CN103769118A - Heavy oil hydrogenation catalyst and preparation method thereof - Google Patents
Heavy oil hydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN103769118A CN103769118A CN201210408208.8A CN201210408208A CN103769118A CN 103769118 A CN103769118 A CN 103769118A CN 201210408208 A CN201210408208 A CN 201210408208A CN 103769118 A CN103769118 A CN 103769118A
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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
Heavily become bad along with world's crude oil becomes gradually, simultaneously market to light-end products particularly the demand of high-quality clean light-end products increase comparatively fast, hydrogen addition technology is worldwide especially paid attention to.The such as hydrotreatment of the hydrofinishing of various light ends oil, mink cell focus etc.
Mink cell focus is the most complicated part of component in crude oil, wherein includes more metal (Fe, Ca, Na, Ni, V etc.), sulphur, nitrogen and other undesirable components (colloid, asphalitine).In heavy-oil hydrogenation processing procedure, these Impurity depositions, on catalyst, cause the forever poisoning of catalyst, and more seriously blocking catalyst bed, causes continually more catalyst changeout.One of key of heavy Oil Hydrotreating Processes is to develop the catalyst of excellent performance.Its performance not only depends on the chemical state of kind, content and the active specy of active metal, and closely related with catalyst carrier.
For heavy oil hydrogenating treatment catalyst, not only to improve the pore structure of catalyst, improve its performance, extending catalyst service cycle, but also should reduce catalyst cost.The method that reduces catalyst cost comprises cost of material and production cost, and therefore reducing production costs is one of effective way reducing catalyst cost.Reducing the production cost of catalyst will make an effort on catalyst preparation flow.
Woelm Alumina is the carrier material of heavy-oil hydrogenation field extensive use, the preparation process of preparing hydrogenation catalyst mainly comprises: aluminum salt solution carries out plastic with precipitating reagent and reacts, then filter, be dried the aluminum hydroxide solid elastomer powder that obtains suitable form, add peptizing agent or binding agent moulding, again drying and roasting to obtain porous active alumina support, then flood active metal component and make catalyst.
A kind of preparation method of alumina support is disclosed in CN2004100500726.2, CN200610046922.1, with the acid aluminium salt aqueous solution and the alkali metal aluminate aqueous solution in suitable temperature, pH value, neutralize under the time.Neutralization finish after higher than neutral temperature and higher than in and pH value condition under carry out aging.Then, filter, wash, make aluminum oxide dry glue powder.Finally, moulding, roasting obtain alumina support.
CN201010509363.X discloses a kind of preparation method of catalyst for heavy oil hydrogenation demetal, and its process is that boehmite dry glue powder and extrusion aid are mixed, and then adds the aqueous solution that has dissolved physics expanding agent and chemical enlargement agent, is kneaded into plastic; Plastic is extruded on banded extruder to bar, the bar of gained is dried with high-temperature roasting and makes alumina support; Then adopt infusion process supported active metal component, obtain final Hydrodemetalation catalyst through super-dry and roasting.
CN201010276687.3, CN97115112.1 etc. are mixed and made into boehmite dry glue powder and water or the aqueous solution (with extrusion aid) after carrier, then flood active metal component and make catalyst.In mixed process, can produce unavoidably dust.
In above-mentioned prior art, the boehmite (a kind of aluminium hydroxide of concrete form) using is powder-product, in boehmite, aluminium oxide butt content is in 70% left and right, the water containing is generally the crystallization water, and (contents on dry basis is the mass percent that aluminium oxide solid that boehmite obtains while being heated to anhydrous state accounts for boehmite, identical below), not only in preparation process, need the drying time of growing, production efficiency is low, and energy consumption is high; And in the process of moulding, easily cause dust pollution, affect environment, harm people's health.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of heavy-oil hydrogenation catalyst and preparation method thereof.Catalyst prepared by the method is in the high demetalization of maintenance, desulfurization, de-carbon residue activity, simplify the dry run in boehmite preparation process, avoided the dust pollution that causes in forming process, enhanced productivity, reduce energy consumption, and then reduce the cost of catalyst.
