CN103122260A - 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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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 a kind of heavy benzene and washing oil mixture be carried out hydrorefined technique, belong to the hydrogenation technique technical field.
Background technology
Washing oil is the rectifying cut of coal tar under 230-300 ℃, and its output is very large, accounts for the 4-8% of coal tar total amount.Washing oil directly uses as the elutriant of benzene series material usually, namely being used as waste liquid after wash-out discards, but in fact contain the materials such as methylnaphthalene, dimethylnaphthalene, cresols and xylenol in washing oil, these materials all can be made Organic Chemicals and use after extracting, be worth even if washing oil therefore after wash-out remains to have to extract.But in washing oil except containing above-mentioned extractible material, also contain 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 methylnaphthalene, dimethylnaphthalene, cresols and xylenol that extract, therefore need at first above-mentioned Impurity removal to be fallen, industrial common employing catalytic hydrogenation process is removed the above-mentioned impurity in washing oil.
Washing oil hydrogenation process for upgrading need to have the independently reaction environment of equipment and High Temperature High Pressure, but due to the amount of washing oil institute extracting substance less, added value is low, therefore industry member generally believes that washing oil is extracted the value of the product that obtains compares with the cost that 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 of therefore relevant washing oil catalytic hydrogenation process seldom.
Heavy benzene is in the crude benzol course of processing, and isolated heavy constituent by product at the bottom of the tower is a kind of colourless to flaxen oily liquids, and 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.Mainly contain the higher materials of added value such as naphthalene, alpha-methyl-naphthalene, beta-methylnaphthalene, indenes, coumarone in heavy benzene, but the sulphur compound and the nitrogen compound that also contain high-content due to heavy benzene, thereby can't directly obtain high purity product, industrial is also generally to adopt catalytic hydrogenation process to remove sulphur, nitrogen impurity, obtains high purity product.
Up to now, also not about the report of heavy benzene and washing oil mixture through catalytic hydrogenation technique, just washing oil catalytic hydrogenation process and heavy benzene catalytic hydrogenation process there is respectively report in prior art.The technique of the standby gasoline of washing oil Hydrogenation and diesel oil is disclosed as Chinese patent literature CN101486926A; washing oil is mixed the reactor by filling protective material, catalyst for demetalation, Hydrobon catalyst and/or catalyst for hydro-upgrading with hydrogen; the hydrogenated oil that obtains 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, with enter successively the fixed bed pre-hydrogenator after hydrogen mixes and fixed bed master hydrogenator 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 due to the dopant species of heavy benzene and washing oil mixture, adopt hydrogenation technique in above-mentioned technology all can't significantly remove impurity in heavy benzene and washing oil mixture, this is because the washing oil hydrogenation catalyst that adopts in above-mentioned technique and heavy benzene hydrogenation catalyst are not suitable for all impurity of removing in heavy benzene and washing oil mixture, therefore have a lot of organosulfurs in heavy benzene and washing oil mixture and organonitrogen impurity can't be removed fully, thereby affected the purity of resulting 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 the diesel component that extracts very low, and 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 can't significantly be removed impurity in heavy benzene and washing oil mixture, and in prior art also not about the report of heavy benzene and washing oil hydrogenation mixture technique; And then a kind of heavy benzene of a large amount of impurity and hydrofining technology of washing oil mixture can removed in heavy benzene and washing oil mixture proposed.
The washing oil hydrogenation technique that the present invention's while another technical problem to be solved is prior art processes and heavy benzene hydrogenation technique easily cause the aromatic hydroxy compound generation open loop chain-breaking reaction in heavy benzene and washing oil mixture, have reduced thus the cetane value of the diesel component that extracts; And then a kind of heavy benzene of diesel component cetane value and hydrofining technology of washing oil mixture of improving proposed.
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, comprise
(1) heavy benzene and washing oil mixture with after hydrogen mixes, carry out hydrogenation reaction under the effect of one-level hydrogenation catalyst, obtain the one-level hydrogenation products;
(2) the one-level hydrogenation products with after hydrogen mixes, is proceeded hydrogenation reaction under the effect of secondary hydrogenation catalyst, obtains the secondary hydrogenation products, the secondary hydrogenation products is separated obtaining 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 catalyst comprises following component:
All the other are aluminum oxide.
In step (2), the described secondary hydrogenation products of part is separated, and with the described secondary hydrogenation products of rest part with after hydrogen mixes, return to described one-level hydrogenation catalyst and carry out the one-level hydrogenation reaction.
The quality of described rest part secondary hydrogenation products accounts for the 10-40% of all secondary hydrogenation products quality, and the volume ratio that described rest part secondary hydrogenation products 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 by preparing without the template hydrothermal synthesis method; Described beta-molecular sieve is the modified beta molecular sieve after the water vapour heat treated of 360-600 ℃, and the processing pressure of described water vapour is 0.5-6MPa, and the treatment time is 1-5h.
Described aluminum oxide is comprised 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 ℃, and reaction pressure is 3.0～8.0MPa.
The temperature of secondary hydrogenation reaction is 350～400 ℃, and reaction pressure is 4～6MPa.
The preparation of described one-level hydrogenation catalyst comprises the steps:
(1) with the γ-Al of moulding
2O
3Take out after dipping in the soluble zirconium salts solution, obtain γ-Al after drying, roasting
2O
3-ZrO
2Carrier;
(2) add in nickel salt or the nickel hydroxide ammonia soln to dissolving fully, then add quadrol to mix, add at last molybdenum salt to mix, obtain the Mo-Ni co-impregnated solution;
(3) with described γ-Al
2O
3-ZrO
2Take out after carrier floods in described Mo-Ni co-impregnated solution, obtain presoma after drying, roasting;
(4) add entry to dissolving fully in the rare-earth element salt of solubility, then add citric acid and mix the formation mixed solution, take out after described presoma is flooded in described mixed solution, drying, roasting get final product.
