CN102311782B - Method for producing diesel oil by purifying coal tar through hydrogenating - Google Patents
Method for producing diesel oil by purifying coal tar through hydrogenating Download PDFInfo
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Abstract
The invention provides a method for producing diesel oil by purifying coal tar through hydrogenating. According to the method, two hydrogenation reaction areas which are arranged in series are arranged; the first hydrogenation reaction area is filled with a hydrogenation protective agent, and the second hydrogenation reaction area is orderly filled with the hydrogenation protective agent and a hydrogenation main catalyst according to the flow direction of a reaction material flow; when the pressure drop of at least one catalyst bed layer in the first hydrogenation reaction area is decreased to the upper limit of the pressure drop, at least one part of coal tar raw material and hydrogen gas is directly introduced into the second hydrogenation reaction area. By utilizing a switchable process of the first hydrogenation reaction area and an optimized catalyst graded filling scheme, an operation cycle of the device can be effectively prolonged, and a naphtha fraction with a high potential aromatic content and a diesel oil fraction with low sulfur, low nitrogen and high cetane number are produced at the same time.
Description
Technical field
The invention belongs under the existence of hydrogen, by the process of coal tar fraction hydrotreatment, specifically, is a kind of method of producing diesel oil by purifying coal tar through hydrogenating.
Background technology
Along with social economy continues, high speed development, China also increases day by day to the demand of petroleum products.Yet oil belongs to Nonrenewable energy resources, be faced with increasingly exhausted crisis.By contrast, the Chinese coal reserves are abundanter, therefore, by the coal preparing liquid fuel, become a basic orientation of coal processing and utilization.
On the other hand, along with rapid growth international, domestic steel industry, coking industry presents the trend of high growth, and therefore, the output of coal tar is increasing, and the clean processing of coal tar and effective utilization also become more and more important.At present, conventional working method is to cut the various cuts in diversity through the pre-treatment distillation, more various cuts are processed and extracted straight product by methods such as acid-alkali washing, distillation, polymerization, crystallizations; Also some coal tar is directly burnt as low-quality fuel oil after acid-alkali refining, or directly after emulsification, burns as emulsion fuel.In coal tar, the impurity such as institute's sulfur-bearing, nitrogen become sulphur and nitrogen oxide and discharge into the atmosphere and cause topsoil in combustion processes, and in the acid-alkali refining process, can produce large amount of sewage, can serious environment pollution.
For this situation, both at home and abroad part Study entity and individual propose to adopt the method processing treatment coal tar of hydrogenation, produce diesel oil or gasoline, but due to the coal tar kind and nature difference larger, each method all has certain limitation.
A kind of method of producing lightweight fuel oil by coal tar heavy fractioning hydrogenation is disclosed in CN101240191A.The method adopts hydrofining-hydrocracking combined process, in coal tar, cut and hydrogen are mixed into the hydrofining reaction district, effluent after refining is after separation system, obtain petroleum naphtha, diesel oil and last running, wherein last running enters the hydrocracking reaction district, partly or entirely circulation is as hydrorefined charging for the hydrocracking reaction effluent of gained, and remainder enters above-mentioned separation system.
CN1147575C discloses a kind of method that coal tar hydrogenating is produced diesel oil.The method is separated into residual oil and distilled oil by coal tar, distilled oil is carried out to hydrogenation in hydro-refining unit, obtains gasoline, diesel oil through high score, stripping tower.But the coal tar of mentioning in the method is lighter, the distilled oil character obtained after separating is also better, and after hydrotreatment its product diesel cetane-number 35 unit left and right only.
CN1903994A discloses a kind of method of producing fuel oil by coal tar hydrogenation modifying.After removing the full cut of coal tar of moisture and ash content and thinning oil and being mixed in proportion; through successively the deep hydrogenation unit that the shallow degree hydrogenation unit of hydrogenation protecting agent, catalyst for pre-hydrogenation being housed and main hydrogenating catalyst is housed; product after deep hydrogenation is through high-pressure separator, light pressure separator, fractionation; isolate light oil distillate, middle oil distillate and tail oil cut, namely obtain low-sulfur, low nitrogen oil fuel and light-end products.The method main purpose is to produce oil fuel, the diesel oil distillate cetane index of its production<40.