A kind of heavy-oil hydrogenation catalyst, comprises carrier and active component, and described carrier is aluminium oxide, with contents on dry basis be the boehmite moulding preparation below 50%, prepared by the boehmite moulding that preferably contents on dry basis is 30%～50%; Active component is the metal of VIII family and/or VI B family, and wherein VIII family metal is Co or Ni, and VI B family metal is Mo or W.
A preparation method for heavy-oil hydrogenation catalyst, comprises boehmite preparation process; The preparation process of carrier and active constituent loading process.
Boehmite preparation process described in the inventive method, comprises the steps: that (1) aluminum salt solution reacts with plastic in carrying out with precipitating reagent; (2) solid product of filtered and recycled plastic reaction; (3) to obtain after drying contents on dry basis be below 50% to solid product, preferably 35%～50% boehmite.
In above-mentioned preparation method, the reaction of the plastic of step (1) can adopt the method for this area routine, concrete as acid aluminium salt solution with in alkaline precipitating agent, react with plastic, basic aluminium salt solution with in acidic precipitation agent, react etc. with plastic.In and in plastic course of reaction, can add as required suitable auxiliary agent, as one or more in silicon, boron, zirconium, titanium and phosphorus etc.In and the condition of plastic reaction be content well known to those skilled in the art, can require to determine according to specific product character.
In the inventive method, the preparation process of carrier adopts extruded moulding method, in forming process, can add as required suitable auxiliary agent, and auxiliary agent is as one or more in peptizing agent, binding agent, expanding agent and extrusion aid etc.Dry and the roasting of carrier is content well known to those skilled in the art.For example, be dried at 50～140 ℃ dry 3～10 hours, roasting 400～900 ℃ of constant temperature calcinings 1～4 hour etc., specifically can be determined according to the needs of final products.
In the inventive method, the load of active metal component adopts content well known to those skilled in the art, for example, can adopt the mode spraying to flood.Catalyst after dipping is dried 3～10 hours at 50～120 ℃, and at 400～550 ℃, constant temperature calcining 1～4 hour, obtains final catalyst.
Compared with prior art, a kind of heavy-oil hydrogenation catalyst of the present invention and preparation method thereof tool has the following advantages:
(1) after existing plastic dry materials, contents on dry basis is generally 70% left and right, water is wherein essentially the crystallization water, in the inventive method, in keeping heavy-oil hydrogenation catalyst activity, adopting contents on dry basis is the boehmite below 50%, has shortened the drying time of boehmite, amount of water when avoiding or reducing moulding, prevent from causing dust pollution and the harm to people, reduced energy consumption and production cost, improved production efficiency;
(2) result of study shows, it is constant that the thin water aluminium of plan that the contents on dry basis adopting in the inventive method is 30%～50% can be placed retention properties for a long time, meets the requirement of following process and be conducive to kneading and compacting.
The specific embodiment
Illustrate the solution of the present invention and effect below.
