CN102311782A - 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 in the presence of hydrogen, with the process of coal tar fraction hydrotreatment, specifically, is the method that diesel oil is produced in a kind of coal tar hydrogenating upgrading.
Background technology
Along with social economy continues, high speed development, China also increases the demand of petroleum products day by day.Yet oil belongs to Nonrenewable energy resources, is faced with exhausted day by day crisis.By contrast, therefore Chinese coal reserves rich, produces the basic orientation that liquid fuel has become the coal processing and utilization by coal.
On the other hand, along with quick growth international, domestic steel industry, coking industry presents the trend of high growth, and therefore, the output of coal tar is increasing, and the cleaning processing of coal tar also becomes more and more important with effective utilization.At present, conventional working method is to cut the various cuts in the diversity through the pre-treatment distillation, more various cuts is handled the extraction straight product with methods such as acid-alkali washing, distillation, polymerization, crystallizations; Also directly burnt as low-quality fuel oil behind some coal tar process acid-alkali refining, or directly burnt as emulsion fuel after the emulsification.Impurity such as institute's sulfur-bearing, nitrogen become sulphur and nitrogen oxides and discharge into the atmosphere and cause topsoil in the coal tar in combustion processes, and can produce large amount of sewage in the acid-alkali refining process, can serious environment pollution.
To this situation, part Study entity and individual propose to adopt the method processing treatment coal tar of hydrogenation both at home and abroad, produce diesel oil or gasoline, but because coal tar kind and nature difference are bigger, each method all has certain limitation.
A kind of method of producing lightweight fuel oil by coal tar heavy fractioning hydrogenation is disclosed among the CN101240191A.This method adopts unifining-hydrocracking combined process; Cut and hydrogen are mixed into the hydrofining reaction district in the coal tar; Elute after refining obtains petroleum naphtha, diesel oil and last running after separation system, wherein last running gets into the hydrocracking reaction district; Partly or entirely circulation is as hydrorefined charging for the hydrocracking reaction elute of gained, and remainder gets into above-mentioned separation system.
CN1147575C discloses the method that a kind of coal tar hydrogenating is produced diesel oil.This method separates into residual oil and distilled oil with coal tar, and distilled oil is carried out hydrogenation in hydro-refining unit, obtains gasoline, diesel oil through high score, stripping tower.But the coal tar of mentioning in this method is lighter, and the distilled oil character that after separating, obtains is also better, and through its product diesel cetane-number after the hydrotreatment only about 35 units.
CN1903994A discloses a kind of method of producing fuel oil by coal tar hydrogenation modifying.After removing the full cut of coal tar and thinning oil proportional mixing of moisture and ash content; Through 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 successively; Product behind the deep hydrogenation is through HP separator, light pressure separator, fractionation; Isolate light oil distillate, middle oil distillate and tail oil cut, promptly obtain low-sulfur, low nitrogen oil fuel and clean cargo.This method main purpose is to produce oil fuel, diesel oil distillate cetane index＜40 of its production.
CN101629101A discloses a kind of converting and combining method for hydrogenation of different boiling ranges coal tar fraction.This method is separated into first hydrocarbon-fraction and second hydrocarbon-fraction with coal tar earlier, and two cuts get into the first hydrofining reaction district and the second hydrofining reaction district respectively, and the liquid efflunent of two reaction zones separates after mixing.This method is mentioned two refining reaction district products and is mixed the back and get into the 3rd hydrofining reaction district or hydrocracking reaction district, or the second hydrofining reaction district part petroleum naphtha gets into the first hydrofining reaction district, and the hydrogen cracking heavy oil fraction partly circulates.The flow process that this method is mentioned is comparatively complicated, and product diesel cetane-number increase rate is limited.
In addition, nitrogen content in the coal tar fraction, oxygen level, metal content and aromaticity content are high, and it is carried out 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 LP steady running.
Summary of the invention
The purpose of this invention is to provide a kind of coal tar hydrogenating upgrading and produce the method for diesel oil, to be solved is to contain a large amount of aromatic hydrocarbons in the coal tar raw material, 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 placed in-line two hydroconversion reaction zones successively; With a plurality of beds contact reactss in the hydroconversion reaction zone; The agent of filling hydrogenation protecting according to the flow direction of reactant flow, is loaded hydrogenation protecting agent and hydrogenation Primary Catalysts successively in first hydroconversion reaction zone in second hydroconversion reaction zone; The pressure drop of at least one beds reaches in the pressure drop and prescribes a time limit in first hydroconversion reaction zone, and at least a portion of coal tar raw material and hydrogen is directly introduced second hydroconversion reaction zone.
