CN103122260B - Hydrofining technique of mixture of heavy benzene and absorber oil - Google Patents
Hydrofining technique of mixture of heavy benzene and absorber oil Download PDFInfo
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- CN103122260B CN103122260B CN201310033822.5A CN201310033822A CN103122260B CN 103122260 B CN103122260 B CN 103122260B CN 201310033822 A CN201310033822 A CN 201310033822A CN 103122260 B CN103122260 B CN 103122260B
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Abstract
The invention discloses a hydrofining technique of a mixture of heavy benzene and absorber oil. The technique comprises the following steps of: mixing the mixture of the heavy benzene and the absorber oil with hydrogen and then performing a hydrogenation reaction in the presence of a primary hydrogenation catalyst to obtain a primary hydrogenation product; mixing the primary hydrogenation product with hydrogen and then performing hydrogenation reaction again in the presence of a secondary hydrogenation catalyst to obtain a secondary hydrogenation product; separating partial secondary hydrogenation product to obtain a product; and returning the rest secondary hydrogenation product to the primary hydrogenation catalyst to be mixed with hydrogen and then performing primary hydrogenation reaction. The primary hydrogenation catalyst comprises the following components by weight percent: 4-10 wt% of NiO, 10-20 wt% of M0O3 and 0.1-2 wt% of one element or a mixture of multiple elements in rare-earth elements. The secondary hydrogenation catalyst comprises the following components by weight percent: 17-23 wt% of WO3, 7-12 wt% of MoO3, 3-6 wt% of NiO, 14-24 wt% of a ZSM-5 molecular sieve,14-24 wt% of a beta molecular sieve and the balance of aluminum oxide. The technique is particularly suitable for removing a great number of complex impurities from the mixture of the heavy benzene and the absorber oil.
Description
Technical field
The present invention relates to one and hydrorefined technique is carried out to heavy benzene and washing oil mixture, belong to hydrogenation technique technical field.
Background technology
Washing oil is the rectifying cut of coal tar at 230-300 DEG C, and its output is very large, accounts for the 4-8% of coal tar total amount.Washing oil directly uses usually used as the elutriant of benzene series material, namely discarded by as waste liquid after wash-out, but in fact contain the materials such as methylnaphthalene, dimethylnaphthalene, cresols and xylenol in washing oil, these materials all can make Organic Chemicals and use after extracting, and are worth even if the washing oil therefore after wash-out remains to have to extract.But except containing except above-mentioned extractible material in washing oil, also containing the organosulfur impurity such as organonitrogen impurity and dibenzothiophen, quinoline, indoles, dibenzofuran, the existence of these impurity can reduce the purity of the products such as extracted methylnaphthalene, dimethylnaphthalene, cresols and xylenol, therefore need first to be fallen by above-mentioned Impurity removal, industrial usual employing catalytic hydrogenation process removes the above-mentioned impurity in washing oil.
Washing oil hydrogenation process for upgrading needs the reaction environment of independently equipment and High Temperature High Pressure, but due to washing oil institute extracting substance amount less, added value is low, therefore industry member generally believes and to be extracted by washing oil compared with cost that the value of the product that obtains and equipment, energy consumption spend, the rate of profit of washing oil catalytic hydrogenation process is very low, be unsuitable for carrying out industrial production, the report therefore about washing oil catalytic hydrogenation process is little.
Heavy benzene is in the crude benzol course of processing, isolated heavy constituent by product at the bottom of tower, and be a kind of colourless to flaxen oily liquids, density is between 0.96-0.99g/cm
3, heavy benzene is water insoluble, volatile, inflammable, poisonous, can with the immiscible organic solvents such as benzene, ketone, ester, alcohol.The main material higher containing added values such as naphthalene, alpha-methyl-naphthalene, beta-methylnaphthalene, indenes, coumarones in heavy benzene, but because heavy benzene also contains sulphur compound and the nitrogen compound of high-content, thus directly high purity product cannot be obtained, industrial is also generally adopt catalytic hydrogenation process to remove sulphur, nitrogen impurity, obtains high purity product.
Up to now, also there is no the report about heavy benzene and washing oil mixture through catalytic hydrogenation technique in prior art, just have report respectively to washing oil catalytic hydrogenation process and heavy benzene catalytic hydrogenation process.As Chinese patent literature CN101486926A discloses the technique of washing oil Hydrogenation for gasoline and diesel oil; washing oil is mixed the reactor by loading protective material, catalyst for demetalation, Hydrobon catalyst and/or catalyst for hydro-upgrading with hydrogen; the hydrogenated oil obtained enters high-pressure separator; top obtains hydrogen recycle and uses, and obtains gasoline or diesel oil after lower stream stripping or fractionation.Chinese patent literature CN101712888A discloses a kind of hydrofining technology of heavy benzol, heavy benzol after filtration, mix with hydrogen after enter fixed bed pre-hydrogenator successively and the main hydrogenator of fixed bed carries out selective hydrogenation refining, the hydrogenated oil of gained obtains solvent oil and NAPTHALENE FLAKES. (INDUSTRIAL GRADE） through processes such as cooling, stripping, distillation and rectifying.
Various and the complex shape of dopant species due to heavy benzene and washing oil mixture, adopt the hydrogenation technique in above-mentioned technology all significantly cannot remove impurity in heavy benzene and washing oil mixture, this is that washing oil hydrogenation catalyst owing to adopting in above-mentioned technique and heavy benzene hydrogenation catalyst are not suitable for all impurity removed in heavy benzene and washing oil mixture, therefore have a lot of organosulfur in heavy benzene and washing oil mixture and organonitrogen impurity cannot be removed completely, thus have impact on the purity of obtained product.
And the washing oil hydrogenation technique in above-mentioned technology and heavy benzene hydrogenation technique, easily make the aromatic hydroxy compound generation open loop chain-breaking reaction in heavy benzene and washing oil mixture, make the cetane value of extracted diesel component very low, the added value of diesel oil reduces.
Summary of the invention
Technical problem to be solved by this invention is that in prior art, washing oil hydrogenation technique and heavy benzene hydrogenation technique significantly cannot remove the impurity in heavy benzene and washing oil mixture, and does not also have the report about heavy benzene and washing oil hydrogenation mixture technique in prior art; And then propose a kind ofly can remove a large amount of heavy benzene of impurity and the hydrofining technology of washing oil mixture in heavy benzene and washing oil mixture.
The present invention simultaneously another technical problem to be solved is the aromatic hydroxy compound generation open loop chain-breaking reaction that the washing oil hydrogenation technique of prior art processes and heavy benzene hydrogenation technique easily cause in heavy benzene and washing oil mixture, thus reduces the cetane value of extracted diesel component; And then propose a kind ofly to improve the heavy benzene of diesel component cetane value and the hydrofining technology of washing oil mixture.