The preparation of described secondary hydrogenation catalyst 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, moulding, then drying, roasting obtain carrier;
(2) tungstate, nickel salt are mixed with water form solution I, in solution I, then drying, roasting obtain carrier pre-treatment thing with described carrier impregnation;
(3) molybdenum oxide, nickel salt are mixed with water form the solution II, described carrier pre-treatment thing is immersed in the solution II, then drying, roasting get final product.
The present invention compares with the prior art scheme has following beneficial effect:
(1) hydrofining technology of heavy benzene of the present invention and washing oil mixture, comprise 1) with heavy benzene and washing oil mixture with after hydrogen mixes, hydrogenation obtains the one-level hydrogenation products under the effect of one-level hydrogenation catalyst; The 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) with the one-level hydrogenation products with after hydrogen mixes, proceed hydrogenation and obtain the secondary hydrogenation products under the effect of secondary hydrogenation catalyst, the secondary hydrogenation products is isolated to the upgrading cut; The secondary hydrogenation catalyst comprises the WO of following component: 17-23wt%
3, 7-12wt% MoO
3, 3-6wt% the ZSM-5 molecular sieve, the beta-molecular sieve of 14-24wt% of NiO, 14-24wt%, all the other are aluminum oxide.
At first by the one-level hydrogenation catalyst, a large amount of diene hydrogenations in heavy benzene and washing oil mixture are generated monoolefine, monoolefin hydrogenation generation alkane, simultaneously a large amount of organosulfurs and organonitrogen impurity are carried out the hydrogenation removal; Afterwards on aforesaid basis, by the secondary hydrogenation catalyst, remaining a small amount of alkene, organosulfur and organonitrogen impurity hydrogenation are removed, obtain containing the mixture of high density saturate, obtain highly purified product after the mixture that the secondary hydrogenation is produced separates.
One-level hydrogenation catalyst and secondary hydrogenation catalyst pore distribution that above-mentioned technique is used are wide, be widely used in the removal of various Sulfurs, nitrogen impurity, therefore the two-stage hydrogenation catalyst is used in combination the most of alkene that to remove heavy benzene and washing oil mixture and organosulfur, organonitrogen impurity, thereby obtains highly purified product.Avoided catalyzer that the catalyzer that in the prior art, the washing oil hydrogenation technique uses and heavy benzene hydrogenation technique use can't significantly remove impurity in heavy benzene and washing oil mixture, and existing technique does not have to be used for heavy benzene and washing oil mixture are carried out the hydrogenation catalyst of Impurity removal yet, thereby can't obtain the problem of high purity product.
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, thereby the cetane value content that has guaranteed the diesel component that extracts is very high, thereby obtained the clean fuel of high added value, avoided that in existing technique, washing oil hydrogenation catalyst and crude benzole hydrogenation catalyzer easily make aromatic hydroxy compound open loop chain rupture, thereby reduced 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 products of part is separated, simultaneously, the mixture that the secondary hydrogenation of remainder is produced is with after hydrogen mixes, continue to return one-level hydrogenation catalyst place and carry out hydrogenation reaction, because the content of saturated material in the secondary hydrogenation products is high, be placed on one-level hydrogenation catalyst place and can dilute the alkene that contains in heavy benzene and washing oil mixture material, the concentration of the unsaturated materials such as organosulfur and organonitrogen, avoided the heavy benzene of prior art and the high density unsaturated materials in the washing oil mixture material at one-level hydrogenation catalyst place, autohemagglutination to occur easily, 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, thereby reduce the carbon deposition quantity on one-level hydrogenation catalyst surface.
(3) hydrofining technology of heavy benzene of the present invention and washing oil mixture, 175～235 ℃ of the temperature of one-level hydrogenation reaction, reaction pressure are 3.0～8.0MPa.The temperature of reaction of heavy benzene hydrogenation catalyst is generally 200 ℃, and be unsuitable for the catalysis heavy benzene and the washing oil mixture carries out hydrogenation reaction, and in technique of the present invention the one-level hydrogenation catalyst can be at 175 ℃ 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, thereby saved cost.
(4) hydrofining technology of heavy benzene of the present invention and washing oil mixture, described aluminum oxide is comprised 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).The mixture of low pore volume aluminum oxide and salpeter solution is during as the carrier of binding agent Kaolinite Preparation of Catalyst, owing to itself just 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 and raw material evenly is bonded together with support material; And low pore volume aluminum oxide itself is also the component of carrier, therefore need not to get rid of in the process of carrier roasting, and this removes because of roasting the hole that additive produces with regard to having reduced carrier inside, and then has improved 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 the catalyzer duct in catalyzer, and then catalyzer can be used for removing the impurity of heavy benzene and the various complicated forms of washing oil mixture.
Description of drawings
For content of the present invention more easily is understood, the present invention is further detailed content of the present invention with embodiment by reference to the accompanying drawings;
Fig. 1 is the schema of heavy benzene described in the embodiment of the present invention 6 and 8 and washing oil hydrogenation mixture process for refining;
Fig. 2 is the schema of heavy benzene described in the embodiment of the present invention 7 and 9 and washing oil hydrogenation mixture process for refining;
Fig. 3 is the schema of heavy benzene described in the embodiment of the present invention 10,12 and 14 and washing oil hydrogenation mixture process for refining;
Fig. 4 is the schema of 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) with 8.6gZr (NO
3)
45H
2O(is with ZrO
2The quality meter) be mixed with the Zr (NO of 0.5mol/L
3)
4Solution; Bar shaped γ-Al with 77.4g
2O
3Be immersed in 60 ℃ of Zr (NO
3)
4Take out after 6h in solution, drier 5h, 550 ℃ of roasting 4h obtain γ-Al under 100 ℃
2O
3-ZrO
2Carrier.
