CN1382772A - Process for greatly preparing hihg-quality diesel oil or jet fuel from liquefied coil oil - Google Patents
Process for greatly preparing hihg-quality diesel oil or jet fuel from liquefied coil oil Download PDFInfo
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Abstract
A process for preparing high-quality diesel oil or jet fuel from liquefied coal oil with the highest output includes filtering, stable hydrogenation to obtain diesel oil fraction and tail oil fraction, modifying them by deep hydrogenation, separating its product to obtain gas, naphtha fraction, diesel oil fraction, jet fuel, and tail oil fraction, and cyclic use of hydrogen-enriched gas. Its advantages are high output rate of diesel oil (more than 70 wt.%), low contents of S and N, low density and high hexadecane number.
Description
Technical field
The present invention relates to the method that a kind of liquid hydrocarbon that coal destruction hydrogenation is obtained carries out hydrotreatment.More particularly, be a kind of method of producing diesel oil or rocket engine fuel from liquefied coal coil.
Technical background
Just having begun DCL/Direct coal liquefaction produced the liquid hydrocarbon product 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.
Owing to contain a large amount of alkene in the liquefied coal coil, nitrogen content is generally more than 0.5%, also contain a certain amount of oxygen,, very easily generate and be unfavorable for subsequent transportation and substances processed if untimelyly carry out pre-treatment, therefore to adopt the method for hydrogenation that liquefied coal coil is carried out pre-treatment, alkene in the saturated liquefied coal coil removes oxygen, removes heteroatomss such as nitrogen and sulphur to greatest extent, improve the stability of liquefied coal coil, so claim that also this hydrogenation process is stable hydrogenation.Because liquefied coal coil was as hydrogen supply agent after most of coal liquefaction crafts needed a certain amount of hydrogenation, the technology that has will be as the independent hydrogenation of the liquefied coal coil of hydrogen supply agent, and all the other liquefied coal coils go out coal liquification device as product, the technology that has is with the whole hydrofinings of liquefied coal coil, improve stability, produce hydrogen supply agent simultaneously.
USP4,332,666 disclose a kind of method of producing diesel oil, aviation fuel and Number 2 fuel oil, and the raw material of this method is the cut that is suitable for doing hydrogen supply agent in the liquefied coal coil, extracting goes out naphthenic hydrocarbon as diesel oil, aviation fuel and Number 2 fuel oil from the hydrogenation resultant, and is remaining as hydrogen supply agent.But the yield of diesel oil, aviation fuel product is lower.
Introduced German Kohleoel Process technology in " TECHNOLOGY STATUSREPORT 010-COAL LIQUEFACTION " that the Britain's trade and the Department of Industry publish in October, 1999, this technology is with the online hydrogenation of liquefied coal coil, and portion of product looped back coal liquefaction system as hydrogen supply agent, diesel oil distillate foreign matter content in the product is low, the cetane value height, but its hydrofining technology condition is relatively harsher, and stagnation pressure is up to 30.0MPa.
Summary of the invention
The purpose of this invention is to provide a kind of method from liquefied coal coil greatly preparing hihg-quality diesel oil or rocket engine fuel.
Method provided by the invention is: 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, the tail oil cut can return the deep hydrogenation reforming reactor and contact with hydrocracking catalyst, and hydrogen rich stream returns the deep hydrogenation reforming reactor.
Method provided by the invention can be produced fine-quality diesel oil or rocket engine fuel in maximum ground, provides hydrogen supply agent for coal liquefaction system simultaneously.If as the purpose product, then the yield of diesel oil is more than 70 weight % with diesel oil, the sulphur of diesel oil distillate and the content of nitrogen are extremely low, aromaticity content is lower, density is lower, and cetane value surpasses 45, can satisfy the requirement of " world's fuel oil standard " III class diesel oil to sulphur, nitrogen and aromaticity content; If as the purpose product, then the total recovery of rocket engine fuel has reached 50 weight % with rocket engine fuel, the sulphur of rocket engine fuel cut and the content of nitrogen are very low, and indexs such as freezing point, aromaticity content and smoke point have reached requirement.
Description of drawings
Accompanying drawing is the method flow synoptic diagram from liquefied coal coil greatly preparing hihg-quality diesel oil or rocket engine fuel provided by the invention.
Embodiment
Method provided by the invention comprises the off-line stable hydrogenation of liquefied coal coil and the deep hydrogenation upgrading of stable hydrogenation heavy distillate, describes above-mentioned two steps below respectively in detail.
(1), the off-line stable hydrogenation of liquefied coal coil
Liquefied coal coil after the filtration and hydrogen are mixed into the stable hydrogenation reactor, contact with hydrogenation protecting agent, Hydrobon catalyst, and reaction conditions is: hydrogen dividing potential drop 4.0MPa～20.0MPa, 280 ℃～450 ℃ of temperature of reaction, liquid hourly space velocity 0.1h
-1～10h
-1, hydrogen-oil ratio 300v/v～2800v/v.The stable hydrogenation reactor effluent passes through high-pressure separator, light pressure separator, separation column successively, separate and obtain naphtha fraction, diesel oil distillate and tail oil cut, wherein part tail oil cut is as the hydrogen supply agent of upstream gelatin liquefaction part, and remaining tail oil cut and diesel oil distillate are as the raw material of deep hydrogenation reforming reactor; Isolate light hydrocarbon gas from light pressure separator; Mix with fresh hydrogen from the isolated hydrogen rich stream of high-pressure separator, loop back the stable hydrogenation reactor.
