CN103666553B - Method of hydro-conversion of polycyclic aromatic hydrocarbons - Google Patents
Method of hydro-conversion of polycyclic aromatic hydrocarbons Download PDFInfo
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Abstract
The invention discloses a method of hydro-conversion of polycyclic aromatic hydrocarbons. The method comprises the following steps: (1), in at least one hydrogenation reaction zone, enabling a material containing polycyclic aromatic hydrocarbons to contact with a hydrogenation catalyst for reaction in the presence of a hydrogen gas to obtain a reaction product with polycyclic aromatic hydrocarbons which are partly hydro-generated and saturated; and (2), in at least one hydrogen-cracking reaction zone, enabling the reaction product with polycyclic aromatic hydrocarbons partly hydro-generated and saturated, which is obtained in the step (1) to contact with a hydrogen-cracking catalyst for reaction in the presence of the hydrogen gas, wherein a conversation rate of the polycyclic aromatic hydrocarbons in the material containing the polycyclic aromatic hydrocarbons is over 40wt% by selecting the hydrogenation catalyst and operation conditions of the hydrogenation reaction zone; and relative yield of a monocyclic hydrogenation product in the products is 4%-80%; and the conversion rate of the polycyclic aromatic hydrocarbons based on the total amount of the polycyclic aromatic hydrocarbons in the material containing the polycyclic aromatic hydrocarbons is over 85wt% by selecting the hydro-cracking catalyst and the operation conditions in the hydrogen-cracking reaction zone, and the relative yield of the monocyclic hydrogen-cracking product in the products is 4%-30%.
Description
Technical field
The present invention relates to aromatic hydrogenation method for transformation.
Background technology
Crude resources is heaviness increasingly, main manifestations is that the aromaticity content in crude oil raises gradually, polycyclic aromatic hydrocarbon content particularly in heavy oil fraction raises gradually, and countries in the world increase day by day to the demand of light-end products, therefore, many heavy oil lighting technology are arisen at the historic moment, such as: catalytic cracking technology.But, mink cell focus is in catalytic cracking reaction process, polycyclic aromatic hydrocarbons wherein have quite a few polycondensation in catalytic cracking process be deposition of carbon on a catalyst, or be polymerized to the polycyclic aromatic hydrocarbons of more high molecular, in order to improve feed stock conversion and yield of light oil, to need catalytically cracked material through hydrotreatment to reduce the polycyclic aromatic hydrocarbon content of catalytic cracking feeds.
Such as, CN101463274A discloses a kind of hydrocarbon oil hydrogenation process and catalytic cracking combined technique of improvement, comprise: under hydrogen existence and hydrotreatment reaction conditions, by residual oil, catalytic cracking recycle oil together with optional distillate with hydrotreating catalyst contact reacts, reaction product isolated obtains gas, hydrotreated naphtha, hydrogenated diesel oil and hydrogenation tail oil; Under catalytic cracking reaction condition, by hydrogenation tail oil optionally together with Conventional catalytic cracking stock oil with catalytic cracking catalyst contact reacts, reaction product isolated obtains dry gas, liquefied gas, catalytically cracked gasoline, catalytic cracking diesel oil and catalytic cracking recycle oil; It is characterized in that, before described hydrogenation tail oil is contacted with catalytic cracking catalyst, under being also included in underpressure distillation condition, hydrogenation tail oil is at least cut into light, to weigh two cuts step, wherein, described cutting makes lighting end account for the 10-80 % by weight of hydrogenation tail oil total amount.The method is applicable to hydrocarbon oil conversion to produce more gasoline or diesel product.
CN101538481A discloses a kind of hydrocarbon oil hydrogenation process and catalytic cracking combination method of improvement, comprise: under hydrogen existence and hydrotreatment reaction conditions, by residual oil, catalytic cracking recycle oil together with optional distillate with hydrotreating catalyst contact reacts, reaction product isolated obtains gas, hydrotreated naphtha, hydrogenated diesel oil and hydrogenation tail oil; Under catalytic cracking reaction condition, by Conventional catalytic cracking stock oil optionally together with hydrogenation tail oil with catalytic cracking catalyst contact reacts, reaction product isolated obtains dry gas, liquefied gas, catalytically cracked gasoline, catalytic cracking diesel oil and catalytic cracking recycle oil; Described Conventional catalytic cracking stock oil be selected from light, weigh two kinds of distillates, described is by described heavier feedstocks oil and light stock oil with catalytic cracking catalyst contact reacts, optionally comprises in the reactor of at least two reaction zones I and II in the direction of the flowing along reaction mass together with hydrogenation tail oil respectively and carrying out successively.The method is applicable to hydrocarbon oil conversion to produce more gasoline and diesel oil.
CN1311289A and CN1309163A be disclosed reduces the method that boiling range is sulphur compound in the hydrocarbon charging of 200 DEG C-600 DEG C and polycyclic aromatic hydrocarbon content, the method comprises the steps: to make charging contact with hydrogen on hydroprocessing catalysts, hydrotreated feedstock under hydroprocessing conditions, the cooling effluent of hydrotreatment and the hydrogen-rich gas from hydrotreating reactor, in aftertreatment reactor, on hydroprocessing catalysts, be enough to, at the temperature reducing polycyclic aromatic hydrocarbon content, described effluent be contacted with hydrogen.
The outstanding problem that existing polycyclic aromatic hydrocarbons hydrocracking technology exists is that hydrogen consumption is high.
Summary of the invention
The technical problem to be solved in the present invention be to provide a kind of newly, hydrogen consumes the polycyclic aromatic hydrocarbons hydrogenating conversion process significantly reduced.
