CN100378204C - Combined process for converting coal liquefied oil at maximum - Google Patents
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Abstract
A combined process for converting coal liquefied oil at maximum is carried out by filtering coal liquefied oil, entering it and hydrogen into stabilized hydrogenation reactor, contacting with hydrogenation protective agent and hydrogenation refined catalyst, separating effluent of stabilized hydrogenation reactor to obtain gas, naphtha fraction, diesel oil fraction and tail-oil fraction, stabilized hydrogenation diesel oil fraction and part tail-oil fraction into hydrogenation modified reactor and hydrogenation cracking reactor separately, separating for reactant to obtain gas, naphtha fraction and diesel oil fraction product, and circulating for hydrogen-enriched flow to return into each reactor. The recovery rate of diesel oil is above 92% and cetyl value is beyond 45.
Description
Technical field
The present invention relates to a kind of liquid hydrocarbon that coal destruction hydrogenation is obtained and carry out hydrotreatment and cracked method.More particularly, be a kind of method that the liquefied coal coil maximum is converted into lightweight oil.
Background technology
Just having begun DCL/Direct coal liquefaction produced the liquid hydrocarbon Study on Technology as far back as 1913 in Germany, and will make the skilled industryization of gasoline with the brown coal direct liquefaction in nineteen twenty-seven.Since the world oil crisis first time took place in 1973 since; direct coal liquefaction technology is subjected to the attention of developed country; many DCL/Direct coal liquefaction technologies have been developed in succession; the IGOR technology of Germany's exploitation is online refining with liquefied coal coil; the qualified diesel product of direct production, and the liquefied coal coil of other explained hereafter will just can become the proper fuel oil production through following process.
US4332666 discloses a kind of method of producing diesel oil, aviation fuel and Number 2 fuel oil.The raw material of this technology is the cut that is suitable for doing hydrogen supply agent in the liquefied coal coil, and extracting goes out stable hydrocarbon as diesel oil, aviation fuel and Number 2 fuel oil from the hydrogenation resultant, and remaining is hydrogen supply agent.
CN1382772A discloses a kind of method from liquefied coal coil greatly preparing hihg-quality diesel oil or rocket engine fuel, liquefied coal coil after the filtration and hydrogen enter the stable hydrogenation reactor, contact with hydrogenation protecting agent, Hydrobon catalyst, the stable hydrogenation reactor effluent obtains gas, naphtha fraction, diesel oil distillate and tail oil cut through separation, wherein part tail oil cut loops back coal liquefaction system as hydrogen supply agent, and hydrogen rich stream loops back the stable hydrogenation reactor; The diesel oil distillate, remaining tail oil cut and the hydrogen that obtain from the stable hydrogenation reactor enter the deep hydrogenation reforming reactor, contact with Hydrobon catalyst, hydrocracking catalyst, separate the hydro-upgrading reactor effluent and obtain gas, naphtha fraction, diesel oil distillate and tail oil cut or gas, naphtha fraction, rocket engine fuel, diesel oil distillate and tail oil cut, hydrogen rich stream returns the deep hydrogenation reforming reactor.Though this method can be produced fine-quality diesel oil or rocket engine fuel, because diesel oil distillate and remaining tail oil cut all advance hydroeracking unit, cause the liquid yield of product and diesel yield to descend, see improper from the angle of Technological Economy.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of combined technical method of converting coal liquefied oil at maximum.
Method provided by the invention comprises the following steps:
(1), liquefied coal coil and the hydrogen after the filtration enters the stable hydrogenation reactor, contact with hydrogenation protecting agent, Hydrobon catalyst, the stable hydrogenation reactor effluent obtains gas, naphtha fraction, diesel oil distillate and tail oil cut through separation, wherein part tail oil cut loops back coal liquefaction system as hydrogen supply agent, and hydrogen rich stream loops back the stable hydrogenation reactor;
(2), the diesel oil distillate of step (1) and hydrogen enter the hydro-upgrading reactor, contact with catalyst for hydro-upgrading, the hydro-upgrading reactor effluent obtains gas, naphtha fraction and diesel oil distillate product through separation, and hydrogen rich stream loops back the stable hydrogenation reactor;
(3), remaining tail oil cut and hydrogen enter hydrocracking reactor, with hydrocracking catalyst or contact with Hydrobon catalyst, hydrocracking catalyst successively, separate the hydrocracking reactor effluent and obtain gas, naphtha fraction and diesel oil distillate product, hydrogen rich stream returns the deep hydrogenation reforming reactor.