For solving the problems of the technologies described above, the invention provides the hydrofining technology of a kind of heavy benzene and washing oil mixture, comprising
(1), after heavy benzene and washing oil mixture mix with hydrogen, under the effect of one-level hydrogenation catalyst, carry out hydrogenation reaction, obtain one-level hydrogenation products;
(2) after one-level hydrogenation products mixes with hydrogen, under secondary hydrogenation catalyst action, proceed hydrogenation reaction, obtain secondary hydrogenation product, separation is carried out to secondary hydrogenation product and obtains product;
Described one-level hydrogenation catalyst comprises following component:
NiO4～10wt%
MoO
310～20wt%
Mixture 0.1 ~ the 2wt% of one or more in rare earth element
All the other are carrier γ-Al
2o
3-ZrO
2;
Described secondary hydrogenation catalyzer comprises following component:
All the other are aluminum oxide.
In step (2), the described secondary hydrogenation product of part is separated, and by after secondary hydrogenation product mixes with hydrogen described in rest part, returns described one-level hydrogenation catalyst and carry out one-level hydrogenation reaction.
The quality of described rest part secondary hydrogenation product accounts for the 10-40% of all secondary hydrogenation product qualities, and the volume ratio that described rest part secondary hydrogenation product mixes with hydrogen is 1:(600-1000).
Described one-level hydrogenation catalyst is composed of the following components:
NiO4～10wt%
MoO
310-20wt%
La0.1-2wt%
All the other are carrier γ-Al
2o
3-ZrO
2.
Described ZSM-5 molecular sieve is prepared by Template-free method hydrothermal synthesis method; Described beta-molecular sieve is the modified beta molecular sieve after the water vapour heat treated of 360-600 DEG C, and the processing pressure of described water vapour is 0.5-6MPa, and the treatment time is 1-5h.
Described aluminum oxide is made up of high pore volume aluminum oxide and low pore volume aluminum oxide; The pore volume of described high pore volume aluminum oxide is greater than 0.65cm
3/ g, the pore volume of described low pore volume aluminum oxide is less than 0.40cm
3/ g.
The weight ratio of described high pore volume aluminum oxide and low pore volume aluminum oxide is (52-70): (16-17).
In described heavy benzene and washing oil mixture, the weight ratio of heavy benzene, washing oil is 1:(1 ~ 10).
The volume ratio of described heavy benzene and washing oil mixture, hydrogen is 1:(800-1200).
The volume ratio of described one-level hydrogenation products and hydrogen is 1:(600-1000).
The temperature of one-level hydrogenation reaction is 175 ~ 235 DEG C, and reaction pressure is 3.0 ~ 8.0MPa.
The temperature of secondary hydrogenation reaction is 350 ~ 400 DEG C, and reaction pressure is 4 ~ 6MPa.
The preparation of described one-level hydrogenation catalyst comprises the steps:
(1) by shaping γ-Al
2o
3take out after dipping in soluble zirconium salts solution, after drying, roasting, obtain γ-Al
2o
3-ZrO
2carrier;
(2) in nickel salt or nickel hydroxide, add ammonia soln to after dissolving completely, then add quadrol and mix, finally add molybdenum salt and mix, obtain Mo-Ni co-impregnated solution;
(3) by described γ-Al
2o
3-ZrO
2take out after carrier floods in described Mo-Ni co-impregnated solution, after drying, roasting, obtain presoma;
(4) in the rare-earth element salt of solubility, add water to dissolving completely, then add citric acid and mix formation mixed solution, take out after described presoma is flooded in described mixed solution, drying, roasting.
The preparation of described secondary hydrogenation catalyzer comprises the steps:
(1) aluminum oxide or high pore volume aluminum oxide, beta-molecular sieve or modified beta molecular sieve, ZSM-5 molecular sieve, binding agent and extrusion aid are mixed, shaping, then drying, roasting obtain carrier;
(2) tungstate, nickel salt and water are mixed to form solution I, by described carrier impregnation in solution I, then drying, roasting obtain Vehicle element thing;
(3) molybdenum oxide, nickel salt and water are mixed to form solution II, described Vehicle element thing are immersed in solution II, then drying, roasting.
The present invention has following beneficial effect compared with prior art:
(1) hydrofining technology of heavy benzene of the present invention and washing oil mixture, comprises 1) heavy benzene is mixed with hydrogen with washing oil mixture after, under the effect of one-level hydrogenation catalyst, hydrogenation obtains one-level hydrogenation products; One-level hydrogenation catalyst comprises following component: NiO
4~ 10wt%, MoO
310 ~ 20wt%, the mixture 0.1 ~ 2wt% of one or more in rare earth element, all the other are carrier γ-Al
2o
3-ZrO
2; 2), after being mixed with hydrogen by one-level hydrogenation products, under secondary hydrogenation catalyst action, proceed hydrogenation obtain secondary hydrogenation product, secondary hydrogenation product is isolated to upgrading cut; Secondary hydrogenation catalyzer comprises following component: the WO of 17-23wt%
3, 7-12wt% MoO
3, the ZSM-5 molecular sieve of NiO, 14-24wt% of 3-6wt%, the beta-molecular sieve of 14-24wt%, all the other are aluminum oxide.
First by a large amount of diene hydrogenations in heavy benzene and washing oil mixture are generated monoolefine by one-level hydrogenation catalyst, monoolefin hydrogenation generates alkane, hydrogenation removal is carried out to a large amount of organosulfurs and organonitrogen impurity simultaneously; Afterwards on aforesaid basis, by secondary hydrogenation catalyzer, remaining a small amount of alkene, organosulfur and organonitrogen impurity hydrogenation are removed, obtain the mixture containing high density saturate, after being separated by the mixture that secondary hydrogenation produces, obtain highly purified product.
The one-level hydrogenation catalyst that above-mentioned technique is used and secondary hydrogenation catalyzer pore distribution wide, be widely used in the removal of various Sulfur, nitrogen impurity, therefore two-stage hydrogenation catalyst is used in combination the most of alkene can removing heavy benzene and washing oil mixture and organosulfur, organonitrogen impurity, thus obtains highly purified product.Avoid catalyzer that in prior art, washing oil hydrogenation technique uses and the catalyzer that heavy benzene hydrogenation technique uses and significantly cannot remove impurity in heavy benzene and washing oil mixture, and existing technique is also not used for hydrogenation catalyst heavy benzene and washing oil mixture being carried out to Impurity removal, thus the problem of high purity product cannot be obtained.
And, the two-stage hydrogenation catalyst of above-mentioned technique can make the aromatic hydroxy compound generation open loop of heavy benzene and washing oil mixture but the reaction of not chain rupture, thus ensure that the cetane value content of extracted diesel component is very high, thus obtain the clean fuel of high added value, avoid washing oil hydrogenation catalyst and crude benzole hydrogenation catalyzer in existing technique and easily make aromatic hydroxy compound open loop chain rupture, thus reduce the problem of diesel component cetane value content.