CN101629101A discloses a kind of converting and combining method for hydrogenation of different boiling ranges coal tar fraction.The method first is separated into coal tar the first hydrocarbon-fraction and the second hydrocarbon-fraction, and two cuts enter respectively the first hydrofining reaction district and the second hydrofining reaction district, and the liquid efflunent of two reaction zones separates after mixing.The method is mentioned after two refining reaction district products mix and is entered the 3rd hydrofining reaction district or hydrocracking reaction district, or the second hydrofining reaction district part petroleum naphtha enters the first hydrofining reaction district, and the hydrocracking heavy oil fraction partly circulates.The flow process that the method is mentioned is comparatively complicated, and product diesel cetane-number increase rate is limited.
In addition, in coal tar fraction, nitrogen content, oxygen level, metal content and aromaticity content are high, and it is carried out to hydrotreatment, and it is too fast that high metal content causes the fixed bed catalyst bed pressure drop to rise, and cause the device can't the long period steady running.
Summary of the invention
A kind of method that the purpose of this invention is to provide producing diesel oil by purifying coal tar through hydrogenating, to be solved is in coal tar raw material, to contain a large amount of aromatic hydrocarbons, and nitrogen content, water-content, metal content are all higher, have a strong impact on the fixed bed catalyst problem of running period.
Method provided by the invention comprises: coal tar raw material and hydrogen are under hydrogenation conditions, introduce successively two hydroconversion reaction zones of series connection, with a plurality of beds contact reactss in hydroconversion reaction zone, filling hydrogenation protecting agent in the first hydroconversion reaction zone, according to the flow direction of reactant flow, in the second hydroconversion reaction zone, load successively hydrogenation protecting agent and hydrogenation Primary Catalysts; The pressure drop of at least one beds reaches in pressure drop and prescribes a time limit in the first hydroconversion reaction zone, and at least a portion of coal tar raw material and hydrogen is directly introduced to the second hydroconversion reaction zone.
Described coal tar raw material is the coal tar lighting end of full cut coal tar gained after cutting, and final boiling point is 350～400 ℃.
The hydrogenation Primary Catalysts of take is benchmark, and the admission space of the hydrogenation protecting agent of described the first hydroconversion reaction zone is 5%～50%, and preferably the admission space of the hydrogenation protecting agent of the 15%～30%, second hydroconversion reaction zone is 1%～40%, preferably 5%～15%.
Hydrogenation conditions is: hydrogen dividing potential drop 6.0～17.0MPa, and preferred 8.0～14.0MPa, temperature of reaction is 320～440 ℃, preferably 340～400 ℃, hydrogen to oil volume ratio 400～2500Nm
3/ m
3, volume space velocity 0.3～1.5h during stock liquid
-1.
The pressure drop of at least one beds reaches in pressure drop and prescribes a time limit in the first hydroconversion reaction zone, and at least a portion of coal tar raw material and hydrogen is directly introduced to the second hydroconversion reaction zone.In described pressure drop, be limited to 0.4～0.8 times of reactor design maximum pressure drop, preferably 0.5～0.8 times.One of them preferred scheme is: the first hydroconversion reaction zone arranges a reactor, when reaching in pressure drop, the first reactor pressure decrease prescribes a time limit, stock oil and hydrogen are directly introduced to the second hydroconversion reaction zone, continue the holdout device running, the first reactor is lowered the temperature, is stopped work and change agent, after the first reactor changes the outfit new agent, again cut reactive system.During changing agent, second reaction zone top protective material plays a role, and the protection Primary Catalysts is not contaminated and impact for a long time.Method provided by the invention can be under the prerequisite that guarantees quality product, and the holdout device continuous operation, effectively extend running period.
The hydrogenation protecting agent of described the first hydroconversion reaction zone and the hydrogenation protecting agent of the second hydroconversion reaction zone are all the protective material grating technology that adopt different shapes, different pore size, different metal charge capacity; the protective material grating technology adopted can cause the metal of bed pressure drop in can effective elimination coal tar, simultaneously can saturated part alkene, aromatic hydrocarbons.
