CN104646009A - Inferior heavy oil hydrodesulfurization catalyst and preparation method thereof - Google Patents
Inferior heavy oil hydrodesulfurization catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an inferior heavy oil hydrodesulfurization catalyst and a preparation method thereof. The catalyst takes aluminum oxide as the carrier, and adopts group VIII and group VIB elements especially Ni-Mo as the active components, the catalyst pore volume is 0.45-0.60cm<3>/g, the specific surface area is 205-260m<2>/g, the average pore diameter is 7.0-12.0nm, and the average pore diameter gradually increases from the center to the outer surface along the radial direction of the catalyst particles. According to the preparation method of the catalyst, a concentration continuously increasing acid solution is employed to treat molded and roasted carrier particles. The catalyst provided by the invention has large surface aperture, wide pore channel, excellent diffusion performance, high hydrodesulfurization activity and activity stability.
Description
Technical field
The present invention relates to a kind of hydrotreating catalyst and preparation method thereof, particularly inferior heavy oil Hydrobon catalyst and preparation method thereof.
Background technology
Inferior heavy oil is as higher in the impurity content such as wax tailings, residual oil, usually need to remove the wherein impurity such as most sulphur, to produce oil product and the industrial chemicals such as clean vapour, diesel oil through follow-up processing (as catalytic cracking) through hydrotreatment (as residual hydrogenation).Containing a large amount of resin and asphalts in the inferior heavy oil such as residual oil, this part molecular weight of material is large, complex structure, and diffusion difficulty, therefore requires that catalyst has excellent pore passage structure, to improve de-impurity activity and the stability of catalyst.
The pore structure of catalyst has important impact to its performance.For catalyst for hydroprocessing of heavy oil, need that there is unobstructed duct and larger pore volume.Unobstructed diffusion and the reaction being conducive to macromolecule hydrocarbon material in mink cell focus in duct, thus the reactivity improving catalyst; Avoid metal to deposit simultaneously or react coking causing catalyst aperture block and cause rapid catalyst deactivation, to improve the activity stability of catalyst.Therefore the catalyst for hydroprocessing of heavy oil that a duct is unobstructed, will have good reactivity and activity stability.
In order to improve the pore volume of alumina support and obtain unimpeded duct, generally adopt the method adding expanding agent at present, such as US4,448,896 patent Introductions for raw material, and add carbon powder as expanding agent with a kind of boehmite, obtain alumina support through kneading, extrusion, drying and roasting.Its shortcoming is: add a small amount of carbon powder, then easily form " ink bottle " nibs; Add too much carbon powder, then cause support strength obviously to reduce.
Patent US4,066,574, US4,113,661 and US4,341,625 preparation methods describing a kind of alumina support, namely in Alpha-alumina monohydrate, first add aqueous solution of nitric acid, fully add a certain amount of ammonia spirit again after effect, reach the object expanding carrier pore volume.Although the method can play reaming effect, carrier hole diameter is single distribution by particle exterior surface to center, is unfavorable for the effect playing particle surfaces externally and internally substantially.
Summary of the invention
The object of this invention is to provide a kind of method making the directed reaming of catalyst, though catalyst average pore diameter along particle radial by center to outer surface in increasing gradually; Another object of the present invention is to provide the unobstructed inferior heavy oil Hydrobon catalyst in a kind of duct.
The main points of the inventive method are: 1) first carry out peptization, extruded moulding, drying and roasting to boehmite; 2) acid solution that the particle concentration after shaping and roasting increases continuously is processed, and closed processes, washing and drying under higher than the condition of room temperature; 3) again with the carrier that the solution impregnation containing active metal obtains, obtained final catalyst.
Catalyst of the present invention with aluminium oxide or containing the aluminium oxide of auxiliary agent for carrier, its pore volume is 0.45 ~ 0.60cm
3/ g, specific area is 205 ~ 260m
2/ g, average pore diameter is 7.0 ~ 12.0nm, it is characterized in that along catalyst granules radial direction its average pore diameter from center to outer surface be increase gradually.
The present invention makes the unimpeded principle in catalyst duct be: to the carrier particles after shaping and roasting by its saturated water absorption equal-volume spray acid solution.While spray, the concentration of continuous adjustment of acidity solution, makes it enter into the duct of particle from low to high.Due to the effect of capillary pressure, the low concentration acid solution first sprayed can spread to carrier granular internal layer, and the high concentrated acid solution then sprayed can closer to the skin of carrier granular.Higher than under the condition of room temperature, by the effect between acid solution and aluminium oxide, the bore dia in duct is expanded.Due to the difference of the successively acid solutions of spray, cause its reaming effect different, finally make carrier duct from granular center to outer surface, constantly become large, form open " trumpet type " pore passage structure, thus make that the pore volume of carrier increases, duct is unobstructed.