(2) add ammonia soln to the nickel acetate of 10v% to dissolve fully in 4g nickel acetate (in the NiO quality), add again afterwards the quadrol of 0.32g to mix, add at last the ammonium tetramolybdate of 10g (with MoO
3The quality meter) and mix, obtain the Mo-Ni co-impregnated solution.
(3) with γ-Al
2O
3-ZrO
2Carrier impregnation is taken out after 8h in the Mo-Ni co-impregnated solution of the capacity that equates with its pore volume, and dry 4h, 550 ℃ of roasting 4h obtain presoma under 100 ℃.
(4) lanthanum nitrate (in the lanthanum quality) water of 0.1g is dissolved fully after, add the citric acid of 1g to mix, presoma is put into above-mentioned mixed solution floods 5h, after taking out, at 130 ℃ of dry 4h, 400 ℃ of roasting 6h obtain one-level hydrogenation catalyst 1.
The NiO that contains 4wt% in described one-level hydrogenation catalyst 1, the MoO of 10wt%
3, the La of 0.1wt%, all the other are γ-Al
2O
3-ZrO
2
Preparation secondary hydrogenation catalyst:
(1) 52g aluminum oxide, 15g beta-molecular sieve, 8gZSM-5 molecular sieve, 46g Walocel MT 20.000PV and 1g sesbania powder added water mix after, fully mediate and be squeezed into strip, dry 3h under 200 ℃, 380 ℃ of lower roasting 4h obtain carrier;
(2) 0.9mol ammonium tungstate, 0.1mol single nickel salt mixed with 2.5mol water form solution I, with above-mentioned carrier impregnation 2h in solution I, then under 200 ℃ dry 2h, 400 ℃ of roasting 4h obtain carrier pre-treatment thing;
(3) 0.4mol molybdic oxide, 0.2mol nickelous nitrate are mixed formation solution II with 1.5mol water, described carrier pre-treatment thing is immersed in 2h in the solution II, then obtains secondary hydrogenation catalyst 1 at 210 ℃ of dry 2h, 410 ℃ of roasting 5h.
Contain 17wt%WO in secondary hydrogenation catalyst 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) with 7gZrO (NO
3)
22H
2O(is with ZrO
2The quality meter) be mixed with the ZrO (NO of 0.5mol/L
3)
2Solution; Spherical gamma-Al with 63g
2O
3Be immersed in 60 ℃ of Zr (NO
3)
4Take out after 6h in solution, drier 5h, 400 ℃ of roasting 6h obtain γ-Al under 130 ℃
2O
3-ZrO
2Carrier.
(2) add ammonia soln to the nickelous nitrate of 28v% to dissolve fully in 10g nickelous nitrate (in the NiO quality), add again afterwards the quadrol of 0.8g to mix, add at last the Ammonium Heptamolybdate of 20g (with MoO
3The quality meter) and mix, obtain the Mo-Ni co-impregnated solution.
(3) with γ-Al
2O
3-ZrO
2Carrier impregnation is taken out after 10h in the Mo-Ni co-impregnated solution of the capacity that equates with its pore volume, and dry 4h, 400 ℃ of roasting 6h obtain presoma under 130 ℃.
(4) lanthanum oxalate (in the lanthanum quality) water of 2g is dissolved fully after, add the citric acid of 2.5g to mix, presoma is put into above-mentioned mixed solution floods 11h, after taking out, at 100 ℃ of dry 4h, 550 ℃ of roasting 4h obtain one-level hydrogenation catalyst 2.
The NiO that contains 10wt% in described one-level hydrogenation catalyst 2, the MoO of 20wt%
3, the La of 2wt%, all the other are γ-Al
2O
3-ZrO
2
Preparation secondary hydrogenation catalyst:
(1) be 0.65cm with the 70g pore capacities
3After high pore volume aluminum oxide, 30g beta-molecular sieve, 20gZSM-5 molecular sieve, 52g hydroxypropylcellulose and the 5g graphite of/g adds water and mixes, fully mediate and be squeezed into strip, dry 5h under 230 ℃, 430 ℃ of lower roasting 5h obtain carrier;
(2) 2.5mol sodium wolframate, 0.5mol nickelous acetate mixed with 6mol water form solution I, with above-mentioned carrier impregnation 2h in solution I, then under 220 ℃ dry 3h, 380 ℃ of roasting 8h obtain carrier pre-treatment thing;
(3) 1mol molybdenum dioxide, 0.6mol nickelous chloride are mixed formation solution II with 2.5mol water, described carrier pre-treatment thing is immersed in 2h in the solution II, then obtains described secondary hydrogenation catalyst 2 at 210 ℃ of dry 2h, 410 ℃ of roasting 5h.
Contain 23wt%WO in described secondary hydrogenation catalyst 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) with 8gZr (CH
3COO)
2(with ZrO
2The quality meter) be mixed with the Zr (CH of 0.5mol/L
3COO)
2Solution; With the sheet γ of 75g-Al
2O
3Be immersed in 60 ℃ of Zr (NO
3)
4Take out after 6h in solution, drier 3h, 500 ℃ of roasting 5h obtain γ-Al under 120 ℃
2O
3-ZrO
2Carrier.