The hydrogenation protecting agent of described the first hydroconversion reaction zone and the hydrogenation protecting agent of the second hydroconversion reaction zone are all 4 kinds of hydrogenation protecting agent of grading loading, the flow direction according to reactant flow is hydrogenation protecting agent I, hydrogenation protecting agent II, hydrogenation protecting agent III and hydrogenation protecting agent IV successively, the 4 kinds of hydrogenation protecting agent integral body of take are benchmark, and the admission space ratio of hydrogenation protecting agent I, hydrogenation protecting agent II, hydrogenation protecting agent III and hydrogenation protecting agent IV is followed successively by: 1%～30%, 20%～50%, 20%～50%, 20%～50%; Its carrier is silicon oxide and/or aluminum oxide, non-activity metal in hydrogenation protecting agent I, and the reactive metal of hydrogenation protecting agent II, hydrogenation protecting agent III and hydrogenation protecting agent IV is selected from group vib metal or group VIII metal or their combination.
Described hydrogenation protecting agent I can be the protective material of a kind of seven apertures in the human head cylinder shape inertia silicon oxide or aluminum oxide, also can be a kind of protective material of bird-nest type inertia.The Raschig ring type protective material that described hydrogenation protecting agent II is diameter 6mm, the Raschig ring type protective material that described hydrogenation protecting agent III is diameter 3.4mm, described hydrogenation protecting agent IV are the trifolium-shaped protective material of diameter 3.4mm.
Hydrogenation protecting agent II consists of: the heavy % of nickel oxide 0.2～5, molybdenum oxide are 1.0～5.0 heavy %, and surplus is silica-alumina; Hydrogenation protecting agent III consists of: the heavy % of nickel oxide 0.5～5, molybdenum oxide are 2.0～8.0 heavy %, and surplus is silica-alumina; Hydrogenation protecting agent IV consists of: the heavy % of nickel oxide 0.5～5, molybdenum oxide are 2.0～8.0 heavy %, and surplus is silica-alumina.
Described the second hydroconversion reaction zone can arrange a plurality of reactors, according to the flow direction of reactant flow, in the second hydroconversion reaction zone, loads successively hydrogenation protecting agent and hydrogenation Primary Catalysts.Hydrogenation Primary Catalysts described in the second hydroconversion reaction zone has two kinds of preferred schemes, and wherein a kind of is to load separately Hydrobon catalyst, and another kind is combination loading Hydrobon catalyst and catalyst for hydro-upgrading.Coal tar fraction carries out hydrogenating desulfurization, hydrodenitrification, aromatic saturation and selective opening cracking reaction at the second hydroconversion reaction zone, and reaction effluent obtains naphtha fraction and diesel oil distillate through cooling, separation and fractionation.The Hydrobon catalyst adopted in the present invention has good hydrogenating desulfurization, hydrodenitrification, hydrogenation deoxidation and aromatic saturation performance, and the catalyst for hydro-upgrading adopted has good selective opening cracking performance.
Consisting of of Hydrobon catalyst: the described catalyzer of take is benchmark, nickel oxide 1～10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 % by weight to being less than or equal to 50 % by weight, phosphorus oxide 1～9 % by weight, surplus is silica-alumina, and the mol ratio of described Tungsten oxide 99.999 and molybdenum oxide is greater than 2.6 to being less than or equal to 30; Silica content in described silica-alumina is 2～45 % by weight, and the content of aluminum oxide is 55～98 % by weight.
Described Hydrobon catalyst preferred group becomes: nickel oxide 1～7 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 15 % by weight to being less than or equal to 45 % by weight, phosphorus oxide 1.5～7.0 % by weight, surplus is silica-alumina, and the mol ratio of described Tungsten oxide 99.999 and molybdenum oxide is greater than 3.1 to being less than or equal to 24.The content of the silicon oxide in described silica-alumina is 5～40 % by weight, and the content of aluminum oxide is 60～95 % by weight.Maturing temperature 450-650 ℃ in described silica-alumina carrier preparation, roasting time is 1-10 hour.Described silica-alumina most probable hole, on the 90 Izod right sides, accounts for 20%～60%, and preferably 30%～50%.