Said 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 ℃.
With the hydrogenation Primary Catalysts is benchmark, and the admission space of the hydrogenation protecting agent of said first hydroconversion reaction zone is 5%～50%, and the admission space of the hydrogenation protecting agent of preferred 15%～30%, second hydroconversion reaction zone is 1%～40%, preferred 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 ℃, preferred 340～400 ℃, hydrogen to oil volume ratio 400～2500Nm
3/ m
3, volume space velocity 0.3～1.5h during liquid stock
-1
The pressure drop of at least one beds reaches in the pressure drop and prescribes a time limit in first hydroconversion reaction zone, and at least a portion of coal tar raw material and hydrogen is directly introduced second hydroconversion reaction zone.Be limited to 0.4～0.8 times of reactor design maximum pressure drop in the said pressure drop, preferred 0.5～0.8 times.One of them preferred scheme is: first hydroconversion reaction zone is provided with a reactor drum; When reaching in the pressure drop, first reactor pressure decrease prescribes a time limit; Raw oil and hydrogen are directly introduced second hydroconversion reaction zone, continue the holdout device running, first reactor drum is lowered the temperature, is stopped work and change agent; Treat that first reactor drum changes the outfit after the new agent, cuts reactive system again.Change during the agent, the second reaction zone top protective material plays a role, the not contaminated for a long time and influence of protection Primary Catalysts.Method provided by the invention can guarantee that the holdout device continuous operation effectively prolongs running period under the product quality premise.
The hydrogenation protecting agent of said first hydroconversion reaction zone all is to adopt the protective material grating of different shapes, different aperture, different metal charge capacity technology with the hydrogenation protecting agent of second hydroconversion reaction zone; The protective material grating technology that is 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 said first hydroconversion reaction zone and the hydrogenation protecting agent of second hydroconversion reaction zone all are 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; With 4 kinds of hydrogenation protecting agent integral body is 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, and non-activity metal among the hydrogenation protecting agent I, the reactive metal of hydrogenation protecting agent II, hydrogenation protecting agent III and hydrogenation protecting agent IV are selected from group vib metal or group VIII metal or their combination.
Said 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 bird-nest type inert protective material.The Raschig ring type protective material that said hydrogenation protecting agent II is diameter 6mm, the Raschig ring type protective material that said hydrogenation protecting agent III is diameter 3.4mm, said hydrogenation protecting agent IV are the trifolium-shaped protective material of diameter 3.4mm.
Hydrogenation protecting agent II consists of: nickel oxide 0.2～5 heavy %, and molybdenum oxide is 1.0～5.0 heavy %, surplus is a silica-alumina; Hydrogenation protecting agent III consists of: nickel oxide 0.5～5 heavy %, and molybdenum oxide is 2.0～8.0 heavy %, surplus is a silica-alumina; Hydrogenation protecting agent IV consists of: nickel oxide 0.5～5 heavy %, and molybdenum oxide is 2.0～8.0 heavy %, surplus is a silica-alumina.
Described second hydroconversion reaction zone can be provided with a plurality of reactor drums, according to the flow direction of reactant flow, loads hydrogenation protecting agent and hydrogenation Primary Catalysts in second hydroconversion reaction zone successively.Hydrogenation Primary Catalysts described in second hydroconversion reaction zone has two kinds of preferred schemes, and wherein a kind of is to load Hydrobon catalyst separately, and another kind is combination loading Hydrobon catalyst and catalyst for hydro-upgrading.Coal tar fraction carries out hydrogenating desulfurization, hydrodenitrification at second hydroconversion reaction zone, aromatic hydrocarbons is saturated and the selective opening cracking reaction, and reaction effluent obtains naphtha fraction and diesel oil distillate through cooling, separation and fractionation.The Hydrobon catalyst that is adopted among the present invention has the saturated performance of good hydrogenating desulfurization, hydrodenitrification, hydrogenation deoxidation and aromatic hydrocarbons, and the catalyst for hydro-upgrading that is adopted has good selective opening cracking performance.