The one of catalyst is prepared as follows:
(1) take boehmite dry glue powder, add water, peptizing agent and extrusion aid, extruded moulding after abundant kneading.Appropriate different auxiliary agent can be added as required in forming process; After drying, roaster is put into 550 ~ 750 DEG C of constant temperature 1 ~ 8 hour;
(2) to the even shower water of (1) gained carrier, while shower water, in water, acid or acid solution is at the uniform velocity added, until reach the saturated water absorption of carrier; Closed processes 1 ~ 4 hour under 40 ~ 95 DEG C of conditions, with water purification washing 1 ~ 3 time, gained material was 105 ~ 300 DEG C of dryings 2 ~ 6 hours;
(3) by the solution impregnation of the nickeliferous and molybdenum strip by (2) gained, dry, 460 ~ 540 DEG C of roasting temperatures 2 ~ 5 hours, obtained final catalyst.
Acid of the present invention or acid solution are nitric acid, acetic acid or phosphoric acid and solution thereof.
Described extrusion aid is the blue or green powder in field or citric acid.Described auxiliary agent can be one or more in the compound of the elements such as phosphorus, boron, fluorine, silicon, titanium, zirconium.
The shape of catalyst of the present invention can change according to different requirements.
Catalyst of the present invention, is applicable to the hydrodesulfurization of inferior heavy oil.
Compared with existing method for preparing catalyst, the advantage of the inventive method is: catalyst pores diameter is open distribution, and surperficial aperture is comparatively large, and duct is unobstructed, and catalyst desulfurizing is active and stability is high.
The average pore diameter radial distribution signal of catalyst of the present invention as shown in Figure 1.
Accompanying drawing explanation
Fig. 1 is catalyst average pore diameter radial distribution schematic diagram.
Detailed description of the invention
Below further illustrate feature of the present invention with embodiment and comparative example.
Embodiment 1
(1) preparation of carrier
Take macropore boehmite dry glue powder (contents on dry basis 71.5wt%) 500g that Yantai Heng Hui Chemical Co., Ltd. produces, add sesbania powder 14g, mix.The acetum 390g being 4.0wt% concentration adds in afore-mentioned materials, and kneading becomes plastic, and then on front crowded formula single-screw extruder, being extruded into diameter is the cylindrical of 1.4mm.120 DEG C of dryings 3.0 hours, then insert in roaster, rise to 650 DEG C with the speed of 180 DEG C/h, constant temperature 3 hours.
(2) process of carrier
Take (1) gained carrier 30 as one kind 0 gram and be placed in rotation vessel, 250g deionized water is evenly sprayed to carrier with the speed of 30mL/ minute, while shower water, in aforementioned deionized water, evenly adds acetic acid with the speed of 3.0g/ minute.Spray is to carrier saturated water absorption, and 50 DEG C of closed processes 2.0 hours, water purification washs 2 times.150 DEG C of dryings 3.0 hours.
(3) preparation of catalyst
Take 281.0 grams of technical grade ammonium heptamolybdates (containing MoO
381wt%), adding 500 grams of concentration is under agitation the ammonia spirit of 18wt%, is stirred to and dissolves completely, then adds 271.0 grams of technical grade nickel nitrates (containing NiO24wt%), be stirred to and dissolve completely, be finally adjusted to 1000mL with the ammonia spirit that concentration is 18w%.Take and be placed in rotation vessel by (2) gained strip, spray into gained metallic solution until saturated, 120 DEG C of dryings 3.0 hours after taking-up, then 500 DEG C of roastings 3 hours, obtain catalyst A.
Embodiment 2
Take aforementioned boehmite dry glue powder 500g, add sesbania powder 14g, mix.The acetum 400g being 3.5wt% concentration adds in afore-mentioned materials, and kneading becomes plastic.The method extrusion identical with embodiment 1, drying and roasting.250g deionized water is evenly sprayed to gained alumina support with the speed of 30mL/ minute, while shower water, in aforementioned deionized water, evenly adds acetic acid with the speed of 4.0g/ minute.Spray is to carrier saturated water absorption, and 60 DEG C of closed processes 3.0 hours, water purification washs 3 times.200 DEG C of dryings 3.0 hours.Catalyst preparation conditions in the same manner as in Example 1 is adopted to obtain catalyst B.