When the hydrogenation Primary Catalysts was the Hydrobon catalyst of combination loading and catalyst for hydro-upgrading, the catalyst for hydro-upgrading admission space accounted for 1%～50% of hydrogenation Primary Catalysts admission space, and preferably 5%～40%.
Consisting of of catalyst for hydro-upgrading: the described catalyzer of take is benchmark, the heavy % of silica-alumina 1～70, the heavy % of y-type zeolite 1～60, the heavy % of aluminum oxide 5～80; In oxide compound, the heavy % of metal component 10～40 of the heavy % of group VIII metal component 1～15, group vib; Wherein silica-alumina has structure of similar to thin diaspore.
Adopt method reconstructed coal tar provided by the invention, lighting end in coal tar can be converted into to naphtha fraction and the diesel oil distillate of high added value, the sulphur content of diesel fraction of gained<50 μ g/g, cetane value>45, the fragrant potential content of gasoline fraction>65% is reformer feed preferably.The present invention fully utilizes tar resource effectively, can alleviate to a certain extent the pressure that the petroleum products demand increases, and is that a kind of cost-effective coal tar processing utilizes means.
Compared with prior art, the present invention be advantageous in that:
(1), the present invention is according to the characteristics of coal tar innage aromaticity content, high impurity content, adopts the switchable operator scheme of the first reaction zone, can make device on original basis, extend at least one times running period.Method provided by the invention can on the basis of existing hydrogenation unit, increase a little guard reactor and supporting pipelines gets final product, and facility investment and process cost are relatively low.
(2), hydrogenation protecting agent of the present invention adopts the protective material grating technology of different shapes, different pore size, different metal charge capacity, can guarantee that the hydrogenation Primary Catalysts has high activity and stability for a long time, thereby further effective prolong operating period.
The accompanying drawing explanation
Accompanying drawing is the schematic flow sheet of producing diesel oil by purifying coal tar through hydrogenating method provided by the present invention.
Embodiment
Below in conjunction with accompanying drawing, method provided by the present invention is further detailed.
Accompanying drawing is the schematic flow sheet of a kind of producing diesel oil by purifying coal tar through hydrogenating method provided by the present invention.As shown in drawings: the full cut 1 of coal tar enters prefractionation system 3 after single filter 2a filters, be separated into coal tar the first lighting end 20, coal tar the second lighting end 21 and coal tar tail oil cut 22, and wherein tail oil cut 22 is as the raw material of producing pitch.Coal tar the first lighting end 20 and coal tar the second lighting end 21 mix in stock oil surge tank 4, after cascade filtration 2b, enter stock oil surge tank 5.After exporting logistics 23 and hydrogen 33 and hydrogen-rich gas 34 mix, stock oil surge tank 5 enters process furnace 6.
Logistics 24 after heating enters the first hydroconversion reaction zone 7 through inlet valve 37, and valve 36 is closing condition.The first hydroconversion reaction zone 7 arranges a reactor, and the multiple hydrogenation protecting agent of grading loading.The first hydroconversion reaction zone 7 reaction effluents 25 enter the second hydroconversion reaction zone after outlet valve 38; the second hydroconversion reaction zone arranges two reactors (8 and 9); in reactor 8, load successively hydrogenation protecting agent and Hydrobon catalyst, in reactor 9, load successively Hydrobon catalyst and catalyst for hydro-upgrading.The reaction effluent 26 of reactor 8, without in the middle of any, separating, directly enters reactor 9.
When the first hydroconversion reaction zone 7 gangway pressure drops reach in pressure drop, prescribe a time limit, close the first hydrogenation inlet valve 37 and outlet valve 38, open valve 36, coal tar and hydrogen mixture stream 24 enter reactor 8 through valve 36, and agent is changed in reactor 7 coolings, shut-down.Question response device 7 changes the outfit after new agent, can again cut reactive system.