(2) hydrofining technology of heavy benzene of the present invention and washing oil mixture, in step (2), the described secondary hydrogenation product of part is separated, simultaneously, after the mixture that the secondary hydrogenation of remainder produces is mixed with hydrogen, continue to return to one-level hydrogenation catalyst place and carry out hydrogenation reaction, because in secondary hydrogenation product, the content of saturate is high, be placed on one-level hydrogenation catalyst place and can dilute the alkene contained in heavy benzene and washing oil mixture material, the concentration of the unsaturated materials such as organosulfur and organonitrogen, easily autohemagglutination is there is in the high density unsaturated materials avoided in the heavy benzene of prior art and washing oil mixture material at one-level hydrogenation catalyst place, produce the problem of high molecular polymer.And, reduce the concentration of unsaturated materials in one-level hydrogenation catalyst place raw material, can avoid one-level hydrogenation catalyst surface that the problem of temperature runaway occurs due to reaction, thus decrease the carbon deposition quantity on one-level hydrogenation catalyst surface.
(3) hydrofining technology of heavy benzene of the present invention and washing oil mixture, the temperature of one-level hydrogenation reaction 175 ~ 235 DEG C, reaction pressure is 3.0 ~ 8.0MPa.The temperature of reaction of heavy benzene hydrogenation catalyst is generally 200 DEG C, and be unsuitable for catalysis heavy benzene and washing oil mixture carries out hydrogenation reaction, and in technique of the present invention one-level hydrogenation catalyst can at 175 DEG C of these lower temperature catalysis heavy benzene and washing oil hydrogenation mixture, not only can remove most of organosulfur and organonitrogen impurity in heavy benzene and washing oil mixture, and the energy that reaction consumes is low, thus save cost.
(4) hydrofining technology of heavy benzene of the present invention and washing oil mixture, described aluminum oxide is made up of high pore volume aluminum oxide and low pore volume aluminum oxide; The pore volume of described high pore volume aluminum oxide is greater than 0.65cm
3/ g, the pore volume of described low pore volume aluminum oxide is less than 0.40cm
3/ g.The weight ratio of described high pore volume aluminum oxide and low pore volume aluminum oxide is (52-70): (16-17).During carrier as binding agent Kaolinite Preparation of Catalyst of the mixture of low pore volume aluminum oxide and salpeter solution, owing to inherently containing a large amount of aluminum oxide or high pore volume aluminum oxide in support material, low pore volume aluminum oxide is easy to mix mutually with support material and be evenly bonded together by raw material; And low pore volume aluminum oxide itself is also the component of carrier, therefore in the process of carrier calcination without the need to getting rid of, this reduces carrier inside because roasting and remove additive and the hole that produces, and then improve the intensity of carrier.In addition, because the pore capacities of low pore volume aluminum oxide is low, join the Tile Width that can improve catalyzer duct in catalyzer, and then catalyzer can be used for the impurity removing various complicated form in heavy benzene and washing oil mixture.
Accompanying drawing explanation
In order to make content of the present invention more easily be understood, the present invention is further detailed content of the present invention with embodiment by reference to the accompanying drawings;
The schema that Fig. 1 is heavy benzene described in the embodiment of the present invention 6 and 8 and washing oil hydrogenation mixture process for refining;
The schema that Fig. 2 is heavy benzene described in the embodiment of the present invention 7 and 9 and washing oil hydrogenation mixture process for refining;
The schema that Fig. 3 is heavy benzene described in the embodiment of the present invention 10,12 and 14 and washing oil hydrogenation mixture process for refining;
The schema that Fig. 4 is heavy benzene described in the embodiment of the present invention 11,13 and 15 and washing oil hydrogenation mixture process for refining.
Embodiment
Embodiment 1
Preparation one-level hydrogenation catalyst:
(1) by 8.6gZr (NO
3)
45H
2o(is with ZrO
2quality meter) be mixed with the Zr (NO of 0.5mol/L
3)
4solution; By the bar shaped γ-Al of 77.4g
2o
3be immersed in 60 DEG C of Zr (NO
3)
4take out after 6h in solution, drier 5h, 550 DEG C of roasting 4h obtain γ-Al at 100 DEG C
2o
3-ZrO
2carrier.
(2) ammonia soln adding 10v% in 4g nickel acetate (in NiO quality) dissolves completely to nickel acetate, and the quadrol adding 0.32g afterwards again mixes, and finally adds the ammonium tetramolybdate of 10g (with MoO
3quality meter) and mix, obtain Mo-Ni co-impregnated solution.
(3) by γ-Al
2o
3-ZrO
2carrier impregnation is taken out after 8h in the Mo-Ni co-impregnated solution of the capacity equal with its pore volume, and at 100 DEG C, dry 4h, 550 DEG C of roasting 4h obtain presoma.
(4), after being dissolved completely with water by the lanthanum nitrate (in lanthanum quality) of 0.1g, the citric acid adding 1g mixes, and presoma is put into above-mentioned mixed solution and floods 5h, and at 130 DEG C of dry 4h after taking-up, 400 DEG C of roasting 6h obtain one-level hydrogenation catalyst 1.
Containing the NiO of 4wt%, the MoO of 10wt% in described one-level hydrogenation catalyst 1
3, the La of 0.1wt%, all the other are γ-Al
2o
3-ZrO
2.
Prepare secondary hydrogenation catalyzer:
(1), after 52g aluminum oxide, 15g beta-molecular sieve, 8gZSM-5 molecular sieve, 46g Walocel MT 20.000PV and 1g sesbania powder being added water and mixing, fully mediate and be squeezed into strip, dry 3h at 200 DEG C, at 380 DEG C, roasting 4h, obtains carrier;
(2) 0.9mol ammonium tungstate, 0.1mol single nickel salt and 2.5mol water are mixed to form solution I, by above-mentioned carrier impregnation 2h in solution I, then at 200 DEG C dry 2h, 400 DEG C of roasting 4h obtain Vehicle element thing;
(3) 0.4mol molybdic oxide, 0.2mol nickelous nitrate and 1.5mol water are mixed to form solution II, described Vehicle element thing is immersed in 2h in solution II, then obtain secondary hydrogenation catalyzer 1 at 210 DEG C of dry 2h, 410 DEG C of roasting 5h.
Containing 17wt%WO in secondary hydrogenation catalyzer 1
3, 5wt%MoO
3, 6wt%NiO, 14wt%ZSM-5 molecular sieve and 20wt% beta-molecular sieve, all the other are aluminum oxide.
Embodiment 2
Preparation one-level hydrogenation catalyst:
(1) by 7gZrO (NO
3)
22H
2o(is with ZrO
2quality meter) be mixed with the ZrO (NO of 0.5mol/L
3)
2solution; By the spherical gamma-Al of 63g
2o
3be immersed in 60 DEG C of Zr (NO
3)
4take out after 6h in solution, drier 5h, 400 DEG C of roasting 6h obtain γ-Al at 130 DEG C
2o
3-ZrO
2carrier.