Embodiment 3
Change the speed that adds of acetic acid in embodiment 1 into 2.5g/ minute, other condition is all identical with embodiment 1, obtain catalyst C.
Embodiment 4
In example 2, in water, evenly add with the speed of 3.0g/ minute the salpeter solution that concentration is 45wt% while Air washer.Spray is to carrier saturated water absorption, and 45 DEG C of closed processes 2.0 hours, water purification washed 2 times, 150 DEG C of dryings 3.0 hours.Catalyst preparation conditions in the same manner as in Example 1 is adopted to obtain catalyst D.
Comparative example 1
The step identical with embodiment 1 and condition is shaping, dry and roasting, and do not carry out acid treatment.Catalyst preparation conditions in the same manner as in Example 1 is adopted to obtain catalyst E.
Comparative example 2
The step identical with embodiment 1 and condition is shaping, dry and roasting, to gained carrier spray concentration be the acetic acid solution of 8wt% to saturated water absorption, 50 DEG C of closed processes 2.0 hours, water purification washs 2 times.150 DEG C of dryings 3.0 hours.Catalyst preparation conditions in the same manner as in Example 1 is adopted to obtain catalyst F.
Comparative example 3
This comparative example is by US4, and 448,896 methods described prepare Kaolinite Preparation of Catalyst after carrier.
Boehmite dry glue powder 500g as hereinbefore, adds sesbania powder 15g, is mixed into 11g high wear-resistant carbon black in dry glue powder, and after abundant kneading, 650 DEG C of roastings 3 hours, obtain carrier.The catalyst preparation conditions identical with embodiment 1 is adopted to obtain catalyst G.
Embodiment 5
This example is physicochemical property and the Activity evaluation of above each routine catalyst.
Carrier or catalyst from granular center to the average pore diameter assay method of outer surface different piece are: first with the pore volume of low-temperature nitrogen adsorption method (BET) working sample, specific area and average pore diameter, then get a certain amount of sample and be placed in attrition of catalyst instrument, grinding process is carried out to sample, adds a certain amount of quartz sand or alumina particle to increase the rate of wear simultaneously.When sample is reduced to a certain degree through polishing particle diameter, the working sample loss in weight also measures its pore structure again, the pore volume total by sample and surface area equal the relation of each several part sum, can calculate pore volume and the specific area of the part polished off, and then calculate its average pore diameter.Determine the average pore diameter from outer surface to granular center different piece thus.
Each routine carrier physicochemical property is in table 1.The physicochemical property of each routine catalyst is in table 2.From table 1 and table 2, carrier of the present invention and its average pore diameter of corresponding catalyst are from granular center to outer surface in increasing gradually, and duct permeability is better; And comparative example carrier and catalyst average pore diameter do not change.
Evaluation feedstock oil character is in table 3.
During evaluate catalysts, hydrogen and feedstock oil mixing after pass through beds, first through the first reactor Hydrodemetalation catalyst, then in the second reactor more than each routine catalyst, take hydrogen One-through design, HDM catalyst is with batch industrial products.The process conditions evaluating each routine catalyst employing are all identical, are respectively: reaction pressure (hydrogen dividing potential drop), 16.0MPa; Reaction temperature, 385 DEG C; Total liquid hourly space velocity (LHSV), 0.26h
-1; Hydrogen-oil ratio (v), 1000.Single reactor constant temperature zone volume 300cm
3, metal remover filling 100cm
3, above each routine catalyst 194cm
3.Evaluation result is in table 4.
From this example, the inventive method obtains catalyst and has higher hydrodesulfurization activity and good activity stability.
Table 1 carrier physicochemical property
﹡ refers to the average pore diameter of a carrier part
﹡ ﹡ refers to that on carrier cross section, certain a bit accounts for the percentage of its cross sectional radius apart from the distance of carrier particle exterior surface
Table 2 catalyst physicochemical property
Table 3 feedstock oil character
| Character | Husky light normal slag |
| Density (20 DEG C)/gcm -3 | 0.98 |
| S,wt% | 3.9 |
[0058] table 4 catalyst desulfurizing activity stability evaluation result
Claims (8)
1. an inferior heavy oil Hydrobon catalyst take aluminium oxide as carrier, and with VIII and group vib metal for active component, catalyst pore volume is 0.45 ~ 0.60cm
3/ g, specific area is 205 ~ 260m
2/ g, average pore size is 7.0 ~ 12.0nm, it is characterized in that along catalyst granules radial direction its average pore diameter from center to outer surface be increase gradually.