For the hydroconversion reactions of phenanthrene, the present inventor finds under study for action, when adopting the raw material comprising a hydroconversion reaction zone and a hydrocracking reaction zone processing high-content polycyclic aromatic hydrocarbons, by to the catalyzer of two reaction zones and the selection of reaction conditions, reaction can be made to carry out according to the direction of phenanthrene → dihydro phenanthrene → biphenyl selectivity raising.When adopting which to carry out polycyclic aromatic hydrocarbons hydroconversion reactions, while guaranteeing polycyclic aromatic hydrocarbons hydrocracking, hydrogen consumption obviously reduces.
The present invention relates to content to comprise:
1, a kind of method of hydrocracking polycyclic aromatic hydrocarbons, comprise: (1) is at least one hydroconversion reaction zone, in the presence of hydrogen gas by the raw material containing polycyclic aromatic hydrocarbons and hydrogenation catalyst contact reacts, obtain a kind of polycyclic aromatic hydrocarbons and be at least partly hydrogenated satisfied reaction product; (2) at least one hydrocracking reaction zone, reaction product at least partly by hydrotreated lube base oil of the polycyclic aromatic hydrocarbons that in the presence of hydrogen gas step (1) obtained and hydrocracking catalyst contact reacts; Wherein, the hydrogenation catalyst of described hydroconversion reaction zone and the selection of operational condition make the transformation efficiency containing the polycyclic aromatic hydrocarbons in the raw material of polycyclic aromatic hydrocarbons be more than 40 % by weight, and wherein the yield advantage of monocycle hydrogenation products is 4-80%; It is more than 85 % by weight that the described hydrocracking catalyst of hydrocracking reaction zone and the selection of operational condition make with the transformation efficiency of the polycyclic aromatic hydrocarbons being benchmark containing the polycyclic aromatic hydrocarbons total amount in the raw material of polycyclic aromatic hydrocarbons, and wherein the yield advantage of monocycle hydrocrackates is 4-30%.
2, the method according to 1, it is characterized in that, the hydrogenation catalyst of described hydroconversion reaction zone and the selection of operational condition make the transformation efficiency containing the polycyclic aromatic hydrocarbons in the raw material of polycyclic aromatic hydrocarbons be more than 55 % by weight, and wherein the yield advantage of monocycle hydrogenation products is 10-75%; The described hydrocracking catalyst of hydrocracking reaction zone and the selection of operational condition make the polycyclic aromatic hydrocarbons transformation efficiency to be benchmark containing the polycyclic aromatic hydrocarbons total amount in the raw material of polycyclic aromatic hydrocarbons be more than 90 % by weight, and wherein the yield advantage of monocycle hydrocrackates is 5-20%.
3, the method according to 1 or 2, is characterized in that, the operational condition of described hydroconversion reaction zone comprises: temperature of reaction is 150-350 DEG C, and reaction pressure is 1-20MPa, and mass space velocity is 0.01-4h
-1, hydrogen to oil volume ratio is 50-900; The reaction conditions of described hydrocracking reaction zone comprises: temperature of reaction is 280-450 DEG C, and reaction pressure is 1-20MPa, mass space velocity 0.1-4h
-1, hydrogen to oil volume ratio 100-900.
4, the method according to 3, is characterized in that, the operational condition of described hydroconversion reaction zone comprises: temperature of reaction is 180-300 DEG C, and reaction pressure is 2-15MPa, and mass space velocity is 0.1-2h
-1, hydrogen to oil volume ratio is 100-800; The reaction conditions of described hydrocracking reaction zone comprises: temperature of reaction is 320-400 DEG C, and reaction pressure is 2-15MPa, mass space velocity 0.2-3h
-1, hydrogen to oil volume ratio 200-800.
5, the method according to 4, is characterized in that, the operational condition of described hydroconversion reaction zone comprises: temperature of reaction is 200-300 DEG C, and reaction pressure is 3-12MPa, and mass space velocity is 0.2-1.5h
-1, hydrogen to oil volume ratio is 200-600; The reaction conditions of described hydrocracking reaction zone comprises: temperature of reaction is 320-380 DEG C, and reaction pressure is 3-12MPa, mass space velocity 0.3-2h
-1, hydrogen to oil volume ratio 200-600.
6, the method according to 1 or 2, it is characterized in that, the metal component that described hydrogenation catalyst contains carrier, at least one is selected from group VIB, is benchmark with oxide basis and with catalyzer, the content of described metal component of group VIB is 1-40 % by weight, and vector contg is 60-99 % by weight.
7, method according to 6, it is characterized in that, support selected from alumina in described hydrogenation catalyst, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, silica-magnesias, aluminium oxide-zirconium oxide, silica thoria, silica-berylias, silica-titania, silica-zirconia, titania-zirconia, silica-alumina thoria, silica-alumina-titania, silicaalumina-magnesia, one or more in silica-alumina, zirconia, described metal component of group VIB is selected from molybdenum and/or tungsten, be benchmark with oxide basis and with catalyzer, the content of described metal component of group VIB is 5-25 % by weight, vector contg is 75-95 % by weight.
8, the method according to 7, is characterized in that, the support selected from alumina in described hydrogenation catalyst, described metal component of group VIB is molybdenum, be benchmark with oxide basis and with catalyzer, the content of described metal component of group VIB is 8-15 % by weight, and vector contg is 85-92 % by weight.
9, the method according to 1 or 2, it is characterized in that, described hydrogenation catalyst contains carrier and is selected from the metal component of group VIB and the VIIIth race, be benchmark with oxide basis and with catalyzer, the content of described metal component of group VIB is 1-40 % by weight, the content of described metal component of group VIII is for being greater than 0 % by weight to being less than or equal to 15 % by weight, and vector contg is 45 % by weight to being less than or equal to 99 % by weight.