(2) ammonia soln adding 28v% in 10g nickelous nitrate (in NiO quality) dissolves completely to nickelous nitrate, and the quadrol adding 0.8g afterwards again mixes, and finally adds the Ammonium Heptamolybdate of 20g (with MoO
3quality meter) and mix, obtain Mo-Ni co-impregnated solution.
(3) by γ-Al
2o
3-ZrO
2carrier impregnation is taken out after 10h in the Mo-Ni co-impregnated solution of the capacity equal with its pore volume, and at 130 DEG C, dry 4h, 400 DEG C of roasting 6h obtain presoma.
(4), after being dissolved completely with water by the lanthanum oxalate (in lanthanum quality) of 2g, the citric acid adding 2.5g mixes, and presoma is put into above-mentioned mixed solution and floods 11h, and at 100 DEG C of dry 4h after taking-up, 550 DEG C of roasting 4h obtain one-level hydrogenation catalyst 2.
Containing the NiO of 10wt%, the MoO of 20wt% in described one-level hydrogenation catalyst 2
3, the La of 2wt%, all the other are γ-Al
2o
3-ZrO
2.
Prepare secondary hydrogenation catalyzer:
(1) be 0.65cm by 70g pore capacities
3after the high pore volume aluminum oxide of/g, 30g beta-molecular sieve, 20gZSM-5 molecular sieve, 52g hydroxypropylcellulose and 5g graphite add water and mixes, fully mediate and be squeezed into strip, dry 5h at 230 DEG C, at 430 DEG C, roasting 5h, obtains carrier;
(2) 2.5mol sodium wolframate, 0.5mol nickelous acetate and 6mol water are mixed to form solution I, by above-mentioned carrier impregnation 2h in solution I, then at 220 DEG C dry 3h, 380 DEG C of roasting 8h obtain Vehicle element thing;
(3) 1mol molybdenum dioxide, 0.6mol nickelous chloride and 2.5mol water are mixed to form solution II, described Vehicle element thing is immersed in 2h in solution II, then obtain described secondary hydrogenation catalyzer 2 at 210 DEG C of dry 2h, 410 DEG C of roasting 5h.
Containing 23wt%WO in described secondary hydrogenation catalyzer 2
3, 5wt%MoO
3, 7wt%NiO, 12wt%ZSM-5 molecular sieve and 22wt% beta-molecular sieve, all the other are aluminum oxide.
Embodiment 3
Preparation one-level hydrogenation catalyst:
(1) by 8gZr (CH
3cOO)
2(with ZrO
2quality meter) be mixed with the Zr (CH of 0.5mol/L
3cOO)
2solution; By the sheet γ-Al of 75g
2o
3be immersed in 60 DEG C of Zr (NO
3)
4take out after 6h in solution, drier 3h, 500 DEG C of roasting 5h obtain γ-Al at 120 DEG C
2o
3-ZrO
2carrier.
(2) ammonia soln adding 15v% in 8g nickelous oxalate (in NiO quality) dissolves completely to nickelous oxalate, and the quadrol adding 0.7g afterwards again mixes, and finally adds the ammonium tetramolybdate of 18g (with MoO
3quality meter) and mix, obtain Mo-Ni co-impregnated solution.
(3) by γ-Al
2o
3-ZrO
2carrier impregnation is taken out after 9h in the Mo-Ni co-impregnated solution of the capacity equal with its pore volume, and at 110 DEG C, dry 4h, 450 DEG C of roasting 4.8h obtain presoma.
(4), after being dissolved completely with water by the lanthanum acetate (in lanthanum quality) of 1g, the citric acid adding 2g mixes, and presoma is put into above-mentioned mixed solution and floods 8h, and at 120 DEG C of dry 3h after taking-up, 480 DEG C of roasting 5h obtain one-level hydrogenation catalyst 3.
Containing the NiO of 8wt%, the MoO of 18wt% in one-level hydrogenation catalyst 3
3, the La of 1wt%, all the other are γ-Al
2o
3-ZrO
2.
Prepare secondary hydrogenation catalyzer:
(1), after the modified beta molecular sieve of 60g aluminum oxide, 25g, 15gZSM-5 molecular sieve, 50g hydroxypropylcellulose and 3g graphite are added water mixing, fully mediate and be squeezed into strip, then at 230 DEG C dry 2h, at 400 DEG C, roasting 4h, obtains carrier; ZSM-5 molecular sieve is the molecular sieve of Template-free method Hydrothermal Synthesis, and beta-molecular sieve is processed 1h and obtains by modified beta molecular sieve under 600 DEG C of water vapour and 6MPa pressure;
(2) 2mol ammonium paratungstate, 0.4mol nickelous acetate and 4mol water are mixed to form solution I, by above-mentioned carrier impregnation 2h in solution I, then at 200 DEG C dry 5h, 380 DEG C of roasting 8h obtain Vehicle element thing;
(3) 0.6mol molybdic oxide, 0.5mol nickelous acetate and 2mol water are mixed to form solution II, described Vehicle element thing is immersed in 2h in solution II, then obtain secondary hydrogenation catalyzer 3 at 210 DEG C of dry 2h, 410 DEG C of roasting 5h.
Containing 20wt%WO in secondary hydrogenation catalyzer 3
3, 4wt%MoO
3, 11wt%NiO, 14wt%ZSM-5 molecular sieve and 16wt% modified beta molecular sieve, all the other are aluminum oxide.
Embodiment 4
Preparation one-level hydrogenation catalyst:
(1) by 7gZrO (NO
3)
22H
2o(is with ZrO
2quality meter) be mixed with the ZrO (NO of 0.4mol/L
3)
2solution; By the spherical gamma-Al of 63g
2o
3be immersed in 50 DEG C of Zr (NO
3)
4take out after 8h in solution, drier 3h, 400 DEG C of roasting 6h obtain γ-Al at 130 DEG C
2o
3-ZrO
2carrier.
(2) ammonia soln adding 28v% in 10g nickelous nitrate (in NiO quality) dissolves completely to nickelous nitrate, and the quadrol adding 0.8g afterwards again mixes, and finally adds the Ammonium Heptamolybdate of 20g (with MoO
3quality meter) and mix, obtain Mo-Ni co-impregnated solution.
(3) by γ-Al
2o
3-ZrO
2carrier impregnation is taken out after 10h in the Mo-Ni co-impregnated solution of the capacity equal with its pore volume, and at 130 DEG C, dry 3h, 400 DEG C of roasting 6h obtain presoma.
(4), after being dissolved completely with water by the Sedemesis (in cerium quality) of 2g, the citric acid adding 2.5g mixes, and presoma is put into above-mentioned mixed solution and floods 11h, and at 100 DEG C of dry 5h after taking-up, 550 DEG C of roasting 4h obtain one-level hydrogenation catalyst 4.
The NiO of one-level hydrogenation catalyst 4 containing 10wt%, the MoO of 20wt%
3, the Ce of 2wt%, all the other are γ-Al
2o
3-ZrO
2.
