CN105080583A - Condensed ring aromatic saturation catalyst with strong raw material adaptability - Google Patents
Condensed ring aromatic saturation catalyst with strong raw material adaptability Download PDFInfo
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Abstract
The present invention relates to a condensed ring aromatic saturation catalyst with strong raw material adaptability, and mainly solves the problems that a catalyst in the prior art is not strong in material adaptability, and cannot simultaneously treat sulfur-containing and sulfur-free raw materials. The condensed ring aromatic saturation catalyst comprises the following components by weight: a) 0.2-35wt% of at least one of Group VIII or Group VIB metals; b) 0.2-25wt% of phosphorus; and c ) 40-99.6wt% of a carrier, by the technical scheme, the problem is well solved, and the catalysts can treat sulfur-containing and sulfur-free raw materials, and can be used in condensed ring aromatic saturation industrial production.
Description
Technical field
The present invention relates to the condensed-nuclei aromatics saturation catalyst that a kind of adaptability to raw material is strong, particularly about a kind of can by double ring arene, thrcylic aromatic hydrocarbon or the sulfur-bearing containing condensed-nuclei aromatics mixture or catalyst that sulfur-bearing raw material is effectively unsaturated.
Background technology
Condensed-nuclei aromatics refers to and comprises naphthalene system double ring arene, a hydrocarbon of anthracene, phenanthrene system thrcylic aromatic hydrocarbon.The by-product coal tar of coking of coal is general containing naphthalene 10wt%.200 ~ 250oC the cut obtained during Doak Tar Oil, claims fraction of naphthalene oil, is wherein about 50wt% containing naphthalene.Along with the development of DCL/Direct coal liquefaction industry, the chemical utilization of a large amount of liquefied coal coil is also a difficult problem, and within the scope of 200-360oC cut, the total content of condensed-nuclei aromatics and tetrahydrochysene naphthalene series aromatics is more than more than 60%.Catalytic cracking light cycle oil, total arene content is up to 80%, and naphthalene system double ring arene accounts for about 70%.Usually also containing impurity such as higher sulphur nitrogen in coal tar, liquefied coal coil and catalytic cracking light cycle oil.In the heavy aromatics tail oil of Aromatic Hydrocarbon United Plant, condensed-nuclei aromatics content is greater than 60% usually, but because raw material is from reformer unit, wherein the not impurity such as sulfur-bearing nitrogen substantially.
These raw materials being rich in condensed-nuclei aromatics, because of reasons such as density are high, ignition performance is poor, can not be directly used in vehicle fuel.Usually need remove sulphur nitrogen impurity wherein through hydrogenation process, and make condensed-nuclei aromatics wherein and olefin substitute be improve product property after saturated hydrocarbons, open loop, chain rupture, produce derv fuel, gasoline or chemical products.Therefore, the exploitation of aromatic hydrocarbon saturation catalyst is subject to the attention of petrochemical industry researcher always.
The condensed-nuclei aromatics saturation catalyst that the metal sulfide of alumina load is the most frequently used, the research report of this respect is the abundantest.Patent CN1171429A has invented the preparation method of the aromatic hydrocarbon hydrogenation catalyst of a kind of nickel-loaded and tungsten active metal, and toluene is higher to the conversion ratio of hexahydrotoluene and dimethylbenzene pentamethylene.But these metal components must the good hydrogenation effect of competence exertion after curing, if process not sulfur-bearing Aromatic Hydrocarbon United Plant heavy aromatics tail oil completely, sulfide type catalyst is by because the slow loss of element sulphur and loss of activity gradually.Patent CN103059916A have also been invented a kind of metal sulphide type catalyst for light cycle oil hydro-conversion, and the conversion ratio of polycyclic aromatic hydrocarbon is greater than 30%, has good hydrotreated lube base oil effect.But this catalyst can only be used for the process of sulfur-bearing raw material equally.
In the non-sulfur-bearing raw material of process, the aromatic hydrocarbon hydrogenation catalyst of carried noble metal has to be applied more widely.Patent US20100200462 invents a kind of by platinum, the catalyst of palladium load on silica/zirconia/alumina composite carrier, and due to the formation of platinum-nickel alloys and the use of composite oxide carrier, the sulfur resistive ability of catalyst is the highest can only arrive 1000ppm.In coal tar, liquefied coal coil and catalytic cracking light cycle oil, sulfur content is usually all far above 1000ppm, simultaneously also containing a considerable amount of Nitrogen Impurities.Up to now, the process that the catalyst of carried noble metal is used for high sulfur-bearing condensed-nuclei aromatics raw material is rarely seen in actual industrial process, noble metal easily in sulfur-bearing nitrogen environment the high cost of poisoning and deactivation and noble metal be topmost reason.