10, method according to 9, it is characterized in that, support selected from alumina in described hydrogenation catalyst, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, silica-magnesias, aluminium oxide-zirconium oxide, silica thoria, silica-berylias, silica-titania, silica-zirconia, titania-zirconia, silica-alumina thoria, silica-alumina-titania, silicaalumina-magnesia, one or more in silica-alumina, zirconia, described metal component of group VIB is selected from molybdenum and/or tungsten, the metal component of the VIIIth race is selected from cobalt, nickel, ruthenium, rhodium, palladium, osmium, one or more in iridium and platinum, be benchmark with oxide basis and with catalyzer, the content of described metal component of group VIB is 5-25 % by weight, the content of described metal component of group VIII is 1-5 % by weight, vector contg is 70-94 % by weight.
11, the method according to 10, it is characterized in that, support selected from alumina in described hydrogenation catalyst, described metal component of group VIB is molybdenum, the metal component of the VIIIth race is cobalt, is benchmark with oxide basis and with catalyzer, and the content of described metal component of group VIB is 8-20 % by weight, the content of described metal component of group VIII is 1.5-3 % by weight, and vector contg is 77-90 % by weight.
12, the method according to 1 or 2, it is characterized in that, the metal component that described hydrocracking catalyst contains molecular sieve, heat-resistant inorganic oxide matrix, at least one are selected from group VIB, take catalyzer as benchmark, molecular sieve content in described hydrocracking catalyst is 1-60 % by weight, heat-resistant inorganic oxide matrix content is 15-96 % by weight, with the content of the metal component of group VIB of oxide basis for 3-25 % by weight.
13, method according to 12, it is characterized in that, molecular screening in described hydrocracking catalyst is from Y zeolite, described heat-resistant inorganic oxide is selected from aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, silica-magnesias, aluminium oxide-zirconium oxide, silica thoria, silica-berylias, silica-titania, silica-zirconia, titania-zirconia, silica-alumina thoria, silica-alumina-titania, silicaalumina-magnesia, one or more in silica-alumina, zirconia, described metal component of group VIB is selected from molybdenum and/or tungsten, take catalyzer as benchmark, molecular sieve content in described hydrocracking catalyst is 10-50 % by weight, heat-resistant inorganic oxide matrix content is 30-85 % by weight, be 5 ~ 20 % by weight with the content of the metal component of group VIB of oxide basis.
14, the method according to 12, it is characterized in that, molecular screening in described hydrocracking catalyst is from Y zeolite, described heat-resistant inorganic oxide is selected from aluminum oxide, and described metal component of group VIB is molybdenum, and described metal component of group VIII is cobalt, take catalyzer as benchmark, molecular sieve content in described hydrocracking catalyst is 10-40 % by weight, and heat-resistant inorganic oxide matrix content is 45-85 % by weight, with the content of the metal component of group VIB of oxide basis for 5-15 % by weight.
15, the method according to 1 or 2, it is characterized in that, described hydrocracking catalyst contains molecular sieve, heat-resistant inorganic oxide matrix and is selected from the metal component of group VIB and the VIIIth race, take catalyzer as benchmark, molecular sieve content in described hydrocracking catalyst is 1-60 % by weight, heat-resistant inorganic oxide matrix content is 7 % by weight to being less than or equal to 96 % by weight, be 3 ~ 25 % by weight with the content of the metal component of group VIB of oxide basis, metal component of group VIII content is for being greater than 0 % by weight to being less than or equal to 8 % by weight.
16, method according to 15, it is characterized in that, molecular screening in described hydrocracking catalyst is from Y zeolite, described heat-resistant inorganic oxide is selected from aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, silica-magnesias, aluminium oxide-zirconium oxide, silica thoria, silica-berylias, silica-titania, silica-zirconia, titania-zirconia, silica-alumina thoria, silica-alumina-titania, silicaalumina-magnesia, one or more in silica-alumina, zirconia, described metal component of group VIB is selected from molybdenum and/or tungsten, described metal component of group VIII is selected from cobalt and/or nickel, take catalyzer as benchmark, molecular sieve content in described hydrocracking catalyst is 10-50 % by weight, heat-resistant inorganic oxide matrix content is 25-84 % by weight, with the content of the metal component of group VIB of oxide basis for 5-20 % by weight, metal component of group VIII content is 1-5 % by weight.
17, the method according to 16, it is characterized in that, molecular screening in described hydrocracking catalyst is from Y zeolite, described heat-resistant inorganic oxide is selected from aluminum oxide, described metal component of group VIB is molybdenum, described metal component of group VIII is cobalt, take catalyzer as benchmark, molecular sieve content in described hydrocracking catalyst is 10-40 % by weight, heat-resistant inorganic oxide matrix content is 42-84 % by weight, with the content of the metal component of group VIB of oxide basis for 5-15 % by weight, metal component of group VIII content is 1-3 % by weight.
According to method provided by the invention, wherein said polycyclic aromatic hydrocarbons refers to the condensed-nuclei aromatics of more than three rings, as phenanthrene, anthracene, pyrene and their derivative etc.For phenanthrene, described polycyclic aromatic hydrocarbons is at least partly hydrogenated and saturatedly refers to that comprising luxuriant and rich with fragrance hydrotreated lube base oil becomes dihydro phenanthrene, and luxuriant and rich with fragrance hydrotreated lube base oil becomes tetrahydrochysene phenanthrene, and luxuriant and rich with fragrance hydrotreated lube base oil becomes octahydro phenanthrene, and it is luxuriant and rich with fragrance etc. that luxuriant and rich with fragrance hydrotreated lube base oil becomes perhydro.Described polycyclic aromatic hydrocarbons hydrocracking refer at least be partly hydrogenated saturated after aromatic hydrocarbons in the raw ring-opening reaction of at least one environment-development.