Prepare secondary hydrogenation catalyzer:
(1) to 60g pore capacities be 0.65cm
3adding 16g pore capacities in the high pore volume aluminum oxide of/g, the modified beta molecular sieve of 20g, 10gZSM-5 molecular sieve is 0.4cm
3after the low pore volume aluminum oxide of/g adds water mix with the mixture of 32g17v% salpeter solution, 1g graphite, fully mediate and be squeezed into strip, then at 230 DEG C dry 4h, at 430 DEG C, roasting 6h, obtains carrier; ZSM-5 molecular sieve is the molecular sieve of Template-free method Hydrothermal Synthesis, and beta-molecular sieve is processed 5h and obtains by modified beta molecular sieve under 360 DEG C of water vapour and 0.5MPa pressure;
(2) 1.5mol ammonium tungstate, 0.3mol nickelous nitrate and 3mol water are mixed to form solution I, by above-mentioned carrier impregnation 2h in solution I, then at 200 DEG C dry 5h, 430 DEG C of roasting 5h obtain Vehicle element thing;
(3) 0.5mol molybdic oxide, 0.4mol nickelous nitrate and 2mol water are mixed to form solution II, described Vehicle element thing is immersed in 2h in solution II, then obtain secondary hydrogenation catalyzer 4 at 210 DEG C of dry 2h, 410 DEG C of roasting 5h.
Containing 22wt%WO in secondary hydrogenation catalyzer 4
3, 6wt%MoO
3, 7wt%NiO, 14wt%ZSM-5 molecular sieve and 20wt% modified beta molecular sieve, the high pore volume aluminum oxide of 25wt% and the low pore volume aluminum oxide of 6wt%.
Embodiment 5
Preparation one-level hydrogenation catalyst:
(1) by 5gZrO (NO
3)
22H
2o and 4gZr (CH
3cOO)
2(all with ZrO
2quality meter) be mixed with the Zr salts solution of 0.7mol/L; By the particulate state γ-Al of 81g
2o
3be immersed in 80 DEG C of Zr salts solutions and take out after 4h, drier 3h, 580 DEG C of roasting 5h obtain γ-Al at 140 DEG C
2o
3-ZrO
2carrier.
(2) ammonia soln adding 20v% in 1g nickelous nitrate and 2g nickel hydroxide (all in NiO quality) dissolves completely to nickel hydroxide, and the quadrol adding 0.15g afterwards again mixes, and finally adds the Ammonium Heptamolybdate of 8g (with MoO
3quality meter) and mix, obtain Mo-Ni co-impregnated solution.
(3) by γ-Al
2o
3-ZrO
2carrier impregnation is taken out after 15h in the Mo-Ni co-impregnated solution of the capacity equal with its pore volume, and dry at 100 DEG C, 400 DEG C of roasting 4h obtain presoma.
(4) after the praseodymium acetate (in praseodymium quality) of the praseodymium oxalate of 0.05g and 0.05g being dissolved completely with water, the citric acid adding 0.8g mixes, presoma is put into above-mentioned mixed solution and flood 15h, 120 DEG C of dryings after taking-up, 500 DEG C of roasting 6h obtain one-level hydrogenation catalyst 5.
The NiO of one-level hydrogenation catalyst 5 containing 4wt%, the MoO of 10wt%
3, the Pr of 0.1wt%, all the other are γ-Al
2o
3-ZrO
2.
Prepare secondary hydrogenation catalyzer:
(1) to 65g pore capacities be 0.8cm
3adding 17g pore capacities in the high pore volume aluminum oxide of/g, the modified beta molecular sieve of 26g, 14gZSM-5 molecular sieve is 0.2cm
3after the low pore volume aluminum oxide of/g adds water mix with the mixture of 34g10v% salpeter solution, 2g graphite, fully mediate and be squeezed into strip, then at 230 DEG C dry 4h, at 430 DEG C, roasting 6h, obtains carrier; ZSM-5 molecular sieve is the molecular sieve of Template-free method Hydrothermal Synthesis, and beta-molecular sieve is processed 5h and obtains by modified beta molecular sieve under 420 DEG C of water vapour and 0.3MPa pressure;
(2) 1.5mol ammonium tungstate, 0.3mol nickelous nitrate and 3mol water are mixed to form solution I, by above-mentioned carrier impregnation 2h in solution I, then at 200 DEG C dry 5h, 430 DEG C of roasting 5h obtain Vehicle element thing;
(3) 0.5mol molybdic oxide, 0.4mol nickelous nitrate and 2mol water are mixed to form solution II, described Vehicle element thing is immersed in 2h in solution II, then obtain secondary hydrogenation catalyzer 5 at 210 DEG C of dry 2h, 410 DEG C of roasting 5h.
Containing 23wt%WO in described secondary hydrogenation catalyzer 5
3, 4wt%MoO
3, 7wt%NiO, 19wt%ZSM-5 molecular sieve and 24wt% modified beta molecular sieve, the high pore volume aluminum oxide of 18wt% and the low pore volume aluminum oxide of 5wt%.
Embodiment 6
The hydrofining technology of heavy benzene and washing oil mixture as shown in Figure 1, comprising:
(1) be seated in one-level hydrogenator by the one-level hydrogenation catalyst 1 of 100ml, be the heavy benzene of 1:1 and the mixture of washing oil by weight ratio, pass in this reactor with hydrogen with the volume ratio of 1:800 after mixing, its volume space velocity is 0.75h
-1, the temperature controlled in reactor is 175 DEG C, and pressure is that 3MPa carries out one-level hydrogenation reaction, obtains one-level hydrogenation products;
(2) after one-level hydrogenation products being mixed with 1:600 volume ratio with hydrogen, be incorporated into load have in the secondary hydrogenation reactor of 100ml secondary hydrogenation catalyzer 1 proceed secondary hydrogenation reaction, its volume space velocity is 0.25h
-1temperature of reaction is 350 DEG C, reaction pressure is 4MPa, after reaction, secondary hydrogenation product is introduced high-pressure separator to be separated, the recycle system that the complete hydrogen of unreacted enters from the top of high-pressure separator continues to use, sour water is from the bottom part of high-pressure separator from removing, and middle layer oil phase is delivered to light pressure separator by variable valve and continued to be separated, and finally obtains product.
Embodiment 7
As shown in Figure 2, on the basis of embodiment 6, after the secondary hydrogenation product of 10wt% is mixed with the volume ratio of 1:600 with hydrogen, return in the one-level hydrogenator being filled with one-level hydrogenation catalyst 1 and carry out one-level hydrogenation reaction, simultaneously, the secondary hydrogenation product of all the other 90wt% is carried out later separation according to the process of embodiment 6, obtains product.