(2) add ammonia soln to the nickelous oxalate of 15v% to dissolve fully in 8g nickelous oxalate (in the NiO quality), add again afterwards the quadrol of 0.7g to mix, add at last the ammonium tetramolybdate of 18g (with MoO
3The quality meter) and mix, obtain the Mo-Ni co-impregnated solution.
(3) with γ-Al
2O
3-ZrO
2Carrier impregnation is taken out after 9h in the Mo-Ni co-impregnated solution of the capacity that equates with its pore volume, and dry 4h, 450 ℃ of roasting 4.8h obtain presoma under 110 ℃.
(4) lanthanum acetate (in the lanthanum quality) water of 1g is dissolved fully after, add the citric acid of 2g to mix, presoma is put into above-mentioned mixed solution floods 8h, after taking out, at 120 ℃ of dry 3h, 480 ℃ of roasting 5h obtain one-level hydrogenation catalyst 3.
The NiO that contains 8wt% in one-level hydrogenation catalyst 3, the MoO of 18wt%
3, the La of 1wt%, all the other are γ-Al
2O
3-ZrO
2
Preparation secondary hydrogenation catalyst:
(1) modified beta molecular sieve, 15gZSM-5 molecular sieve, 50g hydroxypropylcellulose and the 3g graphite of 60g aluminum oxide, 25g added water mix after, fully mediate and be squeezed into strip, then under 230 ℃ dry 2h, 400 ℃ of lower roasting 4h obtain carrier; ZSM-5 molecular sieve is the molecular sieve without the template Hydrothermal Synthesis, and modified beta molecular sieve is processed beta-molecular sieve 1h and obtained under 600 ℃ of water vapour and 6MPa pressure;
(2) 2mol ammonium paratungstate, 0.4mol nickelous acetate mixed with 4mol water form solution I, with above-mentioned carrier impregnation 2h in solution I, then under 200 ℃ dry 5h, 380 ℃ of roasting 8h obtain carrier pre-treatment thing;
(3) 0.6mol molybdic oxide, 0.5mol nickelous acetate are mixed formation solution II with 2mol water, described carrier pre-treatment thing is immersed in 2h in the solution II, then obtains secondary hydrogenation catalyst 3 at 210 ℃ of dry 2h, 410 ℃ of roasting 5h.
Contain 20wt%WO in secondary hydrogenation catalyst 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) with 7gZrO (NO
3)
22H
2O(is with ZrO
2The quality meter) be mixed with the ZrO (NO of 0.4mol/L
3)
2Solution; Spherical gamma-Al with 63g
2O
3Be immersed in 50 ℃ of Zr (NO
3)
4Take out after 8h in solution, drier 3h, 400 ℃ of roasting 6h obtain γ-Al under 130 ℃
2O
3-ZrO
2Carrier.
(2) add ammonia soln to the nickelous nitrate of 28v% to dissolve fully in 10g nickelous nitrate (in the NiO quality), add again afterwards the quadrol of 0.8g to mix, add at last the Ammonium Heptamolybdate of 20g (with MoO
3The quality meter) and mix, obtain the Mo-Ni co-impregnated solution.
(3) with γ-Al
2O
3-ZrO
2Carrier impregnation is taken out after 10h in the Mo-Ni co-impregnated solution of the capacity that equates with its pore volume, and dry 3h, 400 ℃ of roasting 6h obtain presoma under 130 ℃.
(4) Sedemesis (in the cerium quality) water of 2g is dissolved fully after, add the citric acid of 2.5g to mix, presoma is put into above-mentioned mixed solution floods 11h, after taking out, at 100 ℃ of dry 5h, 550 ℃ of roasting 4h obtain one-level hydrogenation catalyst 4.
One-level hydrogenation catalyst 4 contains the NiO of 10wt%, the MoO of 20wt%
3, the Ce of 2wt%, all the other are γ-Al
2O
3-ZrO
2
Preparation secondary hydrogenation catalyst:
(1) be 0.65cm to the 60g pore capacities
3Adding the 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 and mixture, the 1g graphite of 32g17v% salpeter solution add water and mixes, fully mediate and be squeezed into strip, then under 230 ℃ dry 4h, 430 ℃ of lower roasting 6h obtain carrier; ZSM-5 molecular sieve is the molecular sieve without the template Hydrothermal Synthesis, and modified beta molecular sieve is processed beta-molecular sieve 5h and obtained under 360 ℃ of water vapour and 0.5MPa pressure;
(2) 1.5mol ammonium tungstate, 0.3mol nickelous nitrate mixed with 3mol water form solution I, with above-mentioned carrier impregnation 2h in solution I, then under 200 ℃ dry 5h, 430 ℃ of roasting 5h obtain carrier pre-treatment thing;
(3) 0.5mol molybdic oxide, 0.4mol nickelous nitrate are mixed formation solution II with 2mol water, described carrier pre-treatment thing is immersed in 2h in the solution II, then obtains secondary hydrogenation catalyst 4 at 210 ℃ of dry 2h, 410 ℃ of roasting 5h.
Contain 22wt%WO in secondary hydrogenation catalyst 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) with 5gZrO (NO
3)
22H
2O and 4gZr (CH
3COO)
2(all with ZrO
2The quality meter) be mixed with the Zr salts solution of 0.7mol/L; With the particulate state γ of 81g-Al
2O
3Be immersed in 80 ℃ of Zr salts solutions and take out after 4h, drier 3h, 580 ℃ of roasting 5h obtain γ-Al under 140 ℃
2O
3-ZrO
2Carrier.