1, the preparation method of boehmite, adopts pH value to swing plastic method, and detailed process comprises the following steps:
A) prepare the acid aluminium salt aqueous solution, in solution with Al
2o
3the concentration of meter is 2～10g/100ml;
B) prepare the basic aluminate aqueous solution, in solution with Al
2o
3the concentration of meter is 8～30g/100ml, or preparation dilute ammonia solution, NH
3content is 8～16 g/100ml;
C) in neutralization end water, add appropriate acid aluminum saline solution, make its pH value be reduced to 2.0～4.0, be suitably 3.0～4.0, optimum is 3.0～3.5, and solution temperature is 50～95 ℃, is suitably 55～75 ℃, and optimum is 60～70 ℃; Stop adding the acid aluminium salt aqueous solution, stablize 3～10 minutes;
D) during the acid aluminium salt aqueous solution and the basic aluminate aqueous solution join continuously and carry out in step (c) simultaneously and plastic react, in and the plastic pH value of reacting be 6.0～8.0, be suitably 6.5～7.5, optimum is 7.0～7.5; In and 10～30 minutes time, be suitably 15～30 minutes, optimum is 15～25 minutes; In and slurries in Al
2o
3the content of weighing scale is 5～10wt%;
E) stop adding the acid aluminium salt aqueous solution, continue again to pass into basic aluminate (or alkaline precipitating agent) solution, make pH value rise to 8.5～12.0, be preferably 9.0～10.0, most preferably be 9.0～9.7, stabilization time, scope was 5～20 minutes, was preferably 5～15 minutes, most preferably was 5～10 minutes;
F) pass into the acid aluminium salt aqueous solution, make pH value be down to 2.0～4.0, be suitably 3.0～4.0, optimum is 3.0～3.5, and stabilization time, scope was 3～10 minutes;
G) pass into basic aluminate (or alkaline precipitating agent) solution, make pH value rise to 8.5～12.0, be suitably 9.0～10.0, optimum is 9.0～9.7, stabilization time, scope was 5～20 minutes, was suitably 5～15 minutes, and optimum is 5～10 minutes;
H) slurries are improved to temperature to 90 ℃～180 ℃, be suitably 90 ℃～150 ℃, optimum is 100～140 ℃, stablizes 0.1h～6.0h;
I) by the material filtering of gained, washing;
J) dry 0.2h～2.5h under 40 ℃～120 ℃ conditions, controls gained material contents on dry basis lower than 50%, and preferably contents on dry basis is 35%～50%, obtains boehmite of the present invention.
2, boehmite (or adding a certain amount of extrusion aid) carries out kneading, extrusion molding; Then at 50～140 ℃ dry 3～10 hours, 400～900 ℃ of constant temperature calcinings 1～4 hour, make alumina support of the present invention.
3, with the active metal solution impregnating carrier preparing, then at 50～120 ℃, be dried 3～10 hours, at 400～550 ℃, constant temperature calcining 1～4 hour, makes heavy-oil hydrogenation catalyst of the present invention.
The catalyst activity hydrogenation metal of preparation is by weight containing MoO as stated above
3or WO
3be 1.0 wt% ~ 20 wt%, preferably 5.0 wt% ~ 15.0 wt%, CoO or NiO are 0.5 wt%～10.0wt%, preferably 1.0 wt% ~ 5.0 wt%.Specific surface area of catalyst is 110～290 m
2/ g, is preferably 120～260 m
2/ g, pore volume is 0.55～1.10 ml/g, is preferably 0.60～0.90 ml/g, pore volume and specific area are measured with nitrogen low-temperature adsorption.
The preparation method of catalyst of the present invention, further illustrate by following examples, but these embodiment can not limit the present invention.
Embodiment 1
By the 2L sodium metaaluminate aqueous solution (with Al
2o
3the concentration of meter is 15g/100mL) and the aqueous solution of 3L aluminum sulfate (with Al
2o
3the concentration of meter is 3g/100mL) be respectively charged in the container of high level, lower even flowmeter flows into and is equipped with in the rustless steel container of 6L water purification belt stirrer and heating jacket, is heated to 60 ℃; Under stirring condition, pass into aluminum sulfate solution, make slurry pH value be down to 3.0, stablize after 10 minutes, two kinds of materials are added in stainless cylinder of steel by certain speed simultaneously, keeping pH value is 7.3, in and plastic react 15 minutes.Then stop adding aluminum sulfate solution, make pH value rise to 9.2, stop adding sodium aluminate solution, stablize a period of time; Pass into aluminum sulfate solution, make slurry pH value be down to 3.0, stablize a period of time; Pass into sodium aluminate solution, make pH value rise to 9.2.Repeat to swing 4 times.After swing finishes, stablize 10 minutes, be warming up to 145 ℃, stablize 3 hours, isolated by filtration mother liquor, washing.At 110 ℃ of temperature dry 0.8 hour, material contents on dry basis was 45%, dried material is placed after 20 days and carried out kneading and compacting, and 100 ℃ of freeze-day with constant temperature 5h, 900 ℃ of constant temperature calcinings 2 hours, obtain carrier A.