Embodiment 8
The hydrofining technology of heavy benzene and washing oil mixture as shown in Figure 1, comprising:
(1) being seated in one-level hydrogenator by the one-level hydrogenation catalyst 2 of 100ml, is the heavy benzene of 1:10 and the mixture of washing oil by weight ratio, and after mixing with the volume ratio of 1:1200 with hydrogen, pass in this reactor, its volume space velocity is 1.0h
-1, the temperature controlled in reactor is 235 DEG C, and pressure is that 8MPa carries out one-level hydrogenation reaction, obtains one-level hydrogenation products;
(2) after one-level hydrogenation products being mixed with 1:1000 volume ratio with hydrogen, be incorporated into load have in the secondary hydrogenation reactor of 100ml secondary hydrogenation catalyzer 2 proceed secondary hydrogenation reaction, its volume space velocity is 1.5h
-1temperature of reaction is 400 DEG C, reaction pressure is 6MPa, after reaction, secondary hydrogenation product is introduced high-pressure separator to be separated, the recycle system that the complete hydrogen of unreacted enters from the top of high-pressure separator continues to use, sour water is from the bottom part of high-pressure separator from removing, and middle layer oil phase is delivered to light pressure separator by variable valve and continued to be separated, and finally obtains product.
Embodiment 9
As shown in Figure 2, on the basis of embodiment 8, after the secondary hydrogenation product of 40wt% is mixed with the volume ratio of 1:1000 with hydrogen, return in the one-level hydrogenator being filled with one-level hydrogenation catalyst 2 and carry out one-level hydrogenation reaction, simultaneously, the secondary hydrogenation product of all the other 60wt% is carried out later separation according to the process of embodiment 8, obtains product.
Embodiment 10
The hydrofining technology of heavy benzene and washing oil mixture as shown in Figure 3, comprising:
(1) be that the heavy benzene of 1:6 and washing oil mixture remove after solid impurity through two-stage filtration and be forced into 10-12MPa by weight ratio, then successively by protective material and metal remover, to remove trace metal impurities in mixture and the easily polymerization reactant such as vinylbenzene, indenes;
(2) be seated in one-level hydrogenator by 100ml one-level hydrogenation catalyst 3, after mixing with the volume ratio of 1:1000 with hydrogen with washing oil mixture through the heavy benzene of above-mentioned process, pass in this reactor, its volume space velocity is 0.4h
-1, the temperature controlled in reactor is 200 DEG C, and pressure is that 5MPa carries out one-level hydrogenation reaction, obtains one-level hydrogenation products;
(3) after one-level hydrogenation products being mixed with 1:800 volume ratio with hydrogen, be incorporated into load have in the secondary hydrogenation reactor of 100ml secondary hydrogenation catalyzer 3 proceed secondary hydrogenation reaction, its volume space velocity is 1.0h
-1temperature of reaction is 375 DEG C, reaction pressure is 5MPa, by secondary hydrogenation product and the heat exchange of one-level hydrogenation products after reaction, temperature is down to about 260 DEG C, carry out heat exchange with heavy benzene and washing oil mixture more afterwards, temperature is down to about 130 DEG C, is cooled to normal temperature after filling into de-salted water and inhibiter in the secondary hydrogenation product after cooling; Above-mentioned normal temperature material is introduced high-pressure separator be separated, the recycle system that the complete hydrogen of unreacted enters from the top of high-pressure separator continues to use, sour water is from the bottom part of high-pressure separator from removing, middle layer oil phase is delivered to light pressure separator by variable valve and is continued to be separated, and obtains product after separation.
Embodiment 11
As shown in Figure 4, on the basis of embodiment 10, after the secondary hydrogenation product of 20wt% is mixed with the volume ratio of 1:700 with hydrogen, return in the one-level hydrogenator being filled with one-level hydrogenation catalyst 3 and carry out one-level hydrogenation reaction, simultaneously, the secondary hydrogenation product of all the other 80wt% is carried out follow-up heat exchange, separation according to the process of embodiment 10, finally obtains product.
Embodiment 12
The hydrofining technology of heavy benzene and washing oil mixture as shown in Figure 3, comprising:
(1) be that the heavy benzene of 1:4 and washing oil mixture remove after solid impurity through two-stage filtration and be forced into 5-10MPa by weight ratio, then successively by protective material and metal remover, to remove trace metal impurities in mixture and the easily polymerization reactant such as vinylbenzene, indenes;
(2) be seated in one-level hydrogenator by 100ml one-level hydrogenation catalyst 4, after mixing with the volume ratio of 1:900 with hydrogen with washing oil mixture through the heavy benzene of above-mentioned process, pass in this reactor, its volume space velocity is 0.9h
-1, the temperature controlled in reactor is 210 DEG C, and pressure is that 4MPa carries out one-level hydrogenation reaction, obtains one-level hydrogenation products;
(3) after one-level hydrogenation products being mixed with 1:700 volume ratio with hydrogen, be incorporated into load have in the secondary hydrogenation reactor of 100ml secondary hydrogenation catalyzer 4 proceed secondary hydrogenation reaction, its volume space velocity is 1.0h
-1temperature of reaction is 360 DEG C, reaction pressure is 5MPa, by secondary hydrogenation product and the heat exchange of one-level hydrogenation products after reaction, temperature is down to about 260 DEG C, carry out heat exchange with heavy benzene and washing oil mixture more afterwards, temperature is down to about 130 DEG C, is cooled to normal temperature after filling into de-salted water and inhibiter in the secondary hydrogenation product after cooling; Above-mentioned normal temperature material is introduced high-pressure separator be separated, the recycle system that the complete hydrogen of unreacted enters from the top of high-pressure separator continues to use, sour water is from the bottom part of high-pressure separator from removing, middle layer oil phase is delivered to light pressure separator by variable valve and is continued to be separated, and obtains product after separation.
Embodiment 13
As shown in Figure 4, on the basis of embodiment 12, after the secondary hydrogenation product of 30wt% is mixed with the volume ratio of 1:800 with hydrogen, return in the one-level hydrogenator being filled with one-level hydrogenation catalyst 4 and carry out one-level hydrogenation reaction, simultaneously, the secondary hydrogenation product of all the other 70wt% is carried out follow-up heat exchange, separation according to the process of embodiment 12, finally obtains product.