Consisting of of Hydrobon catalyst: with said catalyzer is benchmark; Nickel oxide 1～10 weight %; Molybdenum oxide and Tungsten oxide 99.999 sum greater than 10 weight % to smaller or equal to 50 weight %; Phosphorus oxide 1～9 weight %, surplus is a silica-alumina, the mol ratio of said Tungsten oxide 99.999 and molybdenum oxide greater than 2.6 to smaller or equal to 30; Silica content in the said silica-alumina is 2～45 weight %, and the content of aluminum oxide is 55～98 weight %.
Said Hydrobon catalyst preferred group becomes: nickel oxide 1～7 weight %; Molybdenum oxide and Tungsten oxide 99.999 sum greater than 15 weight % to smaller or equal to 45 weight %; Phosphorus oxide 1.5～7.0 weight %; Surplus is a silica-alumina, the mol ratio of said Tungsten oxide 99.999 and molybdenum oxide greater than 3.1 to smaller or equal to 24.The content of the silicon oxide in the said silica-alumina is 5～40 weight %, and the content of aluminum oxide is 60～95 weight %.Maturing temperature 450-650 in the said silica-alumina preparing carriers ℃, roasting time is 1-10 hour.Said silica-alumina most probable hole is right at 90 Izods, accounts for 20%～60%, preferred 30%～50%.
When the hydrogenation Primary Catalysts was Hydrobon catalyst and the catalyst for hydro-upgrading of combination loading, the catalyst for hydro-upgrading admission space accounted for 1%～50%, preferred 5%～40% of hydrogenation Primary Catalysts admission space.
Consisting of of catalyst for hydro-upgrading: with said catalyzer is benchmark, silica-alumina 1～70 heavy %, y-type zeolite 1～60 heavy %, aluminum oxide 5～80 heavy %; In oxide compound, metal component 10～40 heavy % of group VIII metal component 1～15 heavy %, group vib; Wherein silica-alumina has structure of similar to thin diaspore.
Adopt method reconstructed coal tar provided by the invention; Can lighting end in the coal tar be converted into the 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; Fragrant potential content＞65% of gasoline fraction is a reformer feed preferably.The present invention fully utilizes tar resource effectively, can alleviate the pressure that the petroleum products demand increases to a certain extent, is a kind of cost-effective coal tar processing and utilization 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 first reaction zone, can make device on original basis, prolong one times at least 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 aperture, different metal charge capacity, it is high active and stable to guarantee that the hydrogenation Primary Catalysts has for a long time, thus further effective prolong operating period.
Description of drawings
Accompanying drawing is the schematic flow sheet that the diesel oil method is produced in coal tar hydrogenating upgrading provided by the present invention.
Embodiment
Below in conjunction with accompanying drawing method provided by the present invention is further explained.
Accompanying drawing is that the schematic flow sheet of diesel oil method is produced in a kind of coal tar hydrogenating upgrading provided by the present invention.Shown in accompanying drawing: the full cut 1 of coal tar filters 2a through one-level and filters the back and get into prefrationation system 3, is separated into coal tar first lighting end 20, coal tar second lighting end 21 and coal tar tail oil cut 22, and wherein tail oil cut 22 is as production bituminous raw material.Coal tar first lighting end 20 mixes in raw oil surge tank 4 with coal tar second lighting end 21, behind cascade filtration 2b, gets into raw oil surge tank 5.The 5 outlet logistics 23 of raw oil surge tank mix the back with hydrogen 33 and hydrogen-rich gas 34 and get into process furnace 6.
Prescribe a time limit when the 7 gangway pressure drops of first hydroconversion reaction zone reach in the pressure drop, close the first hydrogenation inlet valve 37 and outlet valve 38, open valve 36, coal tar and hydrogen mixture stream 24 get into reactor drums 8 through valve 36, and agent is changed in reactor drum 7 coolings, shut-down.Question response device 7 changes the outfit after the new agent, can cut reactive system again.
The reaction effluent 27 of reactor drum 9 gets into HP separator 11 and carries out gas-liquid separation after interchanger 28 coolings; The hydrogen-rich gas 31 of gained gets into the hydrogen-rich gas 32 of circulating hydrogen compressors 10 pressurizations, pressurization as between cold hydrogen injecting reactor bed, and the hydrogen-rich gas of pressurization 35 returns reaction zone as recycle hydrogen.HP separator 11 separating obtained liquid phase streams 29 get into light pressure separator 12 and carry out further gas-liquid separation, gained gaseous stream 41 and liquid phase stream 30.Wherein liquid phase stream 30 gets into de-hydrogen sulfide column 13 and removes hydrogen sulfide, ammonia and part light hydrocarbon component 19, and gained liquid phase stream 18 gets into separation column 14.Obtain gas 15, naphtha fraction 16 and diesel oil distillate 17 through fractionation.