(2) add ammonia soln to the nickel hydroxide of 20v% to dissolve fully in 1g nickelous nitrate and 2g nickel hydroxide (all in the NiO quality), add again afterwards the quadrol of 0.15g to mix, add at last the Ammonium Heptamolybdate of 8g (with MoO
3The quality meter) and mix, obtain the Mo-Ni co-impregnated solution.
(3) with γ-Al
2O
3-ZrO
2Carrier impregnation is taken out after 15h in the Mo-Ni co-impregnated solution of the capacity that equates with its pore volume, and dry under 100 ℃, 400 ℃ of roasting 4h obtain presoma.
(4) praseodymium oxalate of 0.05g and the praseodymium acetate of 0.05g (in the praseodymium quality) water are dissolved fully after, add the citric acid of 0.8g to mix, presoma is put into above-mentioned mixed solution flood 15h, after taking out, 120 ℃ of dryings, 500 ℃ of roasting 6h obtain one-level hydrogenation catalyst 5.
One-level hydrogenation catalyst 5 contains the NiO of 4wt%, the MoO of 10wt%
3, the Pr of 0.1wt%, all the other are γ-Al
2O
3-ZrO
2
Preparation secondary hydrogenation catalyst:
(1) be 0.8cm to the 65g pore capacities
3Adding the 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 and mixture, the 2g graphite of 34g10v% salpeter solution add water and mixes, fully mediate and be squeezed into strip, then under 230 ℃ dry 4h, 430 ℃ of lower roasting 6h obtain carrier; ZSM-5 molecular sieve is the molecular sieve without the template Hydrothermal Synthesis, and modified beta molecular sieve is processed beta-molecular sieve 5h and obtained under 420 ℃ of water vapour and 0.3MPa pressure;
(2) 1.5mol ammonium tungstate, 0.3mol nickelous nitrate mixed with 3mol water form solution I, with above-mentioned carrier impregnation 2h in solution I, then under 200 ℃ dry 5h, 430 ℃ of roasting 5h obtain carrier pre-treatment thing;
(3) 0.5mol molybdic oxide, 0.4mol nickelous nitrate are mixed formation solution II with 2mol water, described carrier pre-treatment thing is immersed in 2h in the solution II, then obtains secondary hydrogenation catalyst 5 at 210 ℃ of dry 2h, 410 ℃ of roasting 5h.
Contain 23wt%WO in described secondary hydrogenation catalyst 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 comprises as shown in Figure 1:
(1) the one-level hydrogenation catalyst 1 with 100ml is seated in the one-level hydrogenator, is the heavy benzene of 1:1 and the mixture of washing oil with weight ratio, passes in this reactor after mixing with the volume ratio of 1:800 with hydrogen, and its volume space velocity is 0.75h
-1, the temperature of controlling in reactor is 175 ℃, pressure is that 3MPa carries out the one-level hydrogenation reaction, obtains the one-level hydrogenation products;
(2) the one-level hydrogenation products is mixed with the 1:600 volume ratio with hydrogen after, be incorporated into load and have in the secondary hydrogenator of 100ml secondary hydrogenation catalyst 1 and proceed the secondary hydrogenation reaction, its volume space velocity is 0.25h
-1Temperature of reaction is 350 ℃, reaction pressure is 4MPa, after reaction, the secondary hydrogenation products being introduced high-pressure separator separates, the complete hydrogen of unreacted enters the recycle system from the top of high-pressure separator to be continued to use, sour water separates from the bottom of high-pressure separator to be removed, and the middle layer oil phase is delivered to light pressure separator by variable valve and continued to separate, and obtains at last product.
Embodiment 7
As shown in Figure 2, on the basis of embodiment 6, after the secondary hydrogenation products of 10wt% is mixed with the volume ratio of 1:600 with hydrogen, return in the one-level hydrogenator that is filled with one-level hydrogenation catalyst 1 and carry out the one-level hydrogenation reaction, simultaneously, the secondary hydrogenation products of all the other 90wt% is carried out later separation according to the process of embodiment 6, obtain product.
Embodiment 8
The hydrofining technology of heavy benzene and washing oil mixture comprises as shown in Figure 1:
(1) the one-level hydrogenation catalyst 2 with 100ml is seated in the one-level hydrogenator, is the heavy benzene of 1:10 and the mixture of washing oil with weight ratio, after mixing with the volume ratio of 1:1200 with hydrogen, passes in this reactor, and its volume space velocity is 1.0h
-1, the temperature of controlling in reactor is 235 ℃, pressure is that 8MPa carries out the one-level hydrogenation reaction, obtains the one-level hydrogenation products;
(2) the one-level hydrogenation products is mixed with the 1:1000 volume ratio with hydrogen after, be incorporated into load and have in the secondary hydrogenator of 100ml secondary hydrogenation catalyst 2 and proceed the secondary hydrogenation reaction, its volume space velocity is 1.5h
-1Temperature of reaction is 400 ℃, reaction pressure is 6MPa, after reaction, the secondary hydrogenation products being introduced high-pressure separator separates, the complete hydrogen of unreacted enters the recycle system from the top of high-pressure separator to be continued to use, sour water separates from the bottom of high-pressure separator to be removed, and the middle layer oil phase is delivered to light pressure separator by variable valve and continued to separate, and obtains at last product.
Embodiment 9
As shown in Figure 2, on the basis of embodiment 8, after the secondary hydrogenation products of 40wt% is mixed with the volume ratio of 1:1000 with hydrogen, return in the one-level hydrogenator that is filled with one-level hydrogenation catalyst 2 and carry out the one-level hydrogenation reaction, simultaneously, the secondary hydrogenation products of all the other 60wt% is carried out later separation according to the process of embodiment 8, obtain product.