According to method provided by the invention, hydroconversion reaction zone is wherein for the purpose of polycyclic aromatic hydrocarbons hydrotreated lube base oil, therefore, be enough to make the transformation efficiency containing the polycyclic aromatic hydrocarbons in the raw material of polycyclic aromatic hydrocarbons (comprising at least part of hydrotreated lube base oil) to be more than 40 % by weight (such as in described hydroconversion reaction zone, transformation efficiency is 40-100 % by weight), be preferably more than 55 % by weight (such as, transformation efficiency is 55-100 % by weight), (the so-called yield advantage in the application refers to that in aromatic hydrogenation product, a certain specific product is relative to the percentage ratio of aromatic hydrocarbons total in raw material to the yield advantage of wherein monocycle hydrogenation products.Such as, be exactly Zong the yield advantage monocycle hydrogenation products of monocycle hydrogenation products is relative to the percentage ratio of aromatic hydrocarbons in raw material) be 4-80%, be preferably the prerequisite of 10-75%, the present invention does not limit described catalyzer.Such as, what provide in prior art take heat-resistant inorganic oxide as carrier, be the catalyzer of hydrogenation active component by the base metal being selected from least one group VIB and/or the VIIIth race, or the catalyzer etc. being hydrogenation active component by the precious metal being selected from least one the VIIIth race all can be used for the present invention.
In a preferred embodiment, the described catalyzer for hydroconversion reaction zone contains the metal component that carrier and at least one are selected from group VIB, be benchmark with oxide basis and with catalyzer, the content of described metal component of group VIB is 1-40 % by weight, and vector contg is 60-99 % by weight.Support selected from alumina in further preferred described hydrogenation catalyst, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, silica-magnesias, aluminium oxide-zirconium oxide, silica thoria, silica-berylias, silica-titania, silica-zirconia, titania-zirconia, silica-alumina thoria, silica-alumina-titania, silicaalumina-magnesia, one or more in silica-alumina, zirconia, described metal component of group VIB is selected from molybdenum and/or tungsten, be benchmark with oxide basis and with catalyzer, the content of described metal component of group VIB is 5-25 % by weight, vector contg is 75-95 % by weight.Be more preferably the support selected from alumina in described hydrogenation catalyst, described metal component of group VIB is molybdenum, is benchmark with oxide basis and with catalyzer, and the content of described metal component of group VIB is 8-15 % by weight, and vector contg is 85-92 % by weight.
In another preferred embodiment, the described catalyzer for hydroconversion reaction zone contains carrier and is selected from the metal component of group VIB and the VIIIth race, be benchmark with oxide basis and with catalyzer, the content of described metal component of group VIB is 1-40 % by weight, the content of described metal component of group VIII is for being greater than 0 % by weight to being less than or equal to 15 % by weight, and vector contg is 45 % by weight to being less than or equal to 99 % by weight.Support selected from alumina in further preferred described hydrogenation catalyst, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, silica-magnesias, aluminium oxide-zirconium oxide, silica thoria, silica-berylias, silica-titania, silica-zirconia, titania-zirconia, silica-alumina thoria, silica-alumina-titania, silicaalumina-magnesia, one or more in silica-alumina, zirconia, described metal component of group VIB is selected from molybdenum and/or tungsten, the metal component of the VIIIth race is selected from cobalt, nickel, ruthenium, rhodium, palladium, osmium, one or more in iridium and platinum, be benchmark with oxide basis and with catalyzer, the content of described metal component of group VIB is 5-25 % by weight, the content of described metal component of group VIII is 1-5 % by weight, vector contg is 70-94 % by weight.Be more preferably the support selected from alumina in described hydrogenation catalyst, described metal component of group VIB is molybdenum, the metal component of the VIIIth race is cobalt, be benchmark with oxide basis and with catalyzer, the content of described metal component of group VIB is 8-20 % by weight, the content of described metal component of group VIII is 1.5-3 % by weight, and vector contg is 77-90.5 % by weight.
Described hydrocracking reaction zone by through hydroconversion reaction zone by for the purpose of the open loop of the product of at least part of hydrotreated lube base oil, therefore, being enough in described hydrocracking reaction zone make with the transformation efficiency of the polycyclic aromatic hydrocarbons being benchmark containing the polycyclic aromatic hydrocarbons total amount in the raw material of polycyclic aromatic hydrocarbons (comprising at least part of hydrotreated lube base oil and hydrocracking) is more than 85 % by weight, be preferably more than 90 % by weight, wherein the yield advantage of monocycle hydrocrackates is 4-30%, under being preferably the prerequisite of 5-20%, the present invention does not limit described hydrocracking catalyst.Such as, the catalyzer that hydrocracking (or cracking) reacts that is usually used in provided in prior art all can be used for the present invention.
In a preferred embodiment, the described catalyzer for adding cracking reaction district contains the metal component that molecular sieve, heat-resistant inorganic oxide matrix and at least one are selected from group VIB, take catalyzer as benchmark, molecular sieve content in described hydrocracking catalyst is 1-60 % by weight, heat-resistant inorganic oxide matrix content is 7-96 % by weight, with the content of the metal component of group VIB of oxide basis for 3-25 % by weight.Molecular screening in further preferred described hydrocracking catalyst is from Y zeolite, described heat-resistant inorganic oxide is selected from aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, silica-magnesias, aluminium oxide-zirconium oxide, silica thoria, silica-berylias, silica-titania, silica-zirconia, titania-zirconia, silica-alumina thoria, silica-alumina-titania, silicaalumina-magnesia, one or more in silica-alumina, zirconia, described metal component of group VIB is selected from molybdenum and/or tungsten, take catalyzer as benchmark, molecular sieve content in described hydrocracking catalyst is 10-50 % by weight, heat-resistant inorganic oxide matrix content is 30-85 % by weight, be 5 ~ 20 % by weight with the content of the metal component of group VIB of oxide basis.Molecular screening in the described hydrocracking catalyst be more preferably is from Y zeolite, described heat-resistant inorganic oxide is selected from aluminum oxide, described metal component of group VIB is molybdenum, described metal component of group VIII is cobalt, take catalyzer as benchmark, molecular sieve content in described hydrocracking catalyst is 10-40 % by weight, and heat-resistant inorganic oxide matrix content is 45-85 % by weight, with the content of the metal component of group VIB of oxide basis for 5-15 % by weight.