Following embodiment will further explain method provided by the invention, but therefore not limit the present invention.
Embodiment
Present embodiment adopts technical process shown in Figure 1, and two hydroconversion reaction zones are arranged, and first hydroconversion reaction zone is provided with a reactor drum, and second hydroconversion reaction zone is provided with two reactor drums.The filling situation of each reactor catalyst is:
First reactor drum 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; Integer catalyzer with first reactor drum is a benchmark, and above-mentioned protectant admission space per-cent is respectively 13.3%, 28.9%, 28.9% and 28.9%.
Second reactor drum: three beds, on first bed and down 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); Integer catalyzer with first bed is a benchmark, and above-mentioned protectant admission space per-cent is respectively 11.6%, 11.6%, 11.6% and 11.6%.Second bed and the 3rd bed filling Hydrobon catalyst (RTC-2).
The 3rd reactor drum: 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 present embodiment is made up of Hydrobon catalyst and catalyst for hydro-upgrading; With hydrogenation Primary Catalysts integral body is benchmark; The admission space of the hydrogenation protecting agent of 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 among the embodiment is produced by catalyzer branch office of China PetroChemical Corporation Chang Ling catalyst plant.
The full cut of coal tar gets into the prefrationation system after filtering; Be separated into coal tar first lighting end, coal tar second lighting end and tail oil cut; Wherein the tail oil cut gets into the pitch production equipment; Coal tar first lighting end, coal tar second lighting end get into second raw oil surge tank again as the incoming stock oily surge tank of coal tar hydrogenating raw material after filter the second stage, after preheating, get into first reactor drum, second reactor drum and the 3rd reactor drum; Reaction product obtains naphtha fraction and diesel oil distillate after subsequent separation system and fractionating system.Coal tar raw material character is seen table 1, and processing parameter is seen table 2, and naphtha fraction and diesel oil distillate character are seen table 3.
The device continuous operation is after 4000 hours, and first reactor pressure decrease is 0.6 times of reactor design maximum pressure drop.At this moment first reactor drum is cut out, separately first reactor drum is changed agent and handle.Because second reactor head loads a certain amount of hydrogenation protecting agent, 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 first reactor for treatment finishes, and cuts reactive system again.
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 |
| D-86/ ℃ of boiling range ASTM | |
| IBP | 86 |
| 50％ | 255 |
| FBP | 385 |
Table 2 processing parameter
| Processing parameter: | |
| Hydrogen dividing potential drop/MPa | 12.0 |
| 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 drum 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 |
| Back 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 |
| D-86/ ℃ of boiling range ASTM | ||
| IBP/10％ | 79/94 | 186/200 |
| 30％/50％ | 102/109 | 217/237 |
| 70％/90％ | 124/140 | 266/315 |
| FBP | 167 | 366 |
Claims (12)
1. the method for diesel oil is produced in a coal tar hydrogenating upgrading; Comprise: coal tar raw material and hydrogen are under hydrogenation conditions; Introduce placed in-line two hydroconversion reaction zones successively, with a plurality of beds contact reactss in the hydroconversion reaction zone, filling hydrogenation protecting agent in first hydroconversion reaction zone; According to the flow direction of reactant flow, load hydrogenation protecting agent and hydrogenation Primary Catalysts in second hydroconversion reaction zone successively; The pressure drop of at least one beds reaches in the pressure drop and prescribes a time limit in first hydroconversion reaction zone, and at least a portion of coal tar raw material and hydrogen is directly introduced second hydroconversion reaction zone.
2. according to the described method of claim 1, it is characterized in that said coal tar raw material is the coal tar lighting end of full cut coal tar gained after cutting, final boiling point is 350～400 ℃.
3. according to the described method of claim 1, it is characterized in that, is benchmark with the hydrogenation Primary Catalysts, and the admission space of the hydrogenation protecting agent of said first hydroconversion reaction zone is that the admission space of the hydrogenation protecting agent of 5%～50%, second hydroconversion reaction zone is 1%～40%.