Embodiment 10
The hydrofining technology of heavy benzene and washing oil mixture comprises as shown in Figure 3:
(1) be that heavy benzene and the washing oil mixture of 1:6 is forced into 10-12MPa with weight ratio after two-stage filtration is removed solid impurity, then successively by protective material and metal remover, to remove the easily polymerization reactant such as trace metal impurities in mixture and vinylbenzene, indenes;
(2) 100ml one-level hydrogenation catalyst 3 is seated in the one-level hydrogenator, after mixing with the volume ratio of 1:1000 with hydrogen with the washing oil mixture through the heavy benzene of above-mentioned processing, passes in this reactor, its volume space velocity is 0.4h
-1, the temperature of controlling in reactor is 200 ℃, pressure is that 5MPa carries out the one-level hydrogenation reaction, obtains the one-level hydrogenation products;
(3) the one-level hydrogenation products is mixed with the 1:800 volume ratio with hydrogen after, be incorporated into load and have in the secondary hydrogenator of 100ml secondary hydrogenation catalyst 3 and proceed the secondary hydrogenation reaction, its volume space velocity is 1.0h
-1Temperature of reaction is 375 ℃, reaction pressure is 5MPa, after reaction with secondary hydrogenation products and the heat exchange of one-level hydrogenation products, temperature is down to 260 ℃ of left and right, carry out heat exchange with heavy benzene and washing oil mixture more afterwards, temperature is down to 130 ℃ of left and right, is cooled to normal temperature after filling into de-salted water and inhibiter in the secondary hydrogenation products after the cooling; Above-mentioned normal temperature material is introduced high-pressure separator to be separated, the complete hydrogen of unreacted enters the recycle system from the top of high-pressure separator to be continued to use, sour water separates from the bottom of high-pressure separator to be removed, the middle layer oil phase is delivered to light pressure separator by variable valve and is continued to separate, and obtains product after separation.
Embodiment 11
As shown in Figure 4, on the basis of embodiment 10, after the secondary hydrogenation products of 20wt% is mixed with the volume ratio of 1:700 with hydrogen, return in the one-level hydrogenator that is filled with one-level hydrogenation catalyst 3 and carry out the one-level hydrogenation reaction, simultaneously, the secondary hydrogenation products of all the other 80wt% is carried out follow-up heat exchange, separation according to the process of embodiment 10, obtain at last product.
Embodiment 12
The hydrofining technology of heavy benzene and washing oil mixture comprises as shown in Figure 3:
(1) be that heavy benzene and the washing oil mixture of 1:4 is forced into 5-10MPa with weight ratio after two-stage filtration is removed solid impurity, then successively by protective material and metal remover, to remove the easily polymerization reactant such as trace metal impurities in mixture and vinylbenzene, indenes;
(2) 100ml one-level hydrogenation catalyst 4 is seated in the one-level hydrogenator, after mixing with the volume ratio of 1:900 with hydrogen with the washing oil mixture through the heavy benzene of above-mentioned processing, passes in this reactor, its volume space velocity is 0.9h
-1, the temperature of controlling in reactor is 210 ℃, pressure is that 4MPa carries out the one-level hydrogenation reaction, obtains the one-level hydrogenation products;
(3) the one-level hydrogenation products is mixed with the 1:700 volume ratio with hydrogen after, be incorporated into load and have in the secondary hydrogenator of 100ml secondary hydrogenation catalyst 4 and proceed the secondary hydrogenation reaction, its volume space velocity is 1.0h
-1Temperature of reaction is 360 ℃, reaction pressure is 5MPa, after reaction with secondary hydrogenation products and the heat exchange of one-level hydrogenation products, temperature is down to 260 ℃ of left and right, carry out heat exchange with heavy benzene and washing oil mixture more afterwards, temperature is down to 130 ℃ of left and right, is cooled to normal temperature after filling into de-salted water and inhibiter in the secondary hydrogenation products after the cooling; Above-mentioned normal temperature material is introduced high-pressure separator to be separated, the complete hydrogen of unreacted enters the recycle system from the top of high-pressure separator to be continued to use, sour water separates from the bottom of high-pressure separator to be removed, the middle layer oil phase is delivered to light pressure separator by variable valve and is continued to separate, and obtains product after separation.
Embodiment 13
As shown in Figure 4, on the basis of embodiment 12, after the secondary hydrogenation products of 30wt% is mixed with the volume ratio of 1:800 with hydrogen, return in the one-level hydrogenator that is filled with one-level hydrogenation catalyst 4 and carry out the one-level hydrogenation reaction, simultaneously, the secondary hydrogenation products of all the other 70wt% is carried out follow-up heat exchange, separation according to the process of embodiment 12, obtain at last product.
