CN104226237A - Fine heavy-naphtha desulfurization catalyst and preparation method thereof - Google Patents
Fine heavy-naphtha desulfurization catalyst and preparation method thereof Download PDFInfo
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- CN104226237A CN104226237A CN201310259931.9A CN201310259931A CN104226237A CN 104226237 A CN104226237 A CN 104226237A CN 201310259931 A CN201310259931 A CN 201310259931A CN 104226237 A CN104226237 A CN 104226237A
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Abstract
The invention discloses a fine heavy-naphtha desulfurization catalyst and a preparation method thereof. The fine desulfurization catalyst comprises the following components in percentage by weight: 30-80 percent of zinc oxide, 5-30 percent of aluminum oxide, 8-10 percent of an active component, 8-10 percent of an adhesive, 0.5-1.5 percent of a VIII-group metal oxide, 3-5 percent of an adsorption-assistant component and 5-10 percent of an enhancement component. The enhancement component is added into the raw material of the fine desulfurization catalyst, so that the intensity of fine desulfurization catalyst particles can reach up to over 40N/particle; the intensity is high, so that the particles cannot be cracked, and the service life is long.
Description
Technical field
The present invention relates to and to belong in petroleum refining process the process for refining of oil product and desulfurizing agent preparation field, be specifically related to a kind of heavy naphtha fine desulfurization catalyst and preparation method thereof.
Background technology
Along with the continuous enhancing of people's environmental consciousness, various environmental pollution more and more becomes the focus that people pay close attention to.In the recent decade, the developed countries such as America and Europe have promulgated the new standard that a series of oil product cleans successively, and fuel oil has become a kind of trend without sulfuration.No matter and China's fuel oil products, in specification standards or actual mass, all has larger gap with developed countries at present.The sulfur content required by environmental legislation become more and more lower while, the demand of countries in the world to light-end products increases day by day, thus develop fuel oil especially the research work of light-end products ultra-deep desulfurization just seem most important.
The method of desulfurizing oil is a lot, traditional maturation method has hydrodesulfurization (HDS), but in order to realize ultra-deep desulfurization, hydrogenation reaction must be carried out at high temperature under high pressure, and with using highly active catalyst, thus plant investment and operating cost large, hydrodesulfurization simultaneously can cause the remarkable reduction of octane number, therefore, numerous scholar is studied easy to operate, lower-cost non-hydro desulfurizations such as adsorption desulfurize, oxidation sweetening, abstraction desulfurizations, wherein, adsorption desulfurize technology becomes the focus of research both at home and abroad.Compared with additive method, adsorption desulfurize technology has following advantage: operating condition is gentle, investment and operating cost low, desulfurized effect is good, and selectable adsorbent species is many, and adsorbent is renewable, low in the pollution of the environment, meanwhile, adopt absorption method to carry out desulfurizing oil and can not reduce active ingredient in oil product, octane number is not affected.
At present, for adsorption desulfurizing agent, studying more has molecular screen base desulfurizing agent, absorbent charcoal based desulfurizing agent, clay-based desulfurizing agent etc.Adopt clay-based desulfurizing agent and metal oxide to prepare with mechanical mixing, preparation method is comparatively simple, is easy to extensive use, and raw material sources are wide simultaneously, cheap, therefore industrial normal employing clay-based desulfurizing agent.
Chinese invention patent CN1326977C provides a kind of catalytic gasoline absorbing desulfurization catalyst and preparation method, its weight percent consists of: the zinc oxide 10 ~ 85% that particle diameter is 100 ~ 500 μm, silica 5 ~ 80%, aluminium oxide 5 ~ 30% and reduced state nickel 4 ~ 45%, each component exists in hybrid form, adopt roasting technique, intensity is good, desulphurizing activated height, favorable regeneration effect, is applicable to the desulfurization of gasoline.This desulfurizing agent is that one faces hydrogen absorbing desulfurization catalyst.
Chinese invention patent CN1183996C discloses a kind of iron oxide compound desulfurizer and preparation method thereof, belong to Fe-Zn system composite desulfurizing agent, adopt special auxiliary agent, be composited with insoluble molysite, zinc salt active component, each constituent content is (wt%): iron oxide 30 ~ 70%, zinc oxide 5 ~ 30%, auxiliary agent 5 ~ 30%, adopts the preparation technology of compression molding.The present invention has that desulfurization precision is high, low cost and other advantages, and alternative Zinc oxide desulfurizer is widely used in warm fine de-sulfur in oil refinery dry gas, naphtha, coker gasoline, semiwater gas, oven gas etc.