The reaction effluent 27 of reactor 9 enters high-pressure separator 11 and carries out gas-liquid separation after interchanger 28 is cooling, the hydrogen-rich gas 31 of gained enters the hydrogen-rich gas 32 of circulating hydrogen compressor 10 pressurizations, pressurization as between cold hydrogen injecting reactor bed, and the hydrogen-rich gas 35 of pressurization returns to reaction zone as recycle hydrogen.The separating obtained liquid phase stream 29 of high-pressure separator 11 enters light pressure separator 12 and carries out further gas-liquid separation, gained gaseous stream 41 and liquid phase stream 30.Wherein liquid phase stream 30 enters de-hydrogen sulfide column 13 and removes hydrogen sulfide, ammonia and part light hydrocarbon component 19, and gained liquid phase stream 18 enters separation column 14.Through fractionation, obtain gas 15, naphtha fraction 16 and diesel oil distillate 17.
The following examples will be further described method provided by the invention, but not thereby limiting the invention.
Embodiment
The present embodiment adopts technical process shown in Figure 1, and two hydroconversion reaction zones are arranged, and the first hydroconversion reaction zone arranges a reactor, and the second hydroconversion reaction zone arranges two reactors.The filling situation of each reactor catalyst is:
First reactor a: beds; load hydrogenation protecting agent I (RGC-10), hydrogenation protecting agent II (RGC-10A), hydrogenation protecting agent III (RGC-10B) and hydrogenation protecting agent IV (RGC-1) from top to bottom; the integer catalyzer of first reactor of take is benchmark, and above-mentioned protectant admission space per-cent is respectively 13.3%, 28.9%, 28.9% and 28.9%.
Second reactor: three beds, on first bed and lower filling hydrogenation protecting agent I (RGC-10), hydrogenation protecting agent II (RGC-10A), hydrogenation protecting agent III (RGC-10B) and hydrogenation protecting agent IV (RGC-1); The integer catalyzer of first bed of take is benchmark, and above-mentioned protectant admission space per-cent is respectively 11.6%, 11.6%, 11.6% and 11.6%.The second bed and the 3rd bed filling Hydrobon catalyst (RTC-2).
The 3rd reactor: three beds, first bed and second bed filling Hydrobon catalyst (RTC-2), back end hydrogenation catalyst for refining (RTC-2) is loaded in the 3rd bed top filling catalyst for hydro-upgrading (RCC-2), bottom.
The hydrogenation Primary Catalysts of the present embodiment is comprised of Hydrobon catalyst and catalyst for hydro-upgrading; the hydrogenation Primary Catalysts integral body of take is benchmark; the admission space of the hydrogenation protecting agent of the first hydroconversion reaction zone is that the admission space of the hydrogenation protecting agent of 28.6%, the second hydroconversion reaction zone is 10.0%.The admission space of catalyst for hydro-upgrading is 25.0%.
Hydrogenation catalyst used in embodiment is produced by catalyzer branch office of China PetroChemical Corporation Chang Ling catalyst plant.
The full cut of coal tar enters the prefractionation system after filtering, be separated into coal tar the first lighting end, coal tar the second lighting end and tail oil cut, wherein the tail oil cut enters asphalt production device, coal tar the first lighting end, coal tar the second lighting end are as the incoming stock oily surge tank of coal tar hydrogenating raw material, after filtering, the second stage enters second stock oil surge tank again, after preheating, enter the first reactor, the second reactor and the 3rd reactor, reaction product, after subsequent separation system and fractionating system, obtains naphtha fraction and diesel oil distillate.Coal tar raw material character is in Table 1, and processing parameter is in Table 2, and naphtha fraction and diesel oil distillate character are in Table 3.
The device continuous operation is after 4000 hours, and the first reactor pressure decrease is 0.6 times of reactor design maximum pressure drop.At this moment the first reactor is cut out, separately the first reactor is changed to agent and process.Due to a certain amount of hydrogenation protecting agent of the second reactor head filling, can continue the holdout device running and not damage the hydrogenation Primary Catalysts, like this, device can continuous operation at least 8000 hours, and diesel oil distillate is superior in quality.Treat that the first reactor for treatment is complete, again cut reactive system.