Embodiment 14
The hydrofining technology of heavy benzene and washing oil mixture comprises as shown in Figure 3:
(1) be that heavy benzene and the washing oil mixture of 1:7 is forced into 5-10MPa with weight ratio after two-stage filtration is removed solid impurity, then successively by protective material and metal remover, to remove the easily polymerization reactant such as trace metal impurities in mixture and vinylbenzene, indenes;
(2) 100ml one-level hydrogenation catalyst 5 is seated in the one-level hydrogenator, after mixing with the volume ratio of 1:1000 with hydrogen with the washing oil mixture through the heavy benzene of above-mentioned processing, passes in this reactor, its volume space velocity is 0.75h
-1, the temperature of controlling in reactor is 175 ℃, pressure is that 5MPa carries out the one-level hydrogenation reaction, obtains the one-level hydrogenation products;
(3) the one-level hydrogenation products is mixed with the 1:1000 volume ratio with hydrogen after, be incorporated into load and have in the secondary hydrogenator of 100ml secondary hydrogenation catalyst 5 and proceed the secondary hydrogenation reaction, its volume space velocity is 0.4h
-1Temperature of reaction is 400 ℃, reaction pressure is 5MPa, after reaction with secondary hydrogenation products and the heat exchange of one-level hydrogenation products, temperature is down to 260 ℃ of left and right, carry out heat exchange with heavy benzene and washing oil mixture more afterwards, temperature is down to 130 ℃ of left and right, is cooled to normal temperature after filling into de-salted water and inhibiter in the secondary hydrogenation products after the cooling; Above-mentioned normal temperature material is introduced high-pressure separator to be separated, the complete hydrogen of unreacted enters the recycle system from the top of high-pressure separator to be continued to use, sour water separates from the bottom of high-pressure separator to be removed, the middle layer oil phase is delivered to light pressure separator by variable valve and is continued to separate, and obtains product after separation.
Embodiment 15
As shown in Figure 4, on the basis of embodiment 14, after the secondary hydrogenation products of 30wt% is mixed with the volume ratio of 1:1000 with hydrogen, return in the one-level hydrogenator that is filled with one-level hydrogenation catalyst 5 and carry out the one-level hydrogenation reaction, simultaneously, the secondary hydrogenation products of all the other 70wt% is carried out follow-up heat exchange, separation according to the process of embodiment 14, obtain at last product.
Protective material in above-described embodiment and metal remover can be selected any commercially available prod, and two-stage filtration can select in prior art any enforceable mode to carry out.
In above-described embodiment, all hydrogenation catalyst before use, need first carry out prevulcanized.Pre-vulcanization process is: with 2h
-1The liquid air speed passes in the reactor that hydrogenation catalyst is housed and contains 10wt%CS
2Benzole soln, pass into simultaneously the hydrogen of 2MPa, wherein hydrogen and CS
2The volume ratio of benzole soln is 700:1, and lowering the temperature after 12 hours in lasting prevulcanized under 250 ℃ gets final product.
Comparative Examples 1
The hydrofining technology of heavy benzene and washing oil mixture comprises:
(1) the washing oil hydrogenation catalyst with 100ml is seated in the one-level hydrogenator, is the heavy benzene of 1:1 and the mixture of washing oil with weight ratio, passes in this reactor after mixing with the volume ratio of 1:800 with hydrogen, and its volume space velocity is 0.75h
-1, the temperature of controlling in reactor is 175 ℃, pressure is that 3MPa carries out the one-level hydrogenation reaction, obtains the one-level hydrogenation products;
(2) the one-level hydrogenation products is mixed with the 1:600 volume ratio with hydrogen after, be incorporated into load and have in the secondary hydrogenator of 100ml washing oil hydrogenation catalyst and proceed the secondary hydrogenation reaction, its volume space velocity is 0.25h
-1Temperature of reaction is 350 ℃, reaction pressure is 4MPa, after reaction, the secondary hydrogenation products of 90wt% being introduced high-pressure separator separates, the complete hydrogen of unreacted enters the recycle system from the top of high-pressure separator to be continued to use, sour water separates from the bottom of high-pressure separator to be removed, and the middle layer oil phase is delivered to light pressure separator by variable valve and continued to separate, and obtains at last product;
(3) the secondary hydrogenation products of all the other 10wt% is mixed with the volume ratio of 1:600 with hydrogen after, return in the one-level hydrogenator that is filled with the washing oil hydrogenation catalyst and proceed the 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%, all the other are auxiliary agent B and F.
Comparative Examples 2
The hydrofining technology of heavy benzene and washing oil mixture comprises:
(1) the heavy benzene hydrogenation catalyst with 100ml is seated in the one-level hydrogenator, is the heavy benzene of 1:1 and the mixture of washing oil with weight ratio, passes in this reactor after mixing with the volume ratio of 1:800 with hydrogen, and its volume space velocity is 0.75h
-1, the temperature of controlling in reactor is 175 ℃, pressure is that 3MPa carries out the one-level hydrogenation reaction, obtains the one-level hydrogenation products;
(2) the one-level hydrogenation products is mixed with the 1:600 volume ratio with hydrogen after, be incorporated into load and have in the secondary hydrogenator of 100ml heavy benzene hydrogenation catalyst and proceed the secondary hydrogenation reaction, its volume space velocity is 0.25h
-1Temperature of reaction is 350 ℃, reaction pressure is 4MPa, after reaction, the secondary hydrogenation products of 90wt% being introduced high-pressure separator separates, the complete hydrogen of unreacted enters the recycle system from the top of high-pressure separator to be continued to use, sour water separates from the bottom of high-pressure separator to be removed, and the middle layer oil phase is delivered to light pressure separator by variable valve and continued to separate, and obtains at last product;
(3) the secondary hydrogenation products of all the other 10wt% is mixed with the volume ratio of 1:600 with hydrogen after, return in the one-level hydrogenator that is filled with the heavy benzene hydrogenation catalyst and proceed the 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%, all the other are alumina supporter.
Test case
(1) adopt gas chromatograph that organosulfur, the organonitrogen content of the heavy benzene in embodiment 6-15 and Comparative Examples 1-2 and washing oil mixture and the finished product are measured, and calculate its organic sulfur removal rate and organonitrogen decreasing ratio, the results are shown in following table.