Chinese invention patent CN100489062C discloses a kind of concavo-convex rod gasoline desulfurizer, and its drip irrigation device is, concavo-convex rod gasoline desulfurizer is made up of Concave-convex clay rod, iron oxide, aluminium oxide, cupric oxide and zinc oxide.Its preparation method carries out acidification by adding nitric acid after the mixing of desulfurizing agent batching, and extruding airing, crushing and screening, roasting is packaged as finished product.This desulfurizing agent is applicable to the sulfur removal technology of gasoline, diesel oil and aviation kerosine.
The clay-based desulfurizing agent adopting solid mechanical mixing method to prepare is easily little at porosity, specific surface, desulphurizing activated and selective low problem.The general desulfurization scope of existing desulfurizing agent is that 100 ~ 1000ppm takes off to 5 ~ 50ppm, and noble metal component immerses in the high surface area carriers such as molecular sieve by ultra-deep desulfurization agent many employings infusion process or ion-exchange, and preparation method is complicated, is not suitable for large-scale application.
For solving the problem, Chinese invention patent CN101940908B discloses a kind of ultra-deep absorption desulfurizer for light oil and uses thereof.Desulfurizing agent involved in the present invention comprises following component: 10.0 ~ 80.0% zinc oxide, 5.0 ~ 75.0%VIII metal oxide, 1.0 ~ 50.0% help absorbed component, 1.0 ~ 10.0% expanding agents and 10.0 ~ 35.0% adhesives, Homogeneous phase mixing, compressing tablet or extrusion, drying, to bake, obtained desulfurizing agent.Adsorption desulfurizing agent prepared by the present invention does not use noble metal, low price; Adopt mixing, roasting technique, preparation method is simple, easy to operate; The desulphurizing activated height of this desulfurizing agent, favorable regeneration effect, can process the light-end products that sulfur content is extremely low, and after process, light-end products medium sulphide content content can be down to below 0.5ppm, is applicable to low temperature fine de-sulfur process in naphtha, gasoline, diesel oil, aviation kerosine etc.But do not add reinforcing material in the component of this invention desulfurizing agent, sorbent particle intensity is low, easily cracked, affects desulfurized effect.
Summary of the invention
The object of the invention is to provide a kind of heavy naphtha fine desulfurization catalyst and preparation method thereof, and sorbent particle intensity is high, and pressure drop is little, long service life.
For achieving the above object, the technical solution used in the present invention is: a kind of heavy naphtha fine desulfurization catalyst, comprise following component by weight percentage: zinc oxide 30 ~ 80%, aluminium oxide 5 ~ 30%, active component 8 ~ 10%, adhesive 8 ~ 10%, group VIII metal oxide 0.5 ~ 1.5%, help absorbed component 3 ~ 5%, strengthen component 5 ~ 10%.
In technique scheme, described aluminium oxide is selected from boehmite, gibbsite, bayerite, boehmite, gama-alumina, Alpha-alumina, δ-aluminium oxide, θ-aluminium oxide or their mixture, the boehmite of preferred macropore.
In technique scheme, described active component is rare earth element.
In technique scheme, described adhesive is kaolin, attapulgite, the sweet soil of sheep, diatomite or imvite, preferred attapulgite.
In technique scheme, described group VIII metal oxide is iron oxide, nickel oxide or cobalt oxide, preferential oxidation nickel.
In technique scheme, described in help absorbed component to be titanium oxide, cupric oxide or molybdenum oxide, preferential oxidation molybdenum.
In technique scheme, described enhancing component is alumina cement, can select CS-80 alumina cement.
The embodiment of the present invention also provides the preparation method of the heavy naphtha fine desulfurization catalyst according to any one of a kind of claim 1 ~ 7, comprises the steps:
(1) by formula by described zinc oxide, aluminium oxide, active component, adhesive, group VIII metal oxide, help absorbed component and strengthen component weigh after mix, and add water stir make material base;
(2) step (1) gained catalyst material mold is made fine desulfurization catalyst particle;
(3) catalyst granules at 80 ~ 120 DEG C dry 10 ~ 24 hours, then roasting obtained fine desulfurization catalyst grain products after 3 ~ 4 hours under 550 ~ 600 DEG C of air atmosphere.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1. the present invention adds enhancing component in the raw material of fine desulfurization catalyst, and make the intensity of fine desulfurization catalyst particle can reach more than 40N/ grain, intensity is high, and particle can not be cracked, long service life.