Table 1 coal tar raw material character
| Project | Coal tar raw material |
| Density (20 ℃)/(g/cm3) | 0.9455 |
| Sulphur content/(μ g/g) | 3700 |
| Nitrogen content/(μ g/g) | 5400 |
| Oxygen level/% | 4.2 |
| Basic n content/% | 0.33 |
| Carbon residue content/% | 0.37 |
| Total acid value/(mgKOH/g) | 0.73 |
| Asphalt content/% | 0.2 |
| Boiling range ASTM D-86/ ℃ | |
| IBP | 86 |
| 50％ | 255 |
| FBP | 385 |
Table 2 processing parameter
| Processing parameter: | |
| Hydrogen dividing potential drop/MPa | 12.0 |
| The first temperature of reactor/℃ | 320 |
| The second reactor reaction temperature/℃ | 358 |
| The 3rd reactor reaction temperature/℃ | 363 |
| Total hydrogen-oil ratio/Nm 3/m 3 | 1500 |
| First reactor volume air speed/h -1 | 2.0 |
| Second reactor top protective material volume space velocity/h -1 | 5.0 |
| Catalyst for refining volume space velocity/h -1 | 0.65 |
| Modifying catalyst volume space velocity/h -1 | 2.5 |
| Rear catalyst for refining volume space velocity/h -1 | 20.0 |
Table 3 product property
| Project | Naphtha fraction | Diesel oil distillate |
| Density (20 ℃)/(g/cm 3) | 0.7706 | 0.8470 |
| Sulphur content/(μ g/g) | ＜0.5 | ＜10 |
| Nitrogen content/(μ g/g) | ＜0.5 | ＜1.0 |
| Virtue is dived/% | 74.0 | - |
| Cetane value | - | 49.5 |
| Boiling range ASTM D-86/ ℃ | ||
| IBP/10％ | 79/94 | 186/200 |
| 30％/50％ | 102/109 | 217/237 |
| 70％/90％ | 124/140 | 266/315 |
| FBP | 167 | 366 |
Claims (11)
1. the method for a producing diesel oil by purifying coal tar through hydrogenating, comprise: coal tar raw material and hydrogen are under hydrogenation conditions, introduce successively two hydroconversion reaction zones of series connection, with a plurality of beds contact reactss in hydroconversion reaction zone, filling hydrogenation protecting agent in the first hydroconversion reaction zone, according to the flow direction of reactant flow, in the second hydroconversion reaction zone, load successively hydrogenation protecting agent and hydrogenation Primary Catalysts; The pressure drop of at least one beds reaches in pressure drop and prescribes a time limit in the first hydroconversion reaction zone, at least a portion of coal tar raw material and hydrogen is directly introduced to the second hydroconversion reaction zone, described coal tar raw material is the coal tar lighting end of full cut coal tar gained after cutting, and final boiling point is 350～400 ℃.
2. in accordance with the method for claim 1, it is characterized in that, the hydrogenation Primary Catalysts of take is benchmark, and the admission space of the hydrogenation protecting agent of described the first hydroconversion reaction zone is that the admission space of the hydrogenation protecting agent of the 5%～50%, second hydroconversion reaction zone is 1%～40%.
3. in accordance with the method for claim 2; it is characterized in that; the hydrogenation Primary Catalysts of take is benchmark, and the admission space of the hydrogenation protecting agent of described the first hydroconversion reaction zone is that the admission space of the hydrogenation protecting agent of the 15%～30%, second hydroconversion reaction zone is 5%～15%.
4. in accordance with the method for claim 1, it is characterized in that, hydrogenation conditions is: hydrogen dividing potential drop 6.0～17.0MPa, 320～440 ℃ of temperature of reaction, hydrogen to oil volume ratio 400～2500Nm
3/ m
3, volume space velocity 0.3～1.5h during stock liquid
-1.
5. in accordance with the method for claim 1, it is characterized in that, in described pressure drop, be limited to 0.4～0.8 times of reactor design maximum pressure drop.