(2) adopt the iodine number method to carry out degree of unsaturation mensuration to the heavy benzene in embodiment 6-15 and Comparative Examples 1-2 and washing oil mixture and the finished product, and calculate according to the following formula its hydrogenation reaction rate, the results are shown in following table.
(3) adopt the diesel oil infrared spectrum analyser that the cetane value of the heavy benzene in embodiment 6-15 and Comparative Examples 1-2 and washing oil mixture and the finished product is measured, and calculate according to the following formula its cetane value conservation rate, the results are shown in following table.
(4) with 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.
Can be found out by above result, compare with Comparative Examples 1,2 technique, organic sulfur removal rate, organonitrogen decreasing ratio and the hydrogenation reaction rate of the hydrofining technology of the bright described heavy benzene of this law and washing oil mixture are all higher, therefore as can be 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 is better for the hydrogenation effect of alkene in mixture.
And, to compare with Comparative Examples 1,2 technique as seen from the above table, the bright technique of this law is not easy to make the aromatic hydroxy compound generation open loop chain-breaking reaction in heavy benzene and washing oil mixture, thereby the conservation rate of cetane value is higher.
Have again, the molecular-weight average of comparing embodiment 6-15 one-level hydrogenation products as can be known, part secondary hydrogenation products is returned to sustainable participation one-level hydrogenation in A reactor, can effectively utilize secondary hydrogenation products dilution heavy benzene with high-content saturates and the unsaturates content in the washing oil mixture, thereby effectively reduced unsaturates, the probability of autohemagglutination occurs in the 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 any form that does not exceed the claim protection domain made on this basis and the variation of details, all belong to invention which is intended to be protected.
Claims (14)
1. the hydrofining technology of a heavy benzene and washing oil mixture, comprise
(1) heavy benzene and washing oil mixture with after hydrogen mixes, carry out hydrogenation reaction under the effect of one-level hydrogenation catalyst, obtain the one-level hydrogenation products;
(2) the one-level hydrogenation products with after hydrogen mixes, is proceeded hydrogenation reaction under the effect of secondary hydrogenation catalyst, obtains the secondary hydrogenation products, the secondary hydrogenation products is separated obtaining 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 catalyst comprises following component:
All the other are aluminum oxide.
2. hydrofining technology according to claim 1, it is characterized in that, in step (2), the described secondary hydrogenation products of part is separated, and with the described secondary hydrogenation products of rest part with after hydrogen mixes, return to described one-level hydrogenation catalyst and carry out the one-level hydrogenation reaction.
3. hydrofining technology according to claim 2, it is characterized in that, the quality of described rest part secondary hydrogenation products accounts for the 10-40% of all secondary hydrogenation products quality, and the volume ratio that described rest part secondary hydrogenation products mixes with hydrogen is 1:(600-1000).
4. according to claim 1-3 arbitrary described hydrofining technologies, is characterized in that,
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
5. according to claim 1-4 arbitrary described hydrofining technologies, is characterized in that, described ZSM-5 molecular sieve is by preparing without the template hydrothermal synthesis method; Described beta-molecular sieve is the modified beta molecular sieve after the water vapour heat treated of 360-600 ℃, and the processing pressure of described water vapour is 0.5-6MPa, and the treatment time is 1-5h.
6. according to claim 1-5 arbitrary described hydrofining technologies, is characterized in that, described aluminum oxide is comprised 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.
7. hydrofining technology according to claim 6, 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).
8. according to claim 1-7 arbitrary described hydrofining technologies, is characterized in that, in described heavy benzene and washing oil mixture, the weight ratio of heavy benzene, washing oil is 1:(1～10).
9. according to claim 1-8 arbitrary described hydrofining technologies, is characterized in that, the volume ratio of described heavy benzene and washing oil mixture, hydrogen is 1:(800-1200).
10. according to claim 1-9 arbitrary described hydrofining technologies, is characterized in that, the volume ratio of described one-level hydrogenation products and hydrogen is 1:(600-1000).
11. according to claim 1-10 arbitrary described hydrofining technologies is characterized in that the temperature of one-level hydrogenation reaction is 175～235 ℃, reaction pressure is 3.0～8.0MPa.
12. according to claim 1-11 arbitrary described hydrofining technologies is characterized in that the temperature of secondary hydrogenation reaction is 350～400 ℃, reaction pressure is 4～6MPa.
13. according to claim 1-12 arbitrary described hydrofining technologies is characterized in that the preparation of described one-level hydrogenation catalyst comprises the steps:
(1) with the γ-Al of moulding
2O
3Take out after dipping in the soluble zirconium salts solution, obtain γ-Al after drying, roasting
2O
3-ZrO
2Carrier;
(2) add in nickel salt or the nickel hydroxide ammonia soln to dissolving fully, then add quadrol to mix, add at last molybdenum salt to mix, obtain the Mo-Ni co-impregnated solution;
(3) with described γ-Al
2O
3-ZrO
2Take out after carrier floods in described Mo-Ni co-impregnated solution, obtain presoma after drying, roasting;
(4) add entry to dissolving fully in the rare-earth element salt of solubility, then add citric acid and mix the formation mixed solution, take out after described presoma is flooded in described mixed solution, drying, roasting get final product.
14. according to claim 1-13 arbitrary described hydrofining technologies is characterized in that the preparation of described secondary hydrogenation catalyst 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, moulding, then drying, roasting obtain carrier;
(2) tungstate, nickel salt are mixed with water form solution I, in solution I, then drying, roasting obtain carrier pre-treatment thing with described carrier impregnation;
(3) molybdenum oxide, nickel salt are mixed with water form the solution II, described carrier pre-treatment thing is immersed in the solution II, then drying, roasting get final product.
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