Embodiment 14
The hydrofining technology of heavy benzene and washing oil mixture as shown in Figure 3, comprising:
(1) be that the heavy benzene of 1:7 and washing oil mixture remove after solid impurity through two-stage filtration and be forced into 5-10MPa by weight ratio, then successively by protective material and metal remover, to remove trace metal impurities in mixture and the easily polymerization reactant such as vinylbenzene, indenes;
(2) be seated in one-level hydrogenator by 100ml one-level hydrogenation catalyst 5, after mixing with the volume ratio of 1:1000 with hydrogen with washing oil mixture through the heavy benzene of above-mentioned process, pass in this reactor, its volume space velocity is 0.75h
-1, the temperature controlled in reactor is 175 DEG C, and pressure is that 5MPa carries out one-level hydrogenation reaction, obtains one-level hydrogenation products;
(3) after one-level hydrogenation products being mixed with 1:1000 volume ratio with hydrogen, be incorporated into load have in the secondary hydrogenation reactor of 100ml secondary hydrogenation catalyzer 5 proceed secondary hydrogenation reaction, its volume space velocity is 0.4h
-1temperature of reaction is 400 DEG C, reaction pressure is 5MPa, by secondary hydrogenation product and the heat exchange of one-level hydrogenation products after reaction, temperature is down to about 260 DEG C, carry out heat exchange with heavy benzene and washing oil mixture more afterwards, temperature is down to about 130 DEG C, is cooled to normal temperature after filling into de-salted water and inhibiter in the secondary hydrogenation product after cooling; Above-mentioned normal temperature material is introduced high-pressure separator be separated, the recycle system that the complete hydrogen of unreacted enters from the top of high-pressure separator continues to use, sour water is from the bottom part of high-pressure separator from removing, middle layer oil phase is delivered to light pressure separator by variable valve and is continued to be separated, and obtains product after separation.
Embodiment 15
As shown in Figure 4, on the basis of embodiment 14, after the secondary hydrogenation product of 30wt% is mixed with the volume ratio of 1:1000 with hydrogen, return in the one-level hydrogenator being filled with one-level hydrogenation catalyst 5 and carry out one-level hydrogenation reaction, simultaneously, the secondary hydrogenation product of all the other 70wt% is carried out follow-up heat exchange, separation according to the process of embodiment 14, finally obtains product.
Protective material in above-described embodiment and metal remover can select any commercially available prod, and two-stage filtration can select any enforceable mode in prior art to carry out.
Hydrogenation catalysts all in above-described embodiment before use, first need carry out prevulcanized.Pre-vulcanization process is: with 2h
-1liquid air speed passes into containing 10wt%CS in the reactor that hydrogenation catalyst is housed
2benzole soln, pass into the hydrogen of 2MPa, wherein hydrogen and CS simultaneously
2the volume ratio of benzole soln is 700:1, continues prevulcanized and lower the temperature after 12 hours at 250 DEG C.
Comparative example 1
The hydrofining technology of heavy benzene and washing oil mixture comprises:
(1) be seated in one-level hydrogenator by the washing oil hydrogenation catalyst of 100ml, be the heavy benzene of 1:1 and the mixture of washing oil by weight ratio, pass in this reactor with hydrogen with the volume ratio of 1:800 after mixing, its volume space velocity is 0.75h
-1, the temperature controlled in reactor is 175 DEG C, and pressure is that 3MPa carries out one-level hydrogenation reaction, obtains one-level hydrogenation products;
(2) after one-level hydrogenation products being mixed with 1:600 volume ratio with hydrogen, be incorporated into load have in the secondary hydrogenation reactor of 100ml washing oil hydrogenation catalyst proceed secondary hydrogenation reaction, its volume space velocity is 0.25h
-1temperature of reaction is 350 DEG C, reaction pressure is 4MPa, after reaction, the secondary hydrogenation product of 90wt% is introduced high-pressure separator to be separated, the recycle system that the complete hydrogen of unreacted enters from the top of high-pressure separator continues to use, sour water is from the bottom part of high-pressure separator from removing, and middle layer oil phase is delivered to light pressure separator by variable valve and continued to be separated, and finally obtains product;
(3), after the secondary hydrogenation product of all the other 10wt% being mixed with the volume ratio of 1:600 with hydrogen, return in the one-level hydrogenator being filled with washing oil hydrogenation catalyst and proceed one-level hydrogenation reaction.
Described washing oil hydrogenation catalyst is composed of the following components: the modified molecular screen of the Tungsten oxide 99.999 of 15-30wt%, the nickel oxide of 2-15wt% and 10-45wt%, and all the other are auxiliary agent B and F.
Comparative example 2
The hydrofining technology of heavy benzene and washing oil mixture comprises:
(1) be seated in one-level hydrogenator by the heavy benzene hydrogenation catalyst of 100ml, be the heavy benzene of 1:1 and the mixture of washing oil by weight ratio, pass in this reactor with hydrogen with the volume ratio of 1:800 after mixing, its volume space velocity is 0.75h
-1, the temperature controlled in reactor is 175 DEG C, and pressure is that 3MPa carries out one-level hydrogenation reaction, obtains one-level hydrogenation products;
(2) after one-level hydrogenation products being mixed with 1:600 volume ratio with hydrogen, be incorporated into load have in the secondary hydrogenation reactor of 100ml heavy benzene hydrogenation catalyst proceed secondary hydrogenation reaction, its volume space velocity is 0.25h
-1temperature of reaction is 350 DEG C, reaction pressure is 4MPa, after reaction, the secondary hydrogenation product of 90wt% is introduced high-pressure separator to be separated, the recycle system that the complete hydrogen of unreacted enters from the top of high-pressure separator continues to use, sour water is from the bottom part of high-pressure separator from removing, and middle layer oil phase is delivered to light pressure separator by variable valve and continued to be separated, and finally obtains product;
(3), after the secondary hydrogenation product of all the other 10wt% being mixed with the volume ratio of 1:600 with hydrogen, return in the one-level hydrogenator being filled with heavy benzene hydrogenation catalyst and proceed one-level hydrogenation reaction.
Described heavy benzene hydrogenation catalyst is composed of the following components: the potassium of the molybdenum oxide of 10-24wt%, the nickel oxide of 2.6-8.8wt% and 0.3-1.5wt%, and all the other are alumina supporter.
Test case
(1) adopt gas chromatograph to measure the organosulfur of the heavy benzene in embodiment 6-15 and comparative example 1-2 and washing oil mixture and the finished product, organic nitrogen content, and calculate its organic sulfur removal rate and organonitrogen decreasing ratio, the results are shown in following table.
(2) adopt iodine number method to carry out degree of unsaturation mensuration to the heavy benzene in embodiment 6-15 and comparative example 1-2 and washing oil mixture and the finished product, and calculate its hydrogenation reaction rate according to the following formula, the results are shown in following table.
(3) adopt the cetane value of diesel oil infrared spectrum analyser to the heavy benzene in embodiment 6-15 and comparative example 1-2 and washing oil mixture and the finished product to measure, and calculate its cetane value conservation rate according to the following formula, the results are shown in following table.
(4) using the one-level hydrogenation products of embodiment 6-15 as sample, adopt the molecular-weight average of vapor pressure osmose process (VPO) working sample, measurement result sees the following form.
As can be seen from the above results, compared with the technique of comparative example 1,2, the organic sulfur removal rate of the hydrofining technology of the bright described heavy benzene of this law and washing oil mixture, organonitrogen decreasing ratio and hydrogenation reaction rate are all higher, therefore known, hydrofining technology of the present invention is better for the removal effect of organosulfur and organonitrogen impurity in heavy benzene and washing oil mixture, and the hydrogenation effect for alkene in mixture is better.