4. according to the described method of claim 3; It is characterized in that; With the hydrogenation Primary Catalysts is benchmark, and the admission space of the hydrogenation protecting agent of said first hydroconversion reaction zone is that the admission space of the hydrogenation protecting agent of 15%～30%, second hydroconversion reaction zone is 5%～15%.
5. according to the described method of 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 liquid stock
-1
6. according to the described method of claim 1, it is characterized in that, be limited to 0.4～0.8 times of reactor design maximum pressure drop in the said pressure drop.
7. according to the described method of claim 1; It is characterized in that; The hydrogenation protecting agent of said first hydroconversion reaction zone and the hydrogenation protecting agent of second hydroconversion reaction zone all are 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; With 4 kinds of hydrogenation protecting agent integral body is 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, and non-activity metal among the hydrogenation protecting agent I, the reactive metal of hydrogenation protecting agent II, hydrogenation protecting agent III and hydrogenation protecting agent IV are selected from group vib metal or group VIII metal or their combination.
8. according to the described method of claim 7, it is characterized in that hydrogenation protecting agent II is shaped as Raschig ring, consists of: nickel oxide 0.2～5 heavy %, molybdenum oxide is 1.0～5.0 heavy %, surplus is a silica-alumina; Hydrogenation protecting agent III is shaped as Raschig ring, consists of: nickel oxide 0.5～5 heavy %, and molybdenum oxide is 2.0～8.0 heavy %, surplus is a silica-alumina; Hydrogenation protecting agent IV is shaped as trifolium-shaped, consists of: nickel oxide 0.5～5 heavy %, and molybdenum oxide is 2.0～8.0 heavy %, surplus is a silica-alumina.
9. according to the described method of claim 1, it is characterized in that the hydrogenation Primary Catalysts described in second hydroconversion reaction zone is the Hydrobon catalyst that loads separately, perhaps is the Hydrobon catalyst and the catalyst for hydro-upgrading of combination loading.
10. according to the described method of claim 9; It is characterized in that the consisting of of Hydrobon catalyst: with said catalyzer is benchmark, nickel oxide 1～10 weight %; Molybdenum oxide and Tungsten oxide 99.999 sum greater than 10 weight % to smaller or equal to 50 weight %; Phosphorus oxide 1～9 weight %, surplus is a silica-alumina, the mol ratio of said Tungsten oxide 99.999 and molybdenum oxide greater than 2.6 to smaller or equal to 30; Silica content in the said silica-alumina is 2～45 weight %, and the content of aluminum oxide is 55～98 weight %.
11., it is characterized in that when the hydrogenation Primary Catalysts was Hydrobon catalyst and the catalyst for hydro-upgrading of combination loading, the catalyst for hydro-upgrading admission space accounted for 1%～50% of hydrogenation Primary Catalysts admission space according to the described method of claim 9.
12. the method according to claim 9 or 11 is characterized in that, the consisting of of catalyst for hydro-upgrading: with said catalyzer is benchmark, silica-alumina 1～70 heavy %, y-type zeolite 1～60 heavy %, aluminum oxide 5～80 heavy %; In oxide compound, metal component 10～40 heavy % of group VIII metal component 1～15 heavy %, group vib; Wherein silica-alumina has structure of similar to thin diaspore.
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| CN106147852A (en) * | 2015-04-28 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of by the method for producing diesel by utilizing coal tar component |
| CN106147853A (en) * | 2015-04-28 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of method of coal tar raw material weighted BMO spaces |
| CN107434982A (en) * | 2016-05-27 | 2017-12-05 | 神华集团有限责任公司 | The method and the hydrogenation method for upgrading of coal tar that device and catalyst grade for coal tar hydrogenating upgrading are matched somebody with somebody |
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| CN106147855A (en) * | 2015-04-28 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of hybrid process coal tar and the method for Fischer-Tropsch synthesis oil |
| CN106147852A (en) * | 2015-04-28 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of by the method for producing diesel by utilizing coal tar component |
| CN106147853A (en) * | 2015-04-28 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of method of coal tar raw material weighted BMO spaces |
| 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 |
| 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 |
| 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 |
| CN107434982A (en) * | 2016-05-27 | 2017-12-05 | 神华集团有限责任公司 | The method and the hydrogenation method for upgrading of coal tar that device and catalyst grade for coal tar hydrogenating upgrading are matched somebody with somebody |
| 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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