2., according to catalyst described in claim 1, it is characterized in that the average pore diameter of described catalyst 50% part from granular center to particle diameter is compared with the little 1 ~ 5nm of the average pore diameter of particle diameter 90% to surface portion.
3., according to catalyst described in claim 1, it is characterized in that VIII element be Ni, VIB element is Mo, described catalyst by weight containing NiO2 ~ 5%, MoO
312 ~ 16%.
4. a preparation method for catalyst described in claim 1, is characterized in that: comprise the following steps:
(1) take boehmite dry glue powder, add water, peptizing agent and extrusion aid, extruded moulding after abundant kneading drying, roasting, obtain alumina support;
(2) to the even shower water of (1) gained carrier, while shower water, in water, acid or acid solution is at the uniform velocity added, until reach the saturated water absorption of carrier; Closed processes under higher than the condition of room temperature, then with water purification washing, and dry;
(3) by the solution impregnation of nickeliferous and molybdenum by the strip of (2) gained and dry, roasting, obtained final catalyst.
5. according to preparation method described in claim 4, it is characterized in that: in step (1), the roasting condition of carrier is rise to 550 ~ 750 DEG C with the speed of 100 ~ 200 DEG C/h, constant temperature 2 ~ 5 hours.
6., according to preparation method described in claim 4, it is characterized in that acid described in step (2) is for nitric acid, acetic acid or phosphoric acid.
7. according to preparation method described in claim 4, it is characterized in that: described in step (2), closed processes temperature is 40 ~ 95 DEG C, the time is 1 ~ 4 hour; Described baking temperature is 105 ~ 300 DEG C.
8. according to preparation method described in claim 4, it is characterized in that: in step (3), catalyst sintering temperature is 460 ~ 540 DEG C, and the time is 2 ~ 5 hours.
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Cited By (5)
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| CN106914249A (en) * | 2015-12-24 | 2017-07-04 | 中国石油天然气股份有限公司 | Residuum hydrogenating and metal-eliminating catalyst and preparation method thereof |
| CN106914250A (en) * | 2015-12-24 | 2017-07-04 | 中国石油天然气股份有限公司 | Catalyst for hydrotreatment of residual oil and preparation method thereof |
| CN107983405A (en) * | 2016-10-26 | 2018-05-04 | 中国石油化工股份有限公司 | A kind of preparation method of hydrogenation catalyst |
| CN107983326A (en) * | 2016-10-26 | 2018-05-04 | 中国石油化工股份有限公司 | A kind of preparation method of hydrogenation catalyst shaping carrier |
| CN108452846A (en) * | 2017-10-27 | 2018-08-28 | 中国石油天然气股份有限公司 | Gasoline hydrogenation treatment catalyst and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106914249A (en) * | 2015-12-24 | 2017-07-04 | 中国石油天然气股份有限公司 | Residuum hydrogenating and metal-eliminating catalyst and preparation method thereof |
| CN106914250A (en) * | 2015-12-24 | 2017-07-04 | 中国石油天然气股份有限公司 | Catalyst for hydrotreatment of residual oil and preparation method thereof |
| CN106914250B (en) * | 2015-12-24 | 2019-07-05 | 中国石油天然气股份有限公司 | Catalyst for hydrotreatment of residual oil and preparation method thereof |
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| CN107983405A (en) * | 2016-10-26 | 2018-05-04 | 中国石油化工股份有限公司 | A kind of preparation method of hydrogenation catalyst |
| CN107983326A (en) * | 2016-10-26 | 2018-05-04 | 中国石油化工股份有限公司 | A kind of preparation method of hydrogenation catalyst shaping carrier |
| CN107983405B (en) * | 2016-10-26 | 2020-08-18 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN107983326B (en) * | 2016-10-26 | 2020-08-18 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst forming carrier |
| CN108452846A (en) * | 2017-10-27 | 2018-08-28 | 中国石油天然气股份有限公司 | Gasoline hydrogenation treatment catalyst and preparation method thereof |
| CN108452846B (en) * | 2017-10-27 | 2020-08-07 | 中国石油天然气股份有限公司 | Gasoline hydrofining catalyst and preparation method thereof |
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