And as seen from the above table compared with the technique of comparative example 1,2, the bright technique of this law is not easy the aromatic hydroxy compound generation open loop chain-breaking reaction made in heavy benzene and washing oil mixture, and thus the conservation rate of cetane value is higher.
Have again, the molecular-weight average of comparing embodiment 6-15 one-level hydrogenation products is known, part secondary hydrogenation product is returned in A reactor and continue to participate in one-level hydrogenation, the unsaturates content in the secondary hydrogenation product dilution heavy benzene and washing oil mixture with high-content saturates can be effectively utilized, thus effectively reduce the probability that autohemagglutination occurs unsaturates in one-level hydrogenator, the molecular-weight average of one-level hydrogenation reaction product is significantly reduced.
Although the present invention has carried out detailed elaboration by above-mentioned specific embodiment to it; but; those skilled in the art should be understood that and made on this basis not exceed any form of claims and the change of details, all belong to invention which is intended to be protected.
Claims (13)
1. a hydrofining technology for heavy benzene and washing oil mixture, comprises
(1), after heavy benzene and washing oil mixture mix with hydrogen, under the effect of one-level hydrogenation catalyst, carry out hydrogenation reaction, obtain one-level hydrogenation products;
(2) after one-level hydrogenation products mixes with hydrogen, under secondary hydrogenation catalyst action, proceed hydrogenation reaction, obtain secondary hydrogenation product, separation is carried out to secondary hydrogenation product and obtains product;
Described one-level hydrogenation catalyst comprises following component:
NiO 4～10wt％
MoO
310～20wt％
Mixture 0.1 ~ the 2wt% of one or more in rare earth element
All the other are carrier γ-Al
2o
3-ZrO
2;
Described secondary hydrogenation catalyzer comprises following component:
WO
317-23wt％
MoO
37-12wt％
NiO 3-6wt％
ZSM-5 molecular sieve 14-24wt%
Beta-molecular sieve 14-24wt%
All the other are aluminum oxide;
The volume ratio of described heavy benzene and washing oil mixture, hydrogen is 1:(800-1200); The temperature of one-level hydrogenation reaction is 175 ~ 235 DEG C, and reaction pressure is 3.0 ~ 8.0MPa;
The volume ratio of described one-level hydrogenation products and hydrogen is 1:(600-1000); The temperature of secondary hydrogenation reaction is 350 ~ 400 DEG C, and reaction pressure is 4 ~ 6MPa.
2. hydrofining technology according to claim 1, it is characterized in that, in step (2), the described secondary hydrogenation product of part is separated, and by after secondary hydrogenation product mixes with hydrogen described in rest part, return described one-level hydrogenation catalyst and carry out one-level hydrogenation reaction.
3. hydrofining technology according to claim 2, it is characterized in that, the quality of described rest part secondary hydrogenation product accounts for the 10-40% of all secondary hydrogenation product qualities, and the volume ratio that described rest part secondary hydrogenation product mixes with hydrogen is 1:(600-1000).
4., according to the arbitrary described hydrofining technology of claim 1-3, it is characterized in that,
Described one-level hydrogenation catalyst is composed of the following components:
NiO 4～10wt％
MoO
310-20wt％
La 0.1-2wt％
All the other are carrier γ-Al
2o
3-ZrO
2.
5., according to the arbitrary described hydrofining technology of claim 1-3, it is characterized in that, described ZSM-5 molecular sieve is prepared by Template-free method hydrothermal synthesis method; Described beta-molecular sieve is the modified beta molecular sieve after the water vapour heat treated of 360-600 DEG C, and the processing pressure of described water vapour is 0.5-6MPa, and the treatment time is 1-5h.
6. hydrofining technology according to claim 4, is characterized in that, described ZSM-5 molecular sieve is prepared by Template-free method hydrothermal synthesis method; Described beta-molecular sieve is the modified beta molecular sieve after the water vapour heat treated of 360-600 DEG C, and the processing pressure of described water vapour is 0.5-6MPa, and the treatment time is 1-5h.
7., according to the arbitrary described hydrofining technology of claim 1-3, it is characterized in that, described aluminum oxide is made up of high pore volume aluminum oxide and low pore volume aluminum oxide; The pore volume of described high pore volume aluminum oxide is greater than 0.65cm
3/ g, the pore volume of described low pore volume aluminum oxide is less than 0.40cm
3/ g.
8. hydrofining technology according to claim 4, is characterized in that, described aluminum oxide is made up of high pore volume aluminum oxide and low pore volume aluminum oxide; The pore volume of described high pore volume aluminum oxide is greater than 0.65cm
3/ g, the pore volume of described low pore volume aluminum oxide is less than 0.40cm
3/ g.
9. hydrofining technology according to claim 5, is characterized in that, described aluminum oxide is made up of high pore volume aluminum oxide and low pore volume aluminum oxide; The pore volume of described high pore volume aluminum oxide is greater than 0.65cm
3/ g, the pore volume of described low pore volume aluminum oxide is less than 0.40cm
3/ g.
10. hydrofining technology according to claim 8 or claim 9, it is characterized in that, the weight ratio of described high pore volume aluminum oxide and low pore volume aluminum oxide is (52-70): (16-17).
11. according to claim 1,2,3,6,8 or 9 arbitrary described hydrofining technologies, it is characterized in that, in described heavy benzene and washing oil mixture, the weight ratio of heavy benzene, washing oil is 1:(1 ~ 10).
12. according to the arbitrary described hydrofining technology of claim 1,2,3,6,8 or 9, and it is characterized in that, the preparation of described one-level hydrogenation catalyst comprises the steps:
(1) by shaping γ-Al
2o
3take out after dipping in soluble zirconium salts solution, after drying, roasting, obtain γ-Al
2o
3-ZrO
2carrier;
(2) in nickel salt or nickel hydroxide, add ammonia soln to after dissolving completely, then add quadrol and mix, finally add molybdenum salt and mix, obtain Mo-Ni co-impregnated solution;
(3) by described γ-Al
2o
3-ZrO
2take out after carrier floods in described Mo-Ni co-impregnated solution, after drying, roasting, obtain presoma;
(4) in the rare-earth element salt of solubility, add water to dissolving completely, then add citric acid and mix formation mixed solution, take out after described presoma is flooded in described mixed solution, drying, roasting.
13. according to the arbitrary described hydrofining technology of claim 1,2,3,6,8 or 9, and it is characterized in that, the preparation of described secondary hydrogenation catalyzer comprises the steps:
(1) aluminum oxide or high pore volume aluminum oxide, beta-molecular sieve or modified beta molecular sieve, ZSM-5 molecular sieve, binding agent and extrusion aid are mixed, shaping, then drying, roasting obtain carrier;
(2) tungstate, nickel salt and water are mixed to form solution I, by described carrier impregnation in solution I, then drying, roasting obtain Vehicle element thing;
(3) molybdenum oxide, nickel salt and water are mixed to form solution II, described Vehicle element thing are immersed in solution II, then drying, roasting.
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