Method provided by the invention can be produced fine-quality diesel oil in maximum ground, the total recovery of diesel oil is more than 92 weight %, the sulphur of diesel oil distillate and the content of nitrogen are extremely low, aromaticity content is lower, density is lower, cetane value surpasses 45, can satisfy the requirement of " world's fuel oil standard " III class diesel oil to sulphur, nitrogen and aromaticity content.
Description of drawings
Accompanying drawing is the combined technical method synoptic diagram of converting coal liquefied oil at maximum provided by the invention.
Embodiment
Processing method of the present invention is made of the diesel oil fraction hydrogenating modification of liquefied coal coil stable hydrogenation, stable hydrogenation, three parts of tail oil cut fraction hydrogenation cracking of stable hydrogenation, the existing flow process of describing each several part respectively.
(1), liquefied coal coil stable hydrogenation
After the liquefied coal coil of coal liquefaction system production installs filtration after filtration, after mixing with hydrogen and being heated to temperature of reaction, enter the stable hydrogenation reactor.The stable hydrogenation reactor effluent mainly comprises H
2, lighter hydrocarbons, H
2S, NH
3, the treated oil behind water and the stable hydrogenation; The stable hydrogenation reactor effluent enters high-pressure separator, light pressure separator, separation column in proper order; Isolate light naphthar, heavy naphtha fraction, diesel oil distillate and tail oil cut by separation system; Part tail oil cut loops back coal liquefaction system and does hydrogen supply agent.The isolated hydrogen rich stream of high-pressure separator mixes with new hydrogen, delivers to the stable hydrogenation reactor.
(2), the diesel oil fraction hydrogenating modification of stable hydrogenation
The diesel oil distillate of stable hydrogenation device production is delivered to hydro-upgrading unit, to improve diesel-fuel cetane number.The technical process of the technical process of hydro-upgrading unit and stable hydrogenation device is similar, and the diesel oil distillate in the stable hydrogenation product is with after hydrogen mixes, by the hydro-upgrading reactor, and the C that obtains product liquid and in the hydro-upgrading reactor, generate
1～C
4Gas.The effluent of hydro-upgrading reactor enters high-pressure separator, light pressure separator, separation column in proper order; Isolate light naphtha fraction, heavy naphtha fraction and diesel oil distillate product by separation system.The isolated hydrogen rich stream of high-pressure separator mixes with new hydrogen, delivers to the hydro-upgrading reactor.
(3), the tail oil cut fraction hydrogenation cracking of stable hydrogenation
Remaining tail oil is delivered to hydroeracking unit.If hydrocracking process adopts unformed hydrocracking catalyst, flow process and above-mentioned two covering devices are similar, and remaining stable hydrogenation tail oil and hydrogen mix, by hydrocracking reactor, and the C that obtains product liquid and in hydrocracking reactor, generate
1～C
4Gas.The effluent of hydrocracking reactor enters high-pressure separator, light pressure separator, separation column in proper order; Isolate light naphtha fraction, heavy naphtha fraction and diesel oil distillate product by separation system.The isolated hydrogen rich stream of high-pressure separator mixes with new hydrogen, delivers to hydrocracking reactor.If the good molecular sieve type catalyst of cut selectivity during hydrocracking process adopts is established hydrotreating reactor and hydrocracking reactor in the flow process.Remaining stable hydrogenation tail oil and hydrogen are mixed into hydrotreating reactor, and the hydrotreating reactor effluent mainly is included in the H that removes in the hydrotreating reactor
2S, NH
3And the treated oil after the hydrotreatment; The hydrotreating reactor effluent can enter cracking case, in hydrocracking reactor open loop and chain rupture and hydrogenation saturated reaction can take place, and the hydrocracking reactor effluent mainly comprises H
2, lighter hydrocarbons, H
2S, NH
3, and cracking after product oil, the cracking case effluent enters high-pressure separator, light pressure separator, separation column in proper order; Isolate light naphthar, heavy naphtha fraction, diesel oil distillate by separation system.If hydrocracking process is cyclical operation, separation column can fractionate out the tail oil cut, and this tail oil cut loops back the inlet of hydrocracking reactor.