In another preferred embodiment, the described catalyzer for adding cracking reaction district contains molecular sieve, heat-resistant inorganic oxide matrix and is selected from the metal component of group VIB and the VIIIth race, take catalyzer as benchmark, molecular sieve content in described hydrocracking catalyst is 1-60 % by weight, heat-resistant inorganic oxide matrix content is 7 % by weight to being less than or equal to 96 % by weight, be 3 ~ 25 % by weight with the content of the metal component of group VIB of oxide basis, metal component of group VIII content is for being greater than 0 % by weight to being less than or equal to 8 % by weight.Molecular screening in further preferred described hydrocracking catalyst is from Y zeolite, described heat-resistant inorganic oxide is selected from aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, silica-magnesias, aluminium oxide-zirconium oxide, silica thoria, silica-berylias, silica-titania, silica-zirconia, titania-zirconia, silica-alumina thoria, silica-alumina-titania, silicaalumina-magnesia, one or more in silica-alumina, zirconia, described metal component of group VIB is selected from molybdenum and/or tungsten, described metal component of group VIII is selected from cobalt and/or nickel, take catalyzer as benchmark, molecular sieve content in described hydrocracking catalyst is 10-50 % by weight, heat-resistant inorganic oxide matrix content is 25-84 % by weight, with the content of the metal component of group VIB of oxide basis for 5-20 % by weight, metal component of group VIII content is 1-5 % by weight.Molecular screening in further preferred described hydrocracking catalyst is from Y zeolite, described heat-resistant inorganic oxide is selected from aluminum oxide, described metal component of group VIB is molybdenum, described metal component of group VIII is cobalt, take catalyzer as benchmark, the molecular sieve content in described hydrocracking catalyst is 10-40 % by weight, and heat-resistant inorganic oxide matrix content is 42-84 % by weight, with the content of the metal component of group VIB of oxide basis for 5-15 % by weight, metal component of group VIII content is 1-3 % by weight.
According to method provided by the invention, described hydroconversion reaction zone and hydrocracking reaction can be realize by hydrogenation catalyst and hydrocracking catalyst layering being filled in same reactor, also can be realized by reactor hydrogenation catalyst and hydrocracking catalyst being filled in respectively two or more series connection, this present invention is not particularly limited.
According to method provided by the invention, comprise in described hydroconversion reaction zone and hydrocracking reaction zone and be provided with heat exchanger, the material distillated through hydroconversion reaction zone is through described heat exchanger heat exchange, the temperature of the material entering hydrocracking reaction zone can be regulated more easily, meet the demands to make it.
According to method provided by the invention, wherein, described hydrogenation catalyst and hydrocracking catalyst are before the use, preferably carry out prevulcanized according to the ordinary method in this area, such as, at the temperature of 140 ~ 370 DEG C, carry out prevulcanized with sulphur, hydrogen sulfide or sulfur-bearing raw material, this prevulcanized can be carried out outside device also can be In-situ sulphiding in device, is translated into sulfide type.
Compared with prior art, method provided by the invention has the conversion realizing polycyclic aromatic hydrocarbons under lower hydrogen consumption.Such as, being model compound with phenanthrene, take biphenyl compound as target product, compared with traditional hydroprocessing process, adopts method provided by the invention can significantly improve the product yield of biphenyl compound.
Embodiment
The following examples will further illustrate the present invention, but therefore can not be interpreted as it is limitation of the invention.
Embodiment 1-4 illustrates the hydrogenation catalyst that the present invention uses and preparation thereof.
Embodiment 1
Take Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 11.8 grams, Ammonium Heptamolybdate 17.4 grams, be made into co-impregnated solution 110 milliliters with deionized water.The trifolium-shaped oxidation aluminum strip carrier S 1(of the circumscribed circle diameter 1.4 millimeters of Chang Ling catalyzer branch office is taken from through 600 DEG C of roastings 4 hours by this solution impregnation 100 grams) 6 hours, then 120 DEG C of dryings 4 hours, 420 DEG C of roasting 4h, obtain catalyzer C1.Measure through X-ray fluorescence spectra method, containing CoO in catalyzer C1 is 2.4 % by weight, containing MoO
3be 12.0 % by weight.
Embodiment 2
Take nickelous nitrate 11.7 grams, Ammonium Heptamolybdate 17.4 grams, be made into co-impregnated solution 110 milliliters with deionized water.With this solution impregnation 100 grams of S1 carriers 6 hours, then 120 DEG C of dryings 4 hours, 420 DEG C of roasting 4h, obtained catalyzer C2.Measure through X-ray fluorescence spectra method, containing NiO in catalyzer C2 is 2.4 % by weight, containing MoO
3be 12.0 % by weight.
Embodiment 3
Take nickelous nitrate 9.55 grams, ammonium metawolframate 25.7 grams, be made into co-impregnated solution 110 milliliters with deionized water.With this solution impregnation 100 grams of S1 carriers 6 hours, then 120 DEG C of dryings 4 hours, 420 DEG C of roasting 4h, obtained catalyzer C3.Measure through X-ray fluorescence spectra method, containing NiO in catalyzer C3 is 1.8 % by weight, containing WO
3be 18.5 % by weight.