6. in accordance with the method for claim 1, it is characterized in that, the hydrogenation protecting agent of described the first hydroconversion reaction zone and the hydrogenation protecting agent of the second hydroconversion reaction zone are all 4 kinds of hydrogenation protecting agent of grading loading, the flow direction according to reactant flow is hydrogenation protecting agent I successively, hydrogenation protecting agent II, hydrogenation protecting agent III and hydrogenation protecting agent IV, the 4 kinds of hydrogenation protecting agent integral body of take are benchmark, hydrogenation protecting agent I, hydrogenation protecting agent II, the admission space ratio of hydrogenation protecting agent III and hydrogenation protecting agent IV is followed successively by: 1%～30%, 20%～50%, 20%～50%, 20%～50%, its carrier is silicon oxide and/or aluminum oxide, non-activity metal in hydrogenation protecting agent I, and the reactive metal of hydrogenation protecting agent II, hydrogenation protecting agent III and hydrogenation protecting agent IV is selected from group vib metal or group VIII metal or their combination.
7. in accordance with the method for claim 6, it is characterized in that, hydrogenation protecting agent II is shaped as Raschig ring, consists of: the heavy % of nickel oxide 0.2～5, molybdenum oxide are 1.0～5.0 heavy %, and surplus is silica-alumina; Hydrogenation protecting agent III is shaped as Raschig ring, consists of: the heavy % of nickel oxide 0.5～5, molybdenum oxide are 2.0～8.0 heavy %, and surplus is silica-alumina; Hydrogenation protecting agent IV is shaped as trifolium-shaped, consists of: the heavy % of nickel oxide 0.5～5, molybdenum oxide are 2.0～8.0 heavy %, and surplus is silica-alumina.
8. in accordance with the method for claim 1, it is characterized in that, the hydrogenation Primary Catalysts described in the second hydroconversion reaction zone is the Hydrobon catalyst loaded separately, or is Hydrobon catalyst and the catalyst for hydro-upgrading of combination loading.
9. in accordance with the method for claim 8, it is characterized in that, consisting of of Hydrobon catalyst: the described catalyzer of take is benchmark, nickel oxide 1～10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 % by weight to being less than or equal to 50 % by weight, phosphorus oxide 1～9 % by weight, surplus are silica-alumina, and the mol ratio of described Tungsten oxide 99.999 and molybdenum oxide is greater than 2.6 to being less than or equal to 30; Silica content in described silica-alumina is 2～45 % by weight, and the content of aluminum oxide is 55～98 % by weight.
10. in accordance with the method for claim 8, it is characterized in that, when the hydrogenation Primary Catalysts was the Hydrobon catalyst of combination loading and catalyst for hydro-upgrading, the catalyst for hydro-upgrading admission space accounted for 1%～50% of hydrogenation Primary Catalysts admission space.
11. the method according to claim 8 or 10, is characterized in that, the consisting of of catalyst for hydro-upgrading: the described catalyzer of take is benchmark, the heavy % of silica-alumina 1～70, the heavy % of y-type zeolite 1～60, the heavy % of aluminum oxide 5～80; In oxide compound, the heavy % of metal component 10～40 of the heavy % of group VIII metal component 1～15, group vib; Wherein silica-alumina has structure of similar to thin diaspore.
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| CN106147852B (en) * | 2015-04-28 | 2018-04-13 | 中国石油化工股份有限公司 | A kind of method by producing diesel by utilizing coal tar component |
| CN106147853B (en) * | 2015-04-28 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of method of coal tar raw material weighted BMO spaces |
| CN106147855B (en) * | 2015-04-28 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of method of hybrid process coal tar and Fischer-Tropsch synthesis oil |
| CN107434982B (en) * | 2016-05-27 | 2019-05-03 | 神华集团有限责任公司 | Method that device and catalyst grade for coal tar hydrogenating upgrading are matched and coal tar plus hydrogen method for upgrading |
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| CN1876767A (en) * | 2006-06-28 | 2006-12-13 | 沈和平 | Coal tar hydrocracking method |
| CN1952071A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | Combined method for producing cleaning oil from coal-tar oil |
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| CN1952071A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | Combined method for producing cleaning oil from coal-tar oil |
| CN1876767A (en) * | 2006-06-28 | 2006-12-13 | 沈和平 | Coal tar hydrocracking method |
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