The boiling range scope of the raw materials used liquefied coal coil of the present invention should be in C5～520 ℃ best C5～480 ℃ (ASTM D-1160), and this is because cut is heavy more, and the content of impurity such as metal and bituminous matter is high more, and is big more to the influence in Hydrobon catalyst life-span; Nitrogen content is not more than 1.2 heavy % in the raw material, preferably is not more than 0.8 heavy %; Sulphur content is not more than 2.0 heavy %.
Raw material oil properties and purpose product are largely depended in technological operation handiness of the present invention, and the processing condition of three cover hydrogenation units are wanted rational Match.
The hydrogen dividing potential drop of stable hydrogenation device is 4.0～20.0MPa, and temperature of reaction is 280～450 ℃, and liquid hourly space velocity is 0.1～10h
-1, hydrogen-oil ratio is 300～2800v/v.
Hydro-upgrading unit hydrogen dividing potential drop is 6.0～20.0MPa, and temperature of reaction is 280～450 ℃, and liquid hourly space velocity is 0.1～20h
-1, hydrogen-oil ratio is 400～3000v/v.
Hydroeracking unit hydrogen dividing potential drop is 4.0～20.0MPa, and temperature of reaction is 280～450 ℃, and liquid hourly space velocity is 0.1～20h
-1, hydrogen-oil ratio is 300～2000v/v.
The stable hydrogenation catalyzer is VIA and the VIII family non-precious metal catalyst that loads on unformed aluminum oxide or the silica-alumina supports, and halogen atom-containing not, has very strong hydrogenation denitrification activity, and the group vib metal is selected from Mo or/and W, and VIII family metal is selected from Co or/and Ni.Because liquefied coal coil contains a certain amount of metal and bituminous matter; so an amount of hydrogenation protecting agent of will packing at stable hydrogenation catalyzer top; the loadings of hydrogenation protecting agent determines that itself and stable hydrogenation volume ratio are from 0.03 to 0.35 by foreign matter content in the liquefied coal coil and device running period.
Catalyst for hydro-upgrading is VIA or the VIII family base metal catalysts that contains on unformed aluminum oxide of loading on of molecular sieve or the silica-alumina supports, and the group vib metal is selected from Mo or/and W, and VIII family metal is selected from Co or/and Ni.
Hydrocracking process is the two agent operations of agent of single hop list or single hop.During hydrocracking single hop list agent operation, hydrocracking catalyst is VIA or the VIII family non-precious metal catalyst that loads on amorphous silicon aluminium or unformed silicon magnesium and other modified aluminas, the group vib metal is selected from Mo or/and W, and VIII family metal is selected from Co or/and Ni.When the two agent of hydrocracking single hop are operated, before hydrocracking catalyst, load hydrotreating catalyst, hydrotreating catalyst is VIA or the VIII family non-precious metal catalyst that loads on unformed aluminum oxide or the silica-alumina supports, the group vib metal is selected from Mo or/and W, and VIII family metal is selected from Co or/and Ni; Hydrocracking catalyst is VIA or the VIII family non-precious metal catalyst that loads on the y-type zeolite molecular sieve, and the group vib metal is selected from Mo or/and W, and VIII family metal is selected from Co or/and Ni.
Why the present invention adopts hydrogenation modifying process and hydrocracking process to process diesel oil distillate and tail oil cut in the stable hydrogenation product respectively, be because the diesel oil distillate of utilization hydrogenation modifying process processing stable hydrogenation product, can reduce its aromaticity content, and reaching the purpose that reduces diesel oil distillate density and increase substantially the diesel oil distillate cetane value by appropriate open loop, diesel yield can reach more than the 95 heavy %.The utilization hydrocracking process is processed remaining tail oil, heavier cut can be converted into petroleum naphtha and diesel oil, diesel-fuel cetane number height.Adopt the yield height of above-mentioned operational path diesel oil, its sulphur, nitrogen and aromaticity content can satisfy the standard of world fuel oil standard III class oil, and cetane value reaches more than 45.The petroleum naphtha virtue that obtains in the hydro-upgrading process is dived high, is catalytic reforming feedstock.