Embodiment 4
Take Ammonium Heptamolybdate 17.4 grams, be made into co-impregnated solution 110 milliliters with deionized water.The trifolium-shaped oxidation aluminum strip carrier S 1(of the circumscribed circle diameter 1.4 millimeters of Chang Ling catalyzer branch office is taken from through 600 DEG C of roastings 4 hours by this solution impregnation 100 grams) 6 hours, then 120 DEG C of dryings 4 hours, 420 DEG C of roasting 4h, obtain catalyzer C6.Measure through X-ray fluorescence spectra method, containing MoO in catalyzer C6
3be 12.0 % by weight.
Embodiment 5-7 illustrates that the present invention uses hydrocracking catalyst and preparation thereof.
Embodiment 5
10.87g USY molecular sieve (is taken from Chang Ling catalyzer branch office, butt 0.92) (take from Chang Ling catalyzer branch office with 120g pseudo-boehmite, butt 0.75) and 3g sesbania powder kneading after be extruded into the trifolium bar of 1.4mm, then at 120 DEG C of dry 4h, 600 DEG C of roasting 4h become carrier S 2.Take Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 11.8 grams, Ammonium Heptamolybdate 17.4 grams, be made into co-impregnated solution 90 milliliters with deionized water.With this solution impregnation 100 grams of S2 carriers 6 hours, then 120 DEG C of dryings 4 hours, 420 DEG C of roasting 4h, obtained catalyzer C4.Measure through X-ray fluorescence spectra method, containing CoO in catalyzer C4 is 2.4 % by weight, containing MoO
3be 12.0 % by weight.
Embodiment 6
Take Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 5.9 grams, Ammonium Heptamolybdate 8.7 grams, be made into co-impregnated solution 90 milliliters with deionized water.With this solution impregnation 100 grams of S2 carriers 6 hours, then 120 DEG C of dryings 4 hours, 420 DEG C of roasting 4h, obtained catalyzer C5.Measure through X-ray fluorescence spectra method, containing CoO in catalyzer C5 is 1.2 % by weight, containing MoO
3be 6.0 % by weight.
Embodiment 7
Take Ammonium Heptamolybdate 17.4 grams, be made into co-impregnated solution 90 milliliters with deionized water.With this solution impregnation 100 grams of S2 carriers 6 hours, then 120 DEG C of dryings 4 hours, 420 DEG C of roasting 4h, obtained catalyzer C7.Measure through X-ray fluorescence spectra method, containing MoO in catalyzer C7
3be 12.0 % by weight.
Embodiment 8-15 illustrates the performance of hydrogenation catalyst provided by the invention.
Embodiment 8-9
The Hydrogenation of evaluate catalysts C1, C2, C3, C6 on small fixed hydrogenation reaction device, catalyst levels 0.15 gram.
Presulfiding of catalyst: sulfuration stock oil is the mixing solutions of the hexanaphthene containing 3 % by weight dithiocarbonic anhydride.
Cure conditions: pressure 4.14MPa, temperature 360 DEG C, 3.5 hours time, vulcanized oil feeding rate is 0.2 ml/min.
Reaction raw materials: containing the mixing solutions of the n-decane of luxuriant and rich with fragrance 1.0 % by weight.
Reaction conditions: temperature of reaction is 280 DEG C, reaction pressure is 4.1MPa, and mass space velocity is 0.6h
-1, hydrogen to oil volume ratio is 500.
Gained sample GC-MASS analyzes, and acquired results is in table 1.Wherein, the luxuriant and rich with fragrance transformation efficiency X of reaction, the luxuriant and rich with fragrance product yield Y of monocycle hydrogenation products dihydro and the luxuriant and rich with fragrance selectivity of product S of dihydro are calculated as follows:
X=(percentage composition/(percentage compositions of 1-solvent) of 1-product China and Philippines) × 100%
Percentage composition/(percentage composition of 1-solvent) × 100% of dihydro phenanthrene in Y=product
S=Y/X×100%
Embodiment 10
According to the method evaluation catalyzer of embodiment 6-8, it is 260 DEG C unlike temperature of reaction.Gained sample GC-MASS analyzes, and the results are shown in Table 1.
Embodiment 11
According to the method evaluation catalyzer of embodiment 6-8, it is 240 DEG C unlike temperature of reaction.Gained sample GC-MASS analyzes, and the results are shown in Table 1.
Embodiment 12
According to the method evaluation catalyzer of embodiment 6-8, unlike temperature of reaction 240 DEG C, mass space velocity is 0.45h
-1.Gained sample GC-MASS analyzes, and the results are shown in Table 1.
Embodiment 13
According to the method evaluation catalyzer of embodiment 6-8, unlike temperature of reaction 240 DEG C, mass space velocity is 0.3h
-1.Gained sample GC-MASS analyzes, and the results are shown in Table 1.
Embodiment 14-16 illustrates the performance of hydrocracking catalyst provided by the invention.
Embodiment 14-16
The performance of evaluate catalysts C4, C5, C7 on small fixed hydrogenation reaction device, catalyst levels 0.3 gram.
Presulfiding of catalyst: sulfuration stock oil is the mixing solutions of the hexanaphthene containing 3 % by weight dithiocarbonic anhydride.
Cure conditions: pressure 4.14MPa, temperature 360 DEG C, 3.5 hours time, vulcanized quality air speed 30h
-1
Reaction raw materials: containing the mixing solutions of the hexanaphthene of luxuriant and rich with fragrance 2.0 % by weight.
Reaction conditions: temperature of reaction is 350 DEG C, reaction pressure is 4.1MPa, and mass space velocity is 0.6h
-1, hydrogen to oil volume ratio is 500.
Gained sample GC-MASS analyzes, and acquired results is in table 1.Wherein, the biphenyl class product yield Y of one of the luxuriant and rich with fragrance transformation efficiency X and monocycle hydrocrackates of reaction is calculated as follows:
X=(percentage composition/(percentage compositions of 1-solvent) of 1-product China and Philippines) × 100%
Percentage composition/(percentage composition of 1-solvent) × 100% of biphenyl class product in Y=product
Table 1
Embodiment 17-19 illustrates and the invention provides method and effect thereof.