2. the specific surface of fine desulfurization catalyst particle of the present invention can reach 100m
2/ g, strengthening adsorption effect.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described:
Sulphur compound in heavy naphtha comprises: H
2s, disulphide, mercaptan and derivative thereof, thiophene and derivatives, thioether and derivative thereof etc.
Embodiment one: zinc oxide, aluminium oxide, lanthanum, kaolin, nickel oxide, molybdenum oxide and enhancing component are mixed in mass ratio at 7: 2: 0.8: 0.8: 0.15: 0.3: 0.5, necessity also can add appropriate self-control AT-1 expanding agent, add suitable quantity of water to stir, make material base.
Then above-mentioned catalyst material mold is made fine desulfurization catalyst particle.
Finally by catalyst granules, at 80 ~ 120 DEG C, drying is after 10 ~ 24 hours, and under 550 ~ 600 DEG C of air atmosphere, roasting obtained fine desulfurization catalyst grain products after 3 ~ 4 hours, and specific area can reach 100m
2/ more than g, granule strength can reach more than 40N/ grain.
The present invention adds enhancing component in the raw material of fine desulfurization catalyst, and make the intensity of fine desulfurization catalyst particle can reach more than 40N/ grain, intensity is high, and particle can not be cracked, long service life.The specific surface of fine desulfurization catalyst particle of the present invention can reach 100m
2/ g, strengthening adsorption effect.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from principle of the present invention; can also make some improvement and adjustment, these improve and adjustment also should be considered as protection scope of the present invention.
Claims (8)
1. a heavy naphtha fine desulfurization catalyst, it is characterized in that: comprise following component by weight percentage: zinc oxide 30 ~ 80%, aluminium oxide 5 ~ 30%, active component 8 ~ 10%, adhesive 8 ~ 10%, group VIII metal oxide 0.5 ~ 1.5%, helps absorbed component 3 ~ 5%, strengthens component 5 ~ 10%.
2. heavy naphtha fine desulfurization catalyst according to claim 1, is characterized in that: described aluminium oxide is selected from boehmite, gibbsite, boehmite, gama-alumina, Alpha-alumina, δ-aluminium oxide, θ-aluminium oxide or their mixture.
3. heavy naphtha fine desulfurization catalyst according to claim 1, is characterized in that: described active component is rare earth element.
4. heavy naphtha fine desulfurization catalyst according to claim 1, is characterized in that: described adhesive is kaolin, attapulgite, the sweet soil of sheep, diatomite or imvite.
5. heavy naphtha fine desulfurization catalyst according to claim 1, is characterized in that: described group VIII metal oxide is iron oxide, nickel oxide or cobalt oxide.
6. heavy naphtha fine desulfurization catalyst according to claim 1, is characterized in that: described in help absorbed component to be titanium oxide, cupric oxide or molybdenum oxide.
7. heavy naphtha fine desulfurization catalyst according to claim 1, is characterized in that: described enhancing component is alumina cement.
8. a preparation method for the heavy naphtha fine desulfurization catalyst according to any one of claim 1 ~ 7, is characterized in that: comprise the steps:
(1) by formula by described zinc oxide, aluminium oxide, active component, adhesive, group VIII metal oxide, help absorbed component and strengthen component weigh after mix, and add water stir make material base;
(2) step (1) gained catalyst material mold is made fine desulfurization catalyst particle;
(3) catalyst granules at 80 ~ 120 DEG C dry 10 ~ 24 hours, then roasting obtained fine desulfurization catalyst grain products after 3 ~ 4 hours under 550 ~ 600 DEG C of air atmosphere.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101940908A (en) * | 2009-07-08 | 2011-01-12 | 中国石油化工股份有限公司 | Ultra-deep absorption desulfurizer for light oil and application thereof |
| CN102807888A (en) * | 2012-08-26 | 2012-12-05 | 金堆城钼业股份有限公司 | Reformed raw oil desulfurizing agent and preparation method thereof |
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- 2013-06-24 CN CN201310259931.9A patent/CN104226237A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101940908A (en) * | 2009-07-08 | 2011-01-12 | 中国石油化工股份有限公司 | Ultra-deep absorption desulfurizer for light oil and application thereof |
| CN102807888A (en) * | 2012-08-26 | 2012-12-05 | 金堆城钼业股份有限公司 | Reformed raw oil desulfurizing agent and preparation method thereof |
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Application publication date: 20141224 |