The catalyzer that hydrogenation modifying process is selected for use possesses the coupling of good hydrogenation activity and open loop cracking activity, is fit to the above aromatic hydrocarbons of processing dicyclo, improves its cetane value by open loop.This is that it is saturated performance that this catalyzer at first should have good hydrofining, could provide the reactant that can carry out ring-opening reaction easily to cracking reaction because the back of ring-opening reaction is the aromatic hydrogenation saturated reaction; Secondly, on the basis of saturated reaction, catalyzer should have the selective opening cracking, break hydrogenation saturated reaction equilibrated function, changes the purpose that hydrocarbon structure improves cetane value thereby reach.The cracking function of catalyzer comes from acidic components, and acidic components very easily are subjected to the nitride poisoning and deactivation, and the nitrogen content height is another characteristics of gelatin liquefaction diesel oil.Therefore, high nitrogen-containing must have high cracking activity in the raw material in order to overcome.At last, the hydrogenation activity of catalyzer and cracking activity must mate, if hydrogenation activity hangs down the cracking activity height, then aromatic hydrocarbons can not get well saturated, can't obtain in a large number can be for the reactant of open loop, cause the cracking of " useful " hydro carbons such as straight-chain paraffin easily, cause the generation of small molecules product, diesel yield descends; And if the hydrogenation activity height, cracking activity is low, then the complete hydrogenation saturated reaction of aromatic hydrocarbons is deepened, ring-opening reaction is not enough, causes the hydrogen consumption to increase, but the cetane value increase rate is little.As seen, hydrogenation modifying process catalyst system therefor of the present invention has distinct characteristic.
Hydroeracking unit can be once-through operation, also can cyclical operation.Hydroeracking unit can adopt unformed hydrocracking catalyst, single hop list agent operation; The good molecular sieve type catalyst of cut selectivity in also can adopting, the two agent operations of single hop.The purpose of this device of arrangement is converted into lightweight oil with the tail oil cut exactly in liquefied coal coil hydrogenation process for upgrading flow process, no longer goes out tail oil, reach to greatest extent liquefied coal coil is converted into lightweight oil, and the purpose of the high-yield diesel oil of trying one's best.
Because liquefied coal coil contains a large amount of aromatic hydrocarbons, and the nitrogen content height, difficulty of processing is big.Another characteristics of this technology are stable hydrogenation, hydrogenation modifying process and hydrocracking process matching operation, the properly distributed difficulty of processing, reach device benefit optimizing, if the character variation of stable hydrogenation charging, only need partly improve the operating severity of stable hydrogenation, improve the operating severity of hydroeracking unit simultaneously, reach the properly distributed difficulty of processing, make device benefit optimizing, general operational condition by adjustment cut point maintenance hydrogenation modifying process device is stable.
Below in conjunction with accompanying drawing method provided by the present invention is further detailed, but does not therefore limit the present invention.
Accompanying drawing is the combined technical method synoptic diagram of converting coal liquefied oil at maximum provided by the invention, has omitted the equipment of many necessity among the figure, as pump, air cooler and valve etc.
Flow process is described in detail as follows:
Liquefied coal coil is after pipeline 1 enters strainer 3 filtrations; boost to reaction pressure by feedstock pump; mix with hydrogen-rich gas from pipeline 6; by interchanger 4 heat exchange; again after process furnace 7 heating; enter stabilized hydrogenation reactor 9,, remove impurity such as metal in the stock oil, sulphur and nitrogen by contacting with protective material and Hydrobon catalyst bed.Because hydrofining is strong exothermal reaction, need in the middle of reactor, to introduce cold hydrogen, control reaction temperature.The effluent of stabilized hydrogenation reactor 9 is after pipeline 8 enters interchanger 4 heat exchange, enter high-pressure separator 10, in high-pressure separator 10, be separated into two bursts of logistics, wherein one is a hydrogen-rich stream, wherein be mainly hydrogen, comprise partial vulcanization hydrogen, ammonia simultaneously, this hydrogen-rich stream is after the recycle compressor compression, with after new hydrogen from pipeline 2 mixes, loop back reactor 9 through pipeline 5 through pipeline 6; Another burst logistics enters light pressure separator 12 through pipeline 11, further remove lighter hydrocarbons, these lighter hydrocarbons are through pipeline 13 caterpillars, the bottom effluent of light pressure separator 12 enters fractionating column system 15 through pipeline 14, fractionate out naphtha fraction, diesel oil distillate, tail oil cut, wherein naphtha fraction is through pipeline 16 caterpillars, and diesel oil distillate, tail oil cut are introduced hydro-upgrading, hydroeracking unit through pipeline 17,18 respectively.