Except the catalyst of loaded metal sulfide and noble metal, the exploitation of the catalyst of load novel hydrogenation function ingredients is also seen in report.Patent CN101099934A has invented a kind of metal nitride catalyst for aromatic saturated hydrogenation, and its metal component is nickel and molybdenum, and under the formulation condition optimized, dimethylbenzene and naphthalene almost hydrotreated lube base oil reaction occur completely thereon.Be summed up, metal sulphide type catalyst can only process sulfur-bearing raw material, noble metal type catalyst then can only be used for not sulfur-bearing or low sulfur-bearing raw material, the range of application of metal nitride type catalyst may be wider, but the nitrogenize of metal and preprocessor are too complicated, need to develop the stronger condensed-nuclei aromatics hydrocatalyst for saturating of a kind of adaptability to raw material.
Summary of the invention
One of technical problem to be solved by this invention is the problem of the adaptability to raw material difference of the condensed-nuclei aromatics saturation catalyst existed in conventional art, provides a kind of adaptable condensed-nuclei aromatics saturation catalyst that not only can process high sulfur-bearing raw material but also can process not sulfur-bearing raw material.This catalyst is used in the saturated reaction containing condensed-nuclei aromatics mixture, the advantage such as have that adaptability to raw material is strong, condensed-nuclei aromatics conversion ratio is high and catalyst stability is strong.
Two of technical problem to be solved by this invention is to provide the purposes of the catalyst of one of a kind of technical solution problem.
In order to one of solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of condensed-nuclei aromatics saturation catalyst, comprises following component by weight percentage: at least one a) in the VIII of 0.2 ~ 35wt% or group vib metal; B) phosphorus of 0.2 ~ 25wt%; C) carrier of 40 ~ 99.6wt%.
In technique scheme, in catalyst, the mol ratio of metallic element and P elements is between 3/1 and 1/1; The content of VIII or group vib metal is 0.5 ~ 25wt%; The content of P elements is 0.5 ~ 15wt%; Carrier contains at least one in aluminium oxide, silica, zirconia, titanium oxide, magnesia; The sulfur content of the raw material that catalyst is suitable for is between 0 ~ 1.5wt%; In catalyst, group VIII metal element is selected from least one in cobalt and nickel, and in catalyst, group vib metallic element is selected from least one in molybdenum and tungsten.
The hydrocatalyst for saturating arylhydrocarbon of non-noble metal sulfided thing load, needs the operating conditions such as harsh pressure usually because hydrogenation capability is weak, the run off deactivation prob that brings of element sulphur also limit its use under sweet stock condition.Noble metal is as the catalyst at hydrogenating function center, and production cost is high, and sulfur resistive nitrogen poisoning capability is not strong, is not suitable for high sulfur-bearing raw material.The metal phosphide that VIII or group vib metal and phosphorus are formed has the hydrogenation capability of similar noble metal, and sulfur resistive nitrogen poisoning capability is strong, not only can be used for processing high sulfur-bearing raw material but also can be used for processing not sulfur-bearing raw material, and catalyst low cost of manufacture.
In order to solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of hydrotreated lube base oil method of condensed-nuclei aromatics, take condensed-nuclei aromatics as raw material, under the hydrogen atmosphere of pressure 2.0-15.0MPa, feed sulphur content is between 0-3.0wt%, raw material is by any one catalyst above-mentioned, condensed-nuclei aromatics generation hydrotreated lube base oil reacts, and generates the saturated aromatic hydrocarbons comprising naphthane system.
In technique scheme, preferred technical scheme is, reaction pressure 3.0 ~ 10.0MPa, reaction temperature 320 ~ 450 DEG C, weight space velocity 0.2 ~ 4.0h
-1.
In the present invention, the preparation method of catalyst is as follows: by least one in aluminium oxide, silica, zirconia, titanium oxide, magnesia, after kneading aftershaping, drying, roasting, obtain carrier.The water soluble salt and phosphoric acid, phosphate, phosphorous acid or hypophosphorous acid that are selected from VIII or group vib metal are dissolved in suitable quantity of water, and load on carrier by dipping method, dry and roasting.Before use, catalyst also needs to reduce more than two hours in hydrogen.