Embodiment 17
Reaction unit is the small fixed hydrogenator of two reactors in series, the first reactor charge 0.6 gram catalyzer C1, the second reactor charge 0.3 gram catalyzer C4.
Catalyst vulcanization: sulfuration stock oil is the mixing solutions containing 3 % by weight dithiocarbonic anhydride and hexanaphthene, and cure conditions is: reaction pressure 4.14MPa, temperature of reaction 360 DEG C, 3.5 hours reaction times, and the first reactor vulcanized quality air speed is 15h
-1, the second reactor vulcanized quality air speed is 30h
-1.
Reaction raw materials: containing the mixing solutions of the hexanaphthene of luxuriant and rich with fragrance 2.0 % by weight.
Reaction conditions: temperature of reaction is 350 DEG C, reaction pressure is 4.1MPa, and the first reactor mass space velocity is 0.3h
-1, the second reactor mass space velocity is 0.6h
-1, hydrogen to oil volume ratio is 500.
Gained sample GC-MASS analyzes, and acquired results is in table 2.
Embodiment 18
Method is with embodiment 15, and difference is hydrogenation catalyst is C1, and hydrocracking catalyst is C5.Gained sample GC-MASS analyzes, and acquired results is in table 2.
Embodiment 19
Method is with embodiment 15, and difference is hydrogenation catalyst is C1, and hydrocracking catalyst is C7.Gained sample GC-MASS analyzes, and acquired results is in table 2.
Table 2
Claims (17)
1. the method for a hydrocracking polycyclic aromatic hydrocarbons, comprise: (1) is at least one hydroconversion reaction zone, in the presence of hydrogen gas by the raw material containing polycyclic aromatic hydrocarbons and hydrogenation catalyst contact reacts, obtain a kind of polycyclic aromatic hydrocarbons and be at least partly hydrogenated satisfied reaction product; (2) at least one hydrocracking reaction zone, reaction product at least partly by hydrotreated lube base oil of the polycyclic aromatic hydrocarbons that in the presence of hydrogen gas step (1) obtained and hydrocracking catalyst contact reacts; Wherein, the hydrogenation catalyst of described hydroconversion reaction zone and the selection of operational condition make the transformation efficiency containing the polycyclic aromatic hydrocarbons in the raw material of polycyclic aromatic hydrocarbons be more than 40 % by weight, and wherein the yield advantage of monocycle hydrogenation products is 4-80%; The described hydrocracking catalyst of hydrocracking reaction zone and the selection of operational condition make the polycyclic aromatic hydrocarbons transformation efficiency to be benchmark containing the polycyclic aromatic hydrocarbons total amount in the raw material of polycyclic aromatic hydrocarbons be more than 85 % by weight, and wherein the yield advantage of monocycle hydrocrackates is 4-30%.
2. method according to claim 1, it is characterized in that, the hydrogenation catalyst of described hydroconversion reaction zone and the selection of operational condition make the transformation efficiency containing the polycyclic aromatic hydrocarbons in the raw material of polycyclic aromatic hydrocarbons be more than 55 % by weight, and wherein the yield advantage of monocycle hydrogenation products is 10-75%; The described hydrocracking catalyst of hydrocracking reaction zone and the selection of operational condition make the polycyclic aromatic hydrocarbons transformation efficiency to be benchmark containing the polycyclic aromatic hydrocarbons total amount in the raw material of polycyclic aromatic hydrocarbons be more than 90 % by weight, and wherein the yield advantage of monocycle hydrocrackates is 5-20%.
3. method according to claim 1 and 2, is characterized in that, the operational condition of described hydroconversion reaction zone comprises: temperature of reaction is 150-350 DEG C, and reaction pressure is 1-20MPa, and mass space velocity is 0.01-4h
-1, hydrogen to oil volume ratio is 50-900; The reaction conditions of described hydrocracking reaction zone comprises: temperature of reaction is 280-450 DEG C, and reaction pressure is 1-20MPa, mass space velocity 0.1-4h
-1, hydrogen to oil volume ratio 100-900.
4. method according to claim 3, is characterized in that, the operational condition of described hydroconversion reaction zone comprises: temperature of reaction is 180-300 DEG C, and reaction pressure is 2-15MPa, and mass space velocity is 0.1-2h
-1, hydrogen to oil volume ratio is 100-800; The reaction conditions of described hydrocracking reaction zone comprises: temperature of reaction is 320-400 DEG C, and reaction pressure is 2-15MPa, mass space velocity 0.2-3h
-1, hydrogen to oil volume ratio 200-800.
5. method according to claim 4, is characterized in that, the operational condition of described hydroconversion reaction zone comprises: temperature of reaction is 200-300 DEG C, and reaction pressure is 3-12MPa, and mass space velocity is 0.2-1.5h
- 1, hydrogen to oil volume ratio is 200-600; The reaction conditions of described hydrocracking reaction zone comprises: temperature of reaction is 320-380 DEG C, and reaction pressure is 3-12MPa, mass space velocity 0.3-2h
-1, hydrogen to oil volume ratio 200-600.
6. method according to claim 1 and 2, it is characterized in that, the metal component that described hydrogenation catalyst contains carrier, at least one is selected from group VIB, be benchmark with oxide basis and with catalyzer, the content of described metal component of group VIB is 1-40 % by weight, and vector contg is 60-99 % by weight.
7. method according to claim 6, it is characterized in that, support selected from alumina in described hydrogenation catalyst, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, silica-magnesias, aluminium oxide-zirconium oxide, silica thoria, silica-berylias, silica-titania, silica-zirconia, titania-zirconia, silica-alumina thoria, silica-alumina-titania, silicaalumina-magnesia, one or more in silica-alumina, zirconia, described metal component of group VIB is selected from molybdenum and/or tungsten, be benchmark with oxide basis and with catalyzer, the content of described metal component of group VIB is 5-25 % by weight, vector contg is 75-95 % by weight.