Diesel oil distillate advances surge tank 19 through pipeline 17, boost to reaction pressure by feedstock pump then, mix with hydrogen-rich gas from pipeline 20, enter interchanger 21 heat exchange, after pipeline 22 enters process furnace 23 heating, enter hydro-upgrading reactor 24 again, by contacting with the catalyst for hydro-upgrading bed, further remove impurity such as sulphur and nitrogen, saturated aromatic hydrocarbons wherein, and part open loop.Though ring-opening reaction is thermopositive reaction, hydrofining is strong exothermal reaction, so from total thermopositive reaction that is seen as, need to introduce cold hydrogen, control reaction temperature in the middle of reactor.The effluent of hydro-upgrading reactor 24 is after pipeline 25 enters interchanger 21 heat exchange, enter high-pressure separator 26, in high-pressure separator 26, be separated into two bursts of logistics, wherein one is a hydrogen-rich stream, wherein be mainly hydrogen, comprise partial vulcanization hydrogen, ammonia simultaneously and because the light hydrocarbon that cracking produces, this hydrogen-rich stream is after the recycle compressor compression, with after new hydrogen from pipeline 2 mixes, loop back reactor 24 through pipeline 27 through pipeline 20; Another burst logistics enters light pressure separator 29 through pipeline 28, further remove lighter hydrocarbons, these lighter hydrocarbons are through pipeline 30 caterpillars, and the bottom effluent of light pressure separator 29 enters fractionating column system 32 through pipeline 31, fractionate out naphtha fraction, diesel oil distillate product respectively through pipeline 33,34 caterpillars.
If hydrocracking is single hop pair agent technologies, the tail oil cut advances surge tank 35 through pipeline 17, boosts to reaction pressure by feedstock pump then, mixes with hydrogen-rich gas from pipeline 36, enter interchanger 37 heat exchange, after process furnace 39 heating, enter the refining reaction device 40 of hydrocracking process, again by contacting with the Hydrobon catalyst bed, remove impurity such as sulphur and nitrogen, the mild cracking of heavy distillate in desulfurization, denitrogenation, takes place in fractional saturation aromatic hydrocarbons wherein.Because hydrofining is strong exothermal reaction, need in the middle of reactor, to introduce cold hydrogen, control reaction temperature.The effluent of refining reaction device 40 enters hydrocracking reactor 42 through pipeline 41, by contacting with hydrocracking catalyst, heavy constituent are hydrocracking into the light constituent of our expected product, hydrocracking reaction is the same with the hydrotreatment reaction, need to introduce cold hydrogen, prevent temperature of reaction because heat release causes temperature too high.The effluent of hydrocracking reactor 42 is after pipeline 43 enters interchanger 37 heat exchange, enter high-pressure separator 44, in high-pressure separator 44, be separated into two bursts of logistics, wherein one is a hydrogen-rich stream, wherein be mainly hydrogen, comprise partial vulcanization hydrogen, ammonia simultaneously and because the light hydrocarbon that cracking produces, this hydrogen-rich stream through recycle compressor compression after, with after new hydrogen from pipeline 2 mixes, loop back reactor 40 through pipeline 45 through pipeline 36; Another burst logistics then enters light pressure separator 47 through pipeline 46, further remove lighter hydrocarbons, these lighter hydrocarbons are through pipeline 49 caterpillars, and the bottom effluent of light pressure separator 47 enters fractionating system 50 through pipeline 48, fractionate out naphtha fraction, diesel oil distillate product respectively through pipeline 51,52 caterpillars.If hydrocracking is a circulation process, fractionating system 50 also can fractionate out the tail oil cut, and the tail oil cut loops back cracking case 42 through pipeline 53 and carries out further cracking.If hydrocracking is that single hop list agent technology does not have hydrofining reactor 40, the tail oil feedstock after pipeline 17, surge tank 35, interchanger 37, process furnace 39 heating, is directly advanced cracking case 42 successively.
Method provided by the invention can be produced fine-quality diesel oil in maximum ground, the total recovery of diesel oil is more than 92 weight %, the sulphur of diesel oil distillate and the content of nitrogen are extremely low, aromaticity content is lower, density is lower, cetane value surpasses 45, can satisfy the requirement of " world's fuel oil standard " III class diesel oil to sulphur, nitrogen and aromaticity content.
The following examples will give further instruction to present method, but therefore not limit present method.