By catalyst of the present invention, be applied in the hydrotreated lube base oil reaction of condensed-nuclei aromatics, under the hydrogen atmosphere of pressure 2.0-15.0MPa, feed sulphur content is between 0-3.0wt%, the reaction of condensed-nuclei aromatics generation hydrotreated lube base oil generates the aromatic hydrocarbons of the fractional saturations such as naphthane system, conversion ratio is greater than more than 80%, achieves good technique effect.
Below by embodiment, the invention will be further elaborated.
Detailed description of the invention
In embodiment 1 ~ 5, catalyst preparing all adopts chemical pure level reagent.Sweet stock is Aromatic Hydrocarbon United Plant heavy aromatics tower tail oil, condensed-nuclei aromatics content 72%; High sulfur-bearing raw material is the catalytic cracking light cycle oil of sulfur content 3100ppm, condensed-nuclei aromatics content 65%.Condensed-nuclei aromatics saturation factor and hydrotreated lube base oil selective calculation formula as follows:
[embodiment 1]
90wt% gross porosity silica powder, 10wt% magnesia powder are by roller forming method Kaolinite Preparation of Catalyst body, stand-by after 650oC roasting.With ammonium molybdate, nickel nitrate, diammonium hydrogen phosphate and ammoniacal liquor mixed solution by incipient impregnation method, load 6wt%Mo, 2.1wt%Ni and 5.5wt%P, dry and can obtain catalyst A after roasting 2h in 450oC air.
[embodiment 2]
Zirconium oxychloride is hydrolyzed in ammoniacal liquor, processes 48h under 120oC hydrothermal condition, filtration, washing, drying, then prepares zirconia-type catalyst carrier by the method for kneading, extrusion.With ammonium molybdate, phosphorous acid and ammoniacal liquor mixed solution by incipient impregnation method, load 8.2wt%Mo and 5.7wt%P, dries and can obtain catalyst B after roasting 2h in 380oC air.
[embodiment 3]
90g gross porosity silica and 30g boehmite fully mix, and add 1:1 nitric acid and suitable quantity of water, extrusion, room temperature health after kneading, and 120oC is dried and spent the night, and in 550oC air atmosphere, namely roasting 4h obtains catalyst carrier.With nickel nitrate, phosphoric acid, cerous nitrate and nitric acid mixed solution by incipient impregnation method, load 7.0wt%Ni, 1.5wt%Ce and 3.2%P, dry and namely roasting 2h obtains catalyst C in 450oC air.
[embodiment 4]
Gross porosity silica powder prepares spheric catalyst body by roller forming method.Nickel nitrate, ammonium paratungstate and diammonium hydrogen phosphate mixed solution are by incipient impregnation method, and load 2.0wt%Ni, 9.5wt%Ce and 4.5%P, dry and namely roasting 2h obtains catalyst D in 500oC air.
[embodiment 5]
85wt% gross porosity silica and 15wt% metatitanic acid fully mix, and prepare spheric catalyst body by roller forming method.Cobalt nitrate and hypophosphorous acid mixed solution are by incipient impregnation method, and load 9.0wt%Co and 4.5wt%P, dries and namely roasting 4h obtains catalyst E in 280oC air.
[embodiment 6]
Be mixed into 2g sesbania powder in 100g boehmite, to add 1:1 nitric acid and suitable quantity of water, extrusion, room temperature health after kneading, 120oC is dried and is spent the night, and in 550oC air atmosphere, namely roasting 4h obtains alumina catalyst carrier.Cobalt nitrate, ammonium molybdate, ammonium dihydrogen phosphate (ADP) and ammoniacal liquor mixed solution are by incipient impregnation method, and load 2.5wt%Co, 10.5%Mo and 5.8wt%P, dry and namely roasting 4h obtains catalyst F in 450oC air.
[embodiment 7 ~ 12]
The catalyst of Example 1-6 is used for the reaction of condensed-nuclei aromatics generation hydrotreated lube base oil successively.
All catalyst all need to reduce in hydrogen before use, and pressure 3MPa, reducing condition is as shown in table 1.
Sweet stock 1 consists of 20wt% naphthalene and 80wt% toluene; Sulfur-bearing raw material 2 consists of 20wt% naphthalene and 80wt% toluene, wherein allocates benzothiophene into, and amounting to sulfur content is 520ppm.Reaction pressure 3.0MPa, reaction temperature 360oC, weight space velocity 2h
-1, hydrogen/oil mol ratio is 6:1.For examining or check the sulfur resistive ability of catalyst, naphthalene conversion ratio and saturated selective be all that product analysis result after adopting online 100h calculates.
