salt solution neutralizes plastic reaction etc. with acidic precipitation agent.In neutralization
In plastic course of reaction, suitable auxiliary agent, such as one or more in silicon, boron, zirconium, titanium and phosphorus can be added as needed on.
The condition of neutralization plastic reaction is content well known to those skilled in the art, can be determined according to specific product Property requirements.
The preparation process of carrier adopts extruded moulding method in the inventive method, in forming process, can be as needed
The suitable auxiliary agent of addition, one or more in auxiliary agent such as peptizer, binding agent, expanding agent and extrusion aid.The drying of carrier
It is content well known to those skilled in the art with roasting.For example, it is dried and is dried 3~10 hours at 50~140 DEG C, roasting exists
400~900 DEG C of constant temperature calcinings 1~4 hour etc., specifically can according to final products it needs to be determined that.
The load of active metal component in the inventive method adopts content well known to those skilled in the art, for example, can adopt
Impregnated with the mode for spraying.Catalyst after dipping is dried 3~10 hours at 50~120 DEG C, the constant temperature at 400~550 DEG C
Roasting 1~4 hour, obtains final catalyst.
Compared with prior art, a kind of heavy-oil hydrogenation catalyst of the invention and preparation method thereof has the advantage that：
（1）Contents on dry basis is usually 70% or so after existing plastic dry materials, and water therein is substantially water of crystallization,
In the inventive method, while heavy-oil hydrogenation catalyst activity is kept, contents on dry basis is adopted for the thin water aluminum of less than 50% plan
Stone, shortens the drying time of boehmite, it is to avoid or amount of water during reduction molding, prevent from causing dust pollution and to people
Harm, reduce energy consumption and production cost, improve production efficiency；
（2）Result of study shows that the contents on dry basis adopted in the inventive method can be grown for the thin water aluminum of 30%~50% plan
Time placement retention propertiess are constant, meet the requirement of following process and are conducive to kneading and compacting.
Specific embodiment
The solution of the present invention and effect is specifically described below.
1st, the preparation method of boehmite, using pH value plastic method is swung, and detailed process is comprised the following steps：
A) acid aluminium salt aqueous solution is prepared, with Al in solution2O3The concentration of meter is 2~10g/100ml；
B) basic aluminate aqueous solution is prepared, with Al in solution2O3The concentration of meter is 8~30g/100ml, or prepares dilute ammonia
Aqueous solution, NH3Content is 8~16 g/100ml；
C) appropriate acidity aluminum saline solution is added in neutralization bottom water so as to which pH value is reduced to 2.0~4.0, is conveniently
3.0~4.0, optimum is 3.0~3.5, and solution temperature is 50~95 DEG C, is conveniently 55~75 DEG C, and optimum is 60~70
℃；Stop adding acid aluminium salt aqueous solution, stablize 3~10 minutes；
D) acid aluminium salt aqueous solution is added continuously to step simultaneously with basic aluminate aqueous solution（c）In be neutralized plastic
Reaction, the pH value for neutralizing plastic reaction is 6.0~8.0, is conveniently 6.5~7.5, and optimum is 7.0~7.5；The neutralization time
10~30 minutes, be conveniently 15~30 minutes, and optimum is 15~25 minutes；With Al in neutralization serosity2O3The content of weight meter
For 5~10wt%；
E) stop adding acid aluminium salt aqueous solution, be further continued for being passed through basic aluminate（Or alkaline precipitating agent）Solution, makes pH
Value rises to 8.5~12.0, preferably 9.0~10.0, most preferably 9.0~9.7, and stabilization time scope is 5~20 minutes, preferably
For 5~15 minutes, most preferably 5~10 minutes；
F) acid aluminium salt aqueous solution is passed through, makes pH value be down to 2.0~4.0, be conveniently 3.0~4.0, optimum is 3.0
~3.5, stabilization time scope is 3~10 minutes；
G) it is passed through basic aluminate（Or alkaline precipitating agent）Solution, makes pH value rise to 8.5~12.0, conveniently for 9.0~
10.0, optimum is 9.0~9.7, and stabilization time scope is 5~20 minutes, is conveniently 5~15 minutes, and optimum is 5~10
Minute；
H) serosity is improved into temperature to 90 DEG C~180 DEG C, is conveniently 90 DEG C~150 DEG C, optimum is 100~140 DEG C,
Stable 0.1h~6.0h；
I) by the material filtering of gained, washing；
J) 0.2h~2.5h is dried under the conditions of 40 DEG C~120 DEG C, control resulting material contents on dry basis is less than 50%, preferably
Contents on dry basis is 35%~50%, obtains boehmite of the present invention.