8. method according to claim 7, it is characterized in that, support selected from alumina in described hydrogenation catalyst, described metal component of group VIB is molybdenum, be benchmark with oxide basis and with catalyzer, the content of described metal component of group VIB is 8-15 % by weight, and vector contg is 85-92 % by weight.
9. method according to claim 1 and 2, it is characterized in that, described hydrogenation catalyst contains carrier and is selected from the metal component of group VIB and the VIIIth race, be benchmark with oxide basis and with catalyzer, the content of described metal component of group VIB is 1-40 % by weight, the content of described metal component of group VIII is for being greater than 0 % by weight to being less than or equal to 15 % by weight, and vector contg is 45 % by weight to being less than or equal to 99 % by weight.
10. method according to claim 9, it is characterized in that, support selected from alumina in described hydrogenation catalyst, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, silica-magnesias, aluminium oxide-zirconium oxide, silica thoria, silica-berylias, silica-titania, silica-zirconia, titania-zirconia, silica-alumina thoria, silica-alumina-titania, silicaalumina-magnesia, one or more in silica-alumina, zirconia, described metal component of group VIB is selected from molybdenum and/or tungsten, the metal component of the VIIIth race is selected from cobalt, nickel, ruthenium, rhodium, palladium, osmium, one or more in iridium and platinum, be benchmark with oxide basis and with catalyzer, the content of described metal component of group VIB is 5-25 % by weight, the content of described metal component of group VIII is 1-5 % by weight, vector contg is 70-94 % by weight.
11. methods according to claim 10, it is characterized in that, support selected from alumina in described hydrogenation catalyst, described metal component of group VIB is molybdenum, the metal component of the VIIIth race is cobalt, is benchmark with oxide basis and with catalyzer, and the content of described metal component of group VIB is 8-20 % by weight, the content of described metal component of group VIII is 1.5-3 % by weight, and vector contg is 77-90.5 % by weight.
12. methods according to claim 1 and 2, it is characterized in that, the metal component that described hydrocracking catalyst contains molecular sieve, heat-resistant inorganic oxide matrix, at least one are selected from group VIB, take catalyzer as benchmark, molecular sieve content in described hydrocracking catalyst is 1-60 % by weight, heat-resistant inorganic oxide matrix content is 15-96 % by weight, with the content of the metal component of group VIB of oxide basis for 3-25 % by weight.
13. methods according to claim 12, it is characterized in that, molecular screening in described hydrocracking catalyst is from Y zeolite, described heat-resistant inorganic oxide is selected from aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, silica-magnesias, aluminium oxide-zirconium oxide, silica thoria, silica-berylias, silica-titania, silica-zirconia, titania-zirconia, silica-alumina thoria, silica-alumina-titania, silicaalumina-magnesia, one or more in silica-alumina, zirconia, described metal component of group VIB is selected from molybdenum and/or tungsten, take catalyzer as benchmark, molecular sieve content in described hydrocracking catalyst is 10-50 % by weight, heat-resistant inorganic oxide matrix content is 30-85 % by weight, be 5 ~ 20 % by weight with the content of the metal component of group VIB of oxide basis.
14. methods according to claim 12, it is characterized in that, molecular screening in described hydrocracking catalyst is from Y zeolite, described heat-resistant inorganic oxide is selected from aluminum oxide, described metal component of group VIB is molybdenum, described metal component of group VIII is cobalt, take catalyzer as benchmark, molecular sieve content in described hydrocracking catalyst is 10-40 % by weight, heat-resistant inorganic oxide matrix content is 45-85 % by weight, with the content of the metal component of group VIB of oxide basis for 5-15 % by weight.
15. methods according to claim 1 and 2, it is characterized in that, described hydrocracking catalyst contains molecular sieve, heat-resistant inorganic oxide matrix and is selected from the metal component of group VIB and the VIIIth race, take catalyzer as benchmark, molecular sieve content in described hydrocracking catalyst is 1-60 % by weight, heat-resistant inorganic oxide matrix content is 7 % by weight to being less than 96 % by weight, with the content of the metal component of group VIB of oxide basis for 3-25 % by weight, metal component of group VIII content is for being greater than 0 % by weight to being less than or equal to 8 % by weight.
16. methods according to claim 15, is characterized in that, the molecular screening in described hydrocracking catalyst is from Y zeolite, and described heat-resistant inorganic oxide is selected from aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, silica-magnesias, aluminium oxide-zirconium oxide, silica thoria, silica-berylias, silica-titania, silica-zirconia, titania-zirconia, silica-alumina thoria, silica-alumina-titania, silicaalumina-magnesia, one or more in silica-alumina, zirconia, described metal component of group VIB is selected from molybdenum and/or tungsten, described metal component of group VIII is selected from cobalt and/or nickel, take catalyzer as benchmark, molecular sieve content in described hydrocracking catalyst is 10-50 % by weight, heat-resistant inorganic oxide matrix content is 25-84 % by weight, and with the content of the metal component of group VIB of oxide basis for 5-20 % by weight, metal component of group VIII content is 1-5 % by weight.
17. methods according to claim 16, it is characterized in that, molecular screening in described hydrocracking catalyst is from Y zeolite, described heat-resistant inorganic oxide is selected from aluminum oxide, described metal component of group VIB is molybdenum, described metal component of group VIII is cobalt, take catalyzer as benchmark, molecular sieve content in described hydrocracking catalyst is 10-40 % by weight, heat-resistant inorganic oxide matrix content is 42-84 % by weight, with the content of the metal component of group VIB of oxide basis for 5-15 % by weight, metal component of group VIII content is 1-3 % by weight.
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