All through filtering, its character is listed in table 1 to diesel oil distillate A, B among the embodiment behind the used liquefied coal coil stabilized hydrogenation.Hydrogenation protecting agent, stabilized hydrogenation catalyzer, catalyst for hydro-upgrading, Hydrobon catalyst, hydrocracking catalyst are produced by Sinopec Chang Ling catalyst plant.Test is carried out on medium-sized fixed bed hydrogenation device.
Test raw material is liquefied coal coil A, and the used hydrogenation protecting agent of stable hydrogenation is RG10-A and RG10-B, and the stable hydrogenation catalyzer is RJW-2.The used catalyst for hydro-upgrading of hydrogenation modifying process is RIC-1, and hydrocracking process is that flow process is once passed through in the two agent of single hop, and Hydrobon catalyst is RN-10, and hydrocracking catalyst is RT-5.The processing condition of stable hydrogenation and product tail oil cut character are listed in table 2, and the character of the processing condition of hydrogenation modifying process and hydrocracking, product diesel oil distillate is listed in table 3.
By table as seen, the density of liquefied coal coil is not too high, the processing condition of hydrogenation upgrading are not harsh, the aromatic carbon rate of stable hydrogenation product tail oil cut is 0.41 to be good hydrogen supply dissolvent, the sulphur of hydrogenation modifying process and hydrocracking process handicraft product diesel oil distillate and the content of nitrogen are very low, aromaticity content is lower, has reached the index request of " world's fuel oil standard " III class diesel oil, and it is qualified diesel products that its cetane value surpasses 45.The heavy % in hydrogenation modifying process product diesel oil distillate yield＞95, the yield of hydrocracking process product diesel oil distillate have realized as far as possible liquefied coal coil being converted into the purpose of diesel oil greater than 90 heavy %.
Test raw material is liquefied coal coil B, and the used hydrogenation protecting agent of stable hydrogenation is RG10-A and RG10-B, and the stable hydrogenation catalyzer is RJW-2.The used catalyst for hydro-upgrading of hydrogenation modifying process is RIC-1, and hydrocracking process is that flow process is once passed through in the two agent of single hop, and Hydrobon catalyst is RN-10, and hydrocracking catalyst is RT-5.The processing condition of stable hydrogenation and product tail oil cut character are listed in table 2, and the character of the processing condition of hydrogenation modifying process and hydrocracking, product diesel oil distillate is listed in table 3.
By table as seen, the density of liquefied coal coil is near 1, the processing condition of hydrogenation upgrading are comparatively harsh, the aromatic carbon rate of stable hydrogenation product tail oil cut is 0.43 to be good hydrogen supply dissolvent, the sulphur of hydrogenation modifying process and hydrocracking process handicraft product diesel oil distillate and the content of nitrogen are very low, aromaticity content is lower, has reached the index request of " world's fuel oil standard " III class diesel oil, and it is qualified diesel products that its cetane value surpasses 45.The heavy % in hydrogenation modifying process product diesel oil distillate yield＞95, the yield of hydrocracking process product diesel oil distillate is greater than 88 heavy %.