2nd, boehmite（Or a certain amount of extrusion aid of addition）Carry out kneading, extrusion molding；Then at 50~140 DEG C
It is dried 3~10 hours, in 400~900 DEG C of constant temperature calcinings 1~4 hour, that is, alumina support of the present invention is obtained.
3rd, with the active metal solution impregnating carrier for preparing, then it is dried 3~10 hours at 50~120 DEG C, 400
Constant temperature calcining 1~4 hour at~550 DEG C, that is, be obtained heavy-oil hydrogenation catalyst of the present invention.
The catalyst activity hydrogenation metal for preparing as stated above contains by weight MoO3Or WO3For 1.0 wt% ~ 20
Wt%, preferably 5.0 wt% ~ 15.0 wt%, CoO or NiO be 0.5 wt%~10.0wt%, preferably 1.0 wt% ~ 5.0
wt%.Specific surface area of catalyst is 110~290 m2/ g, preferably 120~260 m2/ g, pore volume is 0.55~1.10 ml/g, excellent
Elect 0.60~0.90 ml/g as, pore volume and specific surface area are determined with nitrogen low-temperature adsorption.
The preparation method of catalyst of the present invention, is further illustrated with following examples, but these embodiments can not limit this
Invention.
Embodiment 1
By 2L sodium metaaluminate aqueous solutions（With Al2O3The concentration of meter is 15g/100mL）With the aqueous solution of 3L aluminum sulfate（With
Al2O3The concentration of meter is 3g/100mL）It is respectively charged in the container of high level, lower even effusion meter is flowed into equipped with the stirring of 6L water purification band
In the rustless steel container of device and heating mantle, 60 DEG C are heated to；Under agitation, aluminum sulfate solution is passed through, drops slurry pH value
To 3.0, after stablizing 10 minutes, two kinds of materials are pressed into certain speed and is added simultaneously in stainless cylinder of steel, keep pH value to be 7.3, neutralization
Plastic is reacted 15 minutes.Then stop adding aluminum sulfate solution, make pH value rise to 9.2, stop adding sodium aluminate solution, it is stable
For a period of time；Aluminum sulfate solution is passed through, makes slurry pH value be down to 3.0, stable a period of time；Sodium aluminate solution is passed through, pH is made
Value rises to 9.2.Repeat to swing 4 times.After swing terminates, stablize 10 minutes, be warming up to 145 DEG C, stablize 3 hours, be separated by filtration mother
Liquid, washing.At a temperature of 110 DEG C be dried 0.8 hour, material contents on dry basis be 45%, by dried material place 20 days it is laggard
Row kneading and compacting, 100 DEG C of freeze-day with constant temperature 5h, 900 DEG C of constant temperature calcinings 2 hours obtain carrier A.
112.53 grams of ammonium heptamolybdate is weighed, the ammonia for adding 900ml concentration to be 12% is subsequently adding 35.46 grams of alkali formula carbon nickel
Stir to being completely dissolved, liquor capacity is adjusted to 1000ml with ammonia, obtain solution L-1.Carrier A solution L-1 solution is satisfied
And dipping, 2h is dried at 110 DEG C, 500 DEG C of roasting 3h obtain catalyst C-A.
Embodiment 2
Compared with Example 1 compared with, in pH swing process solution temperature be 65 DEG C, neutralization pH value be 7.0, serosity Jing filter,
After washing, it is dried 0.8 hour at a temperature of 110 DEG C, material contents on dry basis is 45%, unclassified stores consumption and operating condition and reality
Apply example 1 identical, catalyst C-B is obtained, carrier B is impregnated with solution L-1 solution saturation, 2h, 500 DEG C of roastings are dried at 110 DEG C
3h obtains catalyst C-A.