Take 112.53 grams of ammonium heptamolybdates, adding 900ml concentration is 12% ammoniacal liquor, then adds 35.46 grams, alkali formula carbon nickel to be stirred to completely and dissolves, and liquor capacity is adjusted to 1000ml with ammoniacal liquor, obtains solution L-1.By the saturated dipping of solution L-1 solution for carrier A, at 110 ℃ of dry 2h, 500 ℃ of roasting 3h obtain catalyst C-A.
Embodiment 2
Compare with embodiment 1, in pH swing process, solution temperature is 65 ℃, in and pH value be 7.0, slurries after filtration, washing after, at 110 ℃ of temperature be dried 0.8 hour, material contents on dry basis is 45%, unclassified stores consumption and operating condition are identical with embodiment 1, make catalyst C-B, by the saturated dipping of solution L-1 solution for carrier B, at 110 ℃ of dry 2h, 500 ℃ of roasting 3h obtain catalyst C-A.
Embodiment 3
Compare with embodiment 1, in pH swing process, pH becomes 3.0 from 9.2 and becomes 9.2 process again and repeat 3 times, slurries after filtration, washing after, at 110 ℃ of temperature, be dried 0.8 hour, material contents on dry basis is 45%, and unclassified stores consumption and operating condition are identical with embodiment 1, make support C, by the saturated dipping of solution L-1 solution for support C, at 110 ℃ of dry 2h, 500 ℃ of roasting 3h obtain catalyst C-C.
Embodiment 4
Compare with embodiment 1, in pH swing process, pH becomes 3.0 from 9.2 and becomes 9.2 process again and repeat 5 times, slurries after filtration, washing after, at 110 ℃ of temperature, be dried 0.8 hour, material contents on dry basis is 45%, and unclassified stores consumption and operating condition are identical with embodiment 1, make carrier D, by the saturated dipping of solution L-1 solution for carrier D, at 110 ℃ of dry 2h, 500 ℃ of roasting 3h obtain catalyst C-D.
Embodiment 5
Compare with embodiment 1, slurries after filtration, washing after, at 70 ℃ of temperature, be dried 1 hour, material contents on dry basis is 25%, and material is placed after 2 days and carried out moulding, and unclassified stores consumption and operating condition are identical with embodiment 1, make carrier E, by the saturated dipping of solution L-1 solution for carrier E, at 110 ℃ of dry 2h, 500 ℃ of roasting 3h obtain catalyst C-E.
Embodiment 6
Compare with embodiment 1, slurries after filtration, washing after, at 90 ℃ of temperature, be dried 1.5 hours, material contents on dry basis is 50%, and material is placed after 30 days and carried out moulding, and unclassified stores consumption and operating condition are identical with embodiment 1, make carrier F, by the saturated dipping of solution L-1 solution for carrier F, at 110 ℃ of dry 2h, 500 ℃ of roasting 3h obtain catalyst C-F.
Comparative example 1
According to the disclosed method Kaolinite Preparation of Catalyst of CN200410050726.2 carrier, 70 ℃ of neutral temperatures, in and pH value be 8.0, obtain carrier G, by the saturated dipping of carrier G use solution L-1 solution, at 110 ℃ of dry 2h, 500 ℃ of roasting 3h obtain catalyst C-G.
Comparative example 2
According to the disclosed method Kaolinite Preparation of Catalyst of CN201010509363.X carrier H, by the saturated dipping of solution L-1 solution for carrier H, at 110 ℃ of dry 2h, 500 ℃ of roasting 3h obtain catalyst C-H.
The physico-chemical property data of above-mentioned sample are listed in table 1.