Table 1, raw material oil properties
| |
|
|
| The stock oil numbering | A | B |
| Density (20 ℃), g/cm 3 | 0.935 | 0.9912 |
| S, heavy % | 0.19 | 0.16 |
| N, heavy % | 0.41 | 0.56 |
| Total aromaticity content, heavy % | 71.5 | 72.3 |
| Polycyclic aromatic hydrocarbon content, heavy % | 43.5 | 52.1 |
| Boiling range (ASTM D-1160), ℃ | ||
| Initial boiling point/10% | 124/280 | 170/268 |
| 50％/90％ | 390/470 | 390/475 |
| Do | 500 | 512 |
Table 2, liquefied coal coil stable hydrogenation processing condition and product tail oil cut character
| The stable hydrogenation | Embodiment | 1 | |
| Temperature of reaction, ℃ | 340 | 350 | |
| The hydrogen dividing potential drop, MPa | 14.0 | 14.0 | |
| Volume space velocity, h -1 | 1.0 | 1.0 | |
| Hydrogen-oil ratio, v/v | 1200 | 1200 | |
| Product tail oil cut character | |||
| Density (20 ℃), g/cm 3 | 0.9608 | 0.9802 | |
| H, heavy % | 10.6 | 10.2 | |
| The aromatic carbon rate | 0.41 | 0.43 | |
| Boiling range (ASTM D-1160), ℃ | |||
| Initial boiling point | 378 | 379 | |
| 50％ | 450 | 455 | |
| 90 | 462 | 469 |
Table 3, hydrogenation modifying process and hydrocracking process condition and product diesel oil distillate character
| The hydrogenation modifying | Embodiment | 1 | |
| Temperature of reaction, ℃ | 350 | 350 | |
| The hydrogen dividing potential drop, MPa | 14.0 | 14.0 | |
| Volume space velocity, h -1 | 1.0 | 0.75 | |
| Hydrogen-oil ratio, v/v | 900 | 900 | |
| Product diesel oil distillate yield, heavy % | ＞95 | ＞95 | |
| Product diesel oil distillate character | |||
| Density (20 ℃), g/cm 3 | 0.8540 | 0.8554 | |
| S，ppm | ＜10 | ＜10 | |
| Total aromaticity content, heavy % | 12.5 | 13.2 | |
| Polycyclic aromatic hydrocarbon content, heavy % | 1.8 | 1.9 | |
| Boiling range (ASTM D-86), ℃ | |||
| Initial boiling point | 184 | 184 | |
| 50％ | 267 | 268 | |
| 90％ | 361 | 363 | |
| Cetane value | 46.2 | 46.3 | |
| The hydrocracking process condition | |||
| Temperature of reaction, ℃ | 365 | 365 | |
| The hydrogen dividing potential drop, MPa | 14.0 | 14.0 | |
| Volume space velocity, h -1 | 1.0 | 0.75 | |
| Hydrogen-oil ratio, v/v | 1000 | 1000 | |
| Product diesel oil distillate yield, heavy % | ＞90 | ＞88 | |
| Product diesel oil distillate character | |||
| Density (20 ℃), g/cm 3 | 0.8602 | 0.8674 | |
| S，ppm | ＜10 | ＜10 | |
| Total aromaticity content, heavy % | 13.5 | 14.2 | |
| Polycyclic aromatic hydrocarbon content, heavy % | 2.0 | 2.2 | |
| Boiling range (ASTM D-86), ℃ | |||
| Initial boiling point | 184 | 187 | |
| 50％ | 290 | 292 | |
| 90％ | 368 | 370 | |
| Cetane value | 46.2 | 47.3 |
Claims (7)
1. the combined technical method of a converting coal liquefied oil at maximum is characterized in that this method comprises the following steps:
(1), liquefied coal coil and the hydrogen after the filtration enters the stable hydrogenation reactor, contact with hydrogenation protecting agent, Hydrobon catalyst, the stable hydrogenation reactor effluent obtains gas, naphtha fraction, diesel oil distillate and tail oil cut through separation, wherein part tail oil cut loops back coal liquefaction system as hydrogen supply agent, and hydrogen rich stream loops back the stable hydrogenation reactor;
(2), the diesel oil distillate and the hydrogen of step (1) enters the hydro-upgrading reactor, contacts with catalyst for hydro-upgrading, the hydrogen dividing potential drop is 4.0～20.0MPa, temperature of reaction is 280～450 ℃, liquid hourly space velocity is 0.1～10h
-1, hydrogen-oil ratio is 300～2800v/v, and the hydro-upgrading reactor effluent obtains gas, naphtha fraction and diesel oil distillate product through separation, and hydrogen rich stream loops back the stable hydrogenation reactor;
(3), remaining tail oil cut and hydrogen enter hydrocracking reactor, with hydrocracking catalyst or contact with Hydrobon catalyst, hydrocracking catalyst successively, the hydrogen dividing potential drop is 4.0～20.0MPa, and temperature of reaction is 280～450 ℃, and liquid hourly space velocity is 0.1～20h
-1, hydrogen-oil ratio is 300～2000v/v, separates the hydrocracking reactor effluent and obtains gas, naphtha fraction and diesel oil distillate product, hydrogen rich stream returns the deep hydrogenation reforming reactor.
2. according to the method for claim 1, it is characterized in that described liquefied coal coil boiling range is C5～520 ℃.
3. according to the method for claim 1, the stable hydrogenation catalyzer that it is characterized in that step (1) is VIA and the VIII family non-precious metal catalyst that loads on unformed aluminum oxide or the silica-alumina supports, and halogen atom-containing not, the group vib metal is selected from Mo or/and W, and VIII family metal is selected from Co or/and Ni.