Embodiment 3
Compared with Example 1 compared with solution ph is changed into the 3.0 process repetitions 3 for being changed into 9.2 again from 9.2 in pH swing process
Secondary, serosity is dried 0.8 hour Jing after filtering, wash at a temperature of 110 DEG C, and material contents on dry basis is 45%, unclassified stores consumption
It is same as Example 1 with operating condition, support C is obtained, support C is impregnated with solution L-1 solution saturation, 2h is dried at 110 DEG C,
500 DEG C of roasting 3h obtain catalyst C-C.
Embodiment 4
Compared with Example 1 compared with solution ph is changed into the 3.0 process repetitions 5 for being changed into 9.2 again from 9.2 in pH swing process
Secondary, serosity is dried 0.8 hour Jing after filtering, wash at a temperature of 110 DEG C, and material contents on dry basis is 45%, unclassified stores consumption
It is same as Example 1 with operating condition, carrier D is obtained, carrier D is impregnated with solution L-1 solution saturation, 2h is dried at 110 DEG C,
500 DEG C of roasting 3h obtain catalyst C-D.
Embodiment 5
Compared with Example 1 compared with serosity is dried 1 hour, material contents on dry basis Jing after filtering, wash at a temperature of 70 DEG C
For 25%, material carries out molding after placing 2 days, and unclassified stores consumption and operating condition are same as Example 1, and carrier E is obtained, will
Carrier E is impregnated with solution L-1 solution saturation, and 2h is dried at 110 DEG C, and 500 DEG C of roasting 3h obtain catalyst C-E.
Embodiment 6
Compared with Example 1 compared with serosity is dried 1.5 hours Jing after filtering, wash at a temperature of 90 DEG C, and material butt contains
Measure as 50%, material carries out molding after placing 30 days, and unclassified stores consumption and operating condition are same as Example 1, carrier F be obtained,
Carrier F is impregnated with solution L-1 solution saturation, 2h is dried at 110 DEG C, 500 DEG C of roasting 3h obtain catalyst C-F.
Comparative example 1
Catalyst carrier, 70 DEG C of neutral temperature are prepared according to method disclosed in CN200410050726.2, neutralization pH value is
8.0, carrier G is obtained, carrier G is impregnated with solution L-1 solution saturation, 2h is dried at 110 DEG C, 500 DEG C of roasting 3h are catalyzed
Agent C-G.
Comparative example 2
Catalyst carrier H is prepared according to method disclosed in CN201010509363.X, carrier H solution L-1 solution is satisfied
And dipping, 2h is dried at 110 DEG C, 500 DEG C of roasting 3h obtain catalyst C-H.
The physico-chemical property data of above-mentioned sample are listed in Table 1 below.
The physico-chemical property of the catalyst of table 1
| Sample number into spectrum | C-A | C-B | C-C | C-D | C-E | C-F | C-G | C-H |
| Specific surface/m2·g-1 | 164 | 168 | 159 | 160 | 155 | 169 | 158 | 161 |
| Pore volume/mlg-1 | 0.78 | 0.73 | 0.70 | 0.73 | 0.79 | 0.69 | 0.68 | 0.71 |
| Most probable pore size/nm | 15 | 14 | 16 | 17 | 13 | 15 | 13 | 14 |
| MoO3, % | 7.64 | 8.04 | 7.89 | 7.56 | 7.98 | 8.10 | 7.87 | 8.02 |
| NiO, % | 1.93 | 1.84 | 1.87 | 2.01 | 1.97 | 2.05 | 1.95 | 1.89 |
Activity rating is carried out to prepared catalyst with autoclave, the raw material oil nature of evaluation is shown in Table 2.Appreciation condition
For：Raw material oil mass：300ml, catalytic amount：20ml, temperature：420 DEG C, pressure：14.5MPa, response time 60min.Evaluate
The results are shown in Table 3.