The physico-chemical property of table 1 catalyst
| Sample number into spectrum | C-A | C-B | C-C | C-D | C-E | C-F | C-G | C-H |
| Specific surface/m 2·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 aperture/nm | 15 | 14 | 16 | 17 | 13 | 15 | 13 | 14 |
| MoO 3，% | 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 |
Prepared catalyst is carried out to activity rating with autoclave, the feedstock oil character of evaluation is in table 2.Appreciation condition is: raw material oil mass: 300ml, and catalytic amount: 20ml, temperature: 420 ℃, pressure: 14.5MPa, reaction time 60min.That evaluates the results are shown in Table 3.
Table 2 feedstock oil character
| Project | Data |
| Density (20 ℃)/gcm -1 | 0.985 |
| S/wt% | 2.58 |
| Ni＋V/μg·g －1 | 238.75 |
| CCR/ wt% | 13.94 |
Table 3 evaluating catalyst result
| 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 |
Catalyst prepared by specific surface area of catalyst, pore volume and the comparative example of preparing by the inventive method as can be seen from the above results, is suitable.And in preparation process, shorten drying time, reduced energy resource consumption, improved production efficiency, reduced 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 better than comparative catalyst.Illustrate that catalyst prepared by preparation method of the present invention can meet heavily, the needs of residual oil removing impurities matter.
Claims (9)
1. a heavy-oil hydrogenation catalyst, comprise carrier and active component, carrier is aluminium oxide, active component is the metal of VIII family and/or VI B family, wherein VIII family metal is Co or Ni, VI B family metal is Mo or W, it is characterized in that: described alumina support contents on dry basis is the boehmite moulding preparation below 50%.
2. catalyst according to claim 1, is characterized in that: the boehmite moulding preparation that described alumina support contents on dry basis is 30%～50%.
3. the preparation method of catalyst described in claim 1, is characterized in that: comprise boehmite preparation process; The preparation process of carrier and active constituent loading process.
4. method according to claim 3, is characterized in that: described boehmite preparation process, comprises the steps: that (1) aluminum salt solution reacts with plastic in carrying out with precipitating reagent; (2) solid product of filtered and recycled plastic reaction; (3) to obtain after drying contents on dry basis be below 50% to solid product.
5. method according to claim 4, is characterized in that: to obtain after drying contents on dry basis be 35%～50% boehmite to solid product in step (3).
6. method according to claim 3, is characterized in that: the preparation process of described carrier adopts extruded moulding method, in forming process, adds one or more in peptizing agent, binding agent, expanding agent and extrusion aid.
7. method according to claim 6, is characterized in that: the dry and roasting condition of carrier is as follows: be dried at 50～140 ℃ dry 3～10 hours, roasting was 400～900 ℃ of constant temperature calcinings 1～4 hour.
8. method according to claim 3, is characterized in that: active constituent loading process adopts infusion process.
9. method according to claim 8, is characterized in that: after dipping, at 50～120 ℃, be dried 3～10 hours, at 400～550 ℃, constant temperature calcining 1～4 hour, obtains final catalyst.
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| CN109569575A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Catalyst with hydrogenation catalyst effect and its preparation method and application and heavy-oil hydrogenation depitching matter method |
| CN109569576A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Catalyst with hydrogenation catalyst effect and its preparation method and application and heavy-oil hydrogenation depitching matter method |
| CN109926077A (en) * | 2017-12-15 | 2019-06-25 | 中国石油化工股份有限公司 | A kind of inferior raw material hydrogenation conversion catalyst and preparation method thereof |
| CN109926062A (en) * | 2017-12-15 | 2019-06-25 | 中国石油化工股份有限公司 | A kind of coal tar hydrogenating processing catalyst and preparation method thereof |
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| 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 |
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| CN109926077A (en) * | 2017-12-15 | 2019-06-25 | 中国石油化工股份有限公司 | A kind of inferior raw material hydrogenation conversion catalyst and preparation method thereof |
| CN109926062A (en) * | 2017-12-15 | 2019-06-25 | 中国石油化工股份有限公司 | A kind of coal tar hydrogenating processing 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 |
| 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 |
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