4. according to the method for claim 1, it is characterized in that the stable hydrogenation condition of step (1): the hydrogen dividing potential drop is 4.0～20.0MPa, and temperature of reaction is 280～450 ℃, and liquid hourly space velocity is 0.1～10h
-1, hydrogen-oil ratio is 300～2800v/v.
5. according to the method for claim 1, the catalyst for hydro-upgrading that it is characterized in that step (2) is VIA or the VIII family base metal catalysts that contains on unformed aluminum oxide of loading on of molecular sieve or the silica-alumina supports, the group vib metal is selected from Mo or/and W, and VIII family metal is selected from Co or/and Ni.
6. according to the method for claim 1, when it is characterized in that step (3) hydrocracking single hop list agent operation, hydrocracking catalyst is VIA or the VIII family non-precious metal catalyst that loads on amorphous silicon aluminium or the unformed silicon magnesium, the group vib metal is selected from Mo or/and W, and VIII family metal is selected from Co or/and Ni.
7. according to the method for claim 1, when it is characterized in that the two agent of step (3) hydrocracking single hop are operated, before hydrocracking catalyst, load hydrotreating catalyst, hydrotreating catalyst is VIA or the VIII family non-precious metal catalyst that loads on unformed aluminum oxide or the silica-alumina supports, the group vib metal is selected from Mo or/and W, and VIII family metal is selected from Co or/and Ni; Hydrocracking catalyst is VIA or the VIII family non-precious metal catalyst that loads on the y-type zeolite molecular sieve, and the group vib metal is selected from Mo or/and W, and VIII family metal is selected from Co or/and Ni.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100838999A CN100378204C (en) | 2005-07-15 | 2005-07-15 | Combined process for converting coal liquefied oil at maximum |
| MYPI20063382 MY142375A (en) | 2005-07-15 | 2006-07-14 | A combined process for converting a coal liquefied oil |
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|---|---|---|---|
| CNB2005100838999A CN100378204C (en) | 2005-07-15 | 2005-07-15 | Combined process for converting coal liquefied oil at maximum |
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| CN1896191A CN1896191A (en) | 2007-01-17 |
| CN100378204C true CN100378204C (en) | 2008-04-02 |
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| CNB2005100838999A Active CN100378204C (en) | 2005-07-15 | 2005-07-15 | Combined process for converting coal liquefied oil at maximum |
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| MY (1) | MY142375A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101173190B (en) * | 2007-10-22 | 2012-03-28 | 中国石油集团工程设计有限责任公司抚顺分公司 | Feito synthetic oil processing line |
| CN101993328B (en) * | 2009-08-31 | 2014-08-20 | 中国石油化工股份有限公司 | Catalytic conversion combination method for producing propylene and high-quality fuel oil in high yield |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4332666A (en) * | 1980-05-06 | 1982-06-01 | Exxon Research & Engineering Co. | Coal liquefaction process wherein jet fuel, diesel fuel and/or ASTM No. 2 fuel oil is recovered |
| US6190542B1 (en) * | 1996-02-23 | 2001-02-20 | Hydrocarbon Technologies, Inc. | Catalytic multi-stage process for hydroconversion and refining hydrocarbon feeds |
| CN1382772A (en) * | 2002-02-07 | 2002-12-04 | 中国石油化工股份有限公司 | Process for greatly preparing hihg-quality diesel oil or jet fuel from liquefied coil oil |
-
2005
- 2005-07-15 CN CNB2005100838999A patent/CN100378204C/en active Active
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- 2006-07-14 MY MYPI20063382 patent/MY142375A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4332666A (en) * | 1980-05-06 | 1982-06-01 | Exxon Research & Engineering Co. | Coal liquefaction process wherein jet fuel, diesel fuel and/or ASTM No. 2 fuel oil is recovered |
| US6190542B1 (en) * | 1996-02-23 | 2001-02-20 | Hydrocarbon Technologies, Inc. | Catalytic multi-stage process for hydroconversion and refining hydrocarbon feeds |
| CN1382772A (en) * | 2002-02-07 | 2002-12-04 | 中国石油化工股份有限公司 | Process for greatly preparing hihg-quality diesel oil or jet fuel from liquefied coil oil |
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| MY142375A (en) | 2010-11-30 |
| CN1896191A (en) | 2007-01-17 |
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