The raw material oil nature of table 2
| Project | Data |
| Density（20℃）/g·cm-1 | 0.985 |
| S/wt% | 2.58 |
| Ni+V/ gg- 1 | 238.75 |
| CCR/ wt% | 13.94 |
The evaluating catalyst result of table 3
| Catalyst | C-A | C-B | C-C | C-D | C-E | C-F | C-G | C-H |
| Demetallization per (Ni+V), % | 99 | 99 | 99 | 99 | 99 | 97 | 97 | 98 |
| Desulfurization degree, % | 61 | 62 | 64 | 64 | 62 | 61 | 61 | 60 |
| De- carbon yield, % | 54 | 56 | 56 | 53 | 53 | 52 | 42 | 51 |
As can be seen from the above results, it is prepared by specific surface area of catalyst, pore volume and the comparative example for preparing by the inventive method
Catalyst it is suitable.And drying time is shortened in preparation process, and energy resource consumption is reduced, production efficiency is improve, reduce
Catalyst preparation cost.
As seen from Table 3, the demetalization of catalyst of the present invention and desulfurization performance and comparative catalyst are suitable；De- carbon residue performance is excellent
In comparative catalyst.Illustrate that catalyst prepared by preparation method of the present invention can meet weight, the needs of residual oil removing impurities matter.
Claims (6)
1. a kind of heavy-oil hydrogenation catalyst, including carrier and active component, carrier is aluminium oxide, active component be the VIIIth race and/
Or VI B races metal, wherein VIII race's metal be Co or Ni, VI B races metal be Mo or W, it is characterised in that：Described carrying alumina
Body contents on dry basis is prepared by 30%~50% boehmite molding；Described boehmite preparation process, including it is as follows
Step：（1）Aluminum salt solution is neutralized plastic reaction with precipitant；（2）The solid product of plastic reaction is recovered by filtration；（3）Gu
Body product obtains after drying the boehmite that contents on dry basis is 35%~50%.
2. the preparation method of heavy-oil hydrogenation catalyst described in a kind of claim 1, it is characterised in that：Prepare including boehmite
Process；The preparation process and active component loading process of carrier.
3. method according to claim 2, it is characterised in that：The preparation process of the carrier adopts extruded moulding method,
In forming process, add one or more in peptizer, binding agent, expanding agent and extrusion aid.
4. method according to claim 2, it is characterised in that：It is dried in carrier preparation process and roasting condition is as follows：It is dry
Dry to be dried 3~10 hours at 50~140 DEG C, roasting was in 400~900 DEG C of constant temperature calcinings 1~4 hour.
5. method according to claim 2, it is characterised in that：Active component loading process adopts infusion process.
6. method according to claim 5, it is characterised in that：It is dried 3~10 hours at 50~120 DEG C after dipping,
Constant temperature calcining 1~4 hour at 400~550 DEG C, obtains final catalyst.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104961446A (en) * | 2015-06-16 | 2015-10-07 | 翟晨曦 | Processing method for preparing boehmite for alpha-aluminum-oxide-based ceramic abrasive materials with sol gel technology |
| CN108067246A (en) * | 2016-11-16 | 2018-05-25 | 中国石油天然气股份有限公司 | Preparation method of bulk phase hydrogenation catalyst |
| CN109569576B (en) * | 2017-09-29 | 2021-11-16 | 中国石油化工股份有限公司 | Catalyst with hydrogenation catalysis effect, preparation method and application thereof, and heavy oil hydrogenation asphaltene removal method |
| CN109569575B (en) * | 2017-09-29 | 2021-12-17 | 中国石油化工股份有限公司 | Catalyst with hydrogenation catalysis effect, preparation method and application thereof, and heavy oil hydrogenation asphaltene removal method |
| CN109926077B (en) * | 2017-12-15 | 2021-10-08 | 中国石油化工股份有限公司 | Inferior raw material hydro-conversion catalyst and preparation method thereof |
| CN109926062B (en) * | 2017-12-15 | 2021-10-08 | 中国石油化工股份有限公司 | Coal tar hydrotreating catalyst and preparation method thereof |
| CN116408098A (en) * | 2021-12-30 | 2023-07-11 | 中国石油天然气股份有限公司 | Residual oil hydrogenation catalyst and preparation method and application thereof |
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