Table 1
Claims (10)
1. the condensed-nuclei aromatics saturation catalyst that adaptability to raw material is strong, by weight percentage, comprises following component:
A) at least one in the VIII of 0.2 ~ 35wt% or group vib metallic element;
B) phosphorus of 0.2 ~ 25wt%;
C) carrier of 40 ~ 99.6wt%.
2. the condensed-nuclei aromatics saturation catalyst that adaptability to raw material according to claim 1 is strong, is characterized in that the mol ratio of metallic element and P elements in catalyst is between 3/1 and 1/1.
3. the condensed-nuclei aromatics saturation catalyst that adaptability to raw material according to claim 1 is strong, is characterized in that the content of VIII or group vib metal is 0.5 ~ 25wt%; The content of P elements is 0.5 ~ 15wt%, and the content of carrier is 60 ~ 99%.
4. the condensed-nuclei aromatics saturation catalyst that adaptability to raw material according to claim 1 is strong, is characterized in that at least one contained at carrier in aluminium oxide, silica, zirconia, titanium oxide, magnesia.
5. the condensed-nuclei aromatics saturation catalyst that adaptability to raw material according to claim 1 is strong, is characterized in that in catalyst weight percent, content is 0.5 ~ 15wt% also containing at least one in VIII or group vib metallic element in catalyst.
6. the condensed-nuclei aromatics saturation catalyst that adaptability to raw material according to claim 1 is strong, is characterized in that the sulfur content of the raw material that catalyst is suitable for is between 0 ~ 3.0wt%.
7. the condensed-nuclei aromatics saturation catalyst that adaptability to raw material according to claim 1 is strong, is characterized in that in catalyst, group VIII metal element is selected from least one in cobalt and nickel.
8. the condensed-nuclei aromatics saturation catalyst that adaptability to raw material according to claim 1 is strong, is characterized in that in catalyst, group vib metallic element is selected from least one in molybdenum and tungsten.
9. the hydrotreated lube base oil method of a condensed-nuclei aromatics, take condensed-nuclei aromatics as raw material, under the hydrogen atmosphere of pressure 2.0 ~ 15.0MPa, feed sulphur content is between 0 ~ 3wt%, raw material is by any one catalyst in claim 1 to 8, condensed-nuclei aromatics generation hydrotreated lube base oil reacts, and generates the saturated aromatic hydrocarbons comprising naphthane system.
10. the hydrotreated lube base oil method of condensed-nuclei aromatics according to claim 9, is characterized in that reaction pressure 3.0 ~ 10.0MPa, reaction temperature 320 ~ 450 DEG C, weight space velocity 0.2 ~ 4.0h
-1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106563476A (en) * | 2016-11-09 | 2017-04-19 | 西南化工研究设计院有限公司 | Catalyst used for reaction for preparing tetrahydronaphthalene through naphthalene hydrogenation and preparation method and application of catalyst |
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| CN101041139A (en) * | 2007-04-30 | 2007-09-26 | 京福马(北京)石油化工高新技术有限公司 | Catalyzer for regenerating the waste lubricant oil by hydrogenation and the preparing method |
| CN101687183A (en) * | 2007-06-25 | 2010-03-31 | Ifp公司 | Process for preparing a hydroprocessing catalyst by impregnation of a phosphorus compound |
| CN103030487A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Method of aromatics hydrogenation saturation |
| CN103055909A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Catalyst for light cycle oil selective hydrodesulfurization and preparation method thereof |
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Patent Citations (4)
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| CN101041139A (en) * | 2007-04-30 | 2007-09-26 | 京福马(北京)石油化工高新技术有限公司 | Catalyzer for regenerating the waste lubricant oil by hydrogenation and the preparing method |
| CN101687183A (en) * | 2007-06-25 | 2010-03-31 | Ifp公司 | Process for preparing a hydroprocessing catalyst by impregnation of a phosphorus compound |
| CN103030487A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Method of aromatics hydrogenation saturation |
| CN103055909A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Catalyst for light cycle oil selective hydrodesulfurization and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106563476A (en) * | 2016-11-09 | 2017-04-19 | 西南化工研究设计院有限公司 | Catalyst used for reaction for preparing tetrahydronaphthalene through naphthalene hydrogenation and preparation method and application of catalyst |
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Application publication date: 20151125 |