The raw materials used liquefied coal coil of this method is the product liquid that coal obtains through direct liquefaction, and its boiling range is C
5～540 ℃ are preferably C
5～450 ℃.If the liquefied coal coil cut is heavy more, then the content of impurity such as its 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 2.0 weight % and preferably is not more than 1.2 weight % in the raw material, and sulphur content is not more than 1.0 weight %.The raw material oil properties is largely depended in technological operation handiness of the present invention, as nitrogen content, aromaticity content, boiling range etc.Owing to contain solid particulate in the raw material, if do not remove these solid particulates, will make the reactor bed pressure drop excessive, and shorten the life-span of Hydrobon catalyst.Therefore, raw material must be earlier after filtration device filter, remove in the liquefied coal coil behind the entrained solid particle, just can enter the stable hydrogenation reactor.
Described Hydrobon catalyst can be to load on the VIB on unformed aluminum oxide or the silica-alumina supports or the non-precious metal catalyst of VIII family, and halogen atom-containing not, and preferred Hydrobon catalyst is by 2.4～6.5 weight %NiO, 24～35 weight %WO
3, 0.1～2.1 weight %MgO and surplus unformed aluminum oxide or silica-alumina supports constitute.This catalyzer has very strong hydrodenitrogenationactivity activity, and this is that the relatively low characteristics of sulphur content design at nitrogen content in the liquefied coal coil is very high.The stable hydrogenation catalyzer is halogen atom-containing not, and the water of avoiding the contained oxygen hydrogenation of halogen atom and liquefied coal coil to generate reacts, and causes equipment corrosion.Because liquefied coal coil contains a certain amount of heavy metal and C
7Insolubles, these trace heavy metals very easily are deposited on the Primary Catalysts top, cause reactor pressure reduction to occur, reduce hydrogenation unit running period, and the metal that is deposited on simultaneously on the catalyzer can cause the hydrogenation catalyst permanent deactivation, and C
7Therefore the inactivation of insolubles meeting accelerator activator in stable hydrogenation technology, has adopted the protective material technology, with having higher demetalization and taking off C
7The hydrogenation protecting agent of insolubles function is seated in the Primary Catalysts top, avoids the generation of above-mentioned phenomenon.This hydrogenation protecting agent is by 1.0～5.0 heavy %NiO, 5.5～10.0 heavy %MoO
3The γ-Al that diplopore distributes that has with surplus
2O
3Carrier is formed.This protectant specific surface ≮ 180m
2/ g, pore volume ≮ 0.6mL/g, crushing strength ≮ 12N/mm.The hydrogenation protecting agent can be used one or more, and the loadings of hydrogenation protecting agent determines that the volume ratio of hydrogenation protecting agent and Hydrobon catalyst is 0.03～0.35 by foreign matter content in the liquefied coal coil and device running period.
Liquefied coal coil off-line stable hydrogenation is meant that the stable hydrogenation device is not serially connected with coal liquification device, have independent raw material supply system and product gathering system, hydrogenation unit is shutting down voluntarily, the hydrogenation unit shutting down does not influence other device running, and the hydrogenation unit running is not subjected to the influence of other device running status yet.Adopt the off-line hydrogenation can avoid the influence of the water vapour that is rich in the liquefied coal coil, CO in the upstream gelatin liquefaction part gas phase to hydrogenation catalyst
xCan not enter the stable hydrogenation device, reduce by CO
xHydrogenation generates CH
4The meaningless hydrogen consumption that causes.The off-line hydrogenation technique can be avoided the influence of gelatin liquefaction part unplanned shutdown to the stable hydrogenation device.If adopt online hydrogenation technique, when gelatin liquefaction partly went wrong and causes hydrogenation unit to stop in emergency, when temperature of reactor drops to below 100 ℃, the water in the gas phase can be absorbed by catalyzer, cause the catalyzer mechanical property to descend, have a strong impact on catalyst life.
Not good enough for preventing coal liquefaction system separating device separating effect, cause carrying secretly in the liquefied coal coil gelatin liquefaction process catalyst system therefor, before stable hydrogenation device feedstock pump, install filtration unit additional, filter out the solid particulate in the liquefied coal coil, prevent the too fast inactivation of hydrogenation catalyst, improve the hydrogenation catalyst life-span, prolong stable hydrogenation device running period.
(2), the deep hydrogenation upgrading of stable hydrogenation heavy distillate
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, reaction conditions is: hydrogen dividing potential drop 6.0MPa～20.0MPa, 280 ℃～450 ℃ of temperature of reaction, liquid hourly space velocity 0.1h
-1～20h
-1, hydrogen-oil ratio 400v/v～3000v/v.The stable hydrogenation reactor effluent passes through high-pressure separator, light pressure separator, separation column successively, separate and obtain naphtha fraction, diesel oil distillate and tail oil cut or naphtha fraction, rocket engine fuel, diesel oil distillate and tail oil cut, naphtha fraction arene underwater content height wherein, can be used as the charging of catalytic reforming, part tail oil cut can return the deep hydrogenation reforming reactor and contact with hydrocracking catalyst, and the tail oil cut also can directly go out device; Isolate light hydrocarbon gas from light pressure separator; Mix with fresh hydrogen from the isolated hydrogen rich stream of high-pressure separator, loop back the stable hydrogenation reactor.
Why the selected depth hydrogenation modifying process is as the second step processing means in the present invention, be because the present invention produces diesel oil with maximum or rocket engine fuel is a purpose, to be converted into relative lighter fraction than last running by the deep hydrogenation upgrading, reduce the aromaticity content of charging simultaneously, and reach the purpose that reduces diesel oil distillate density, improves the diesel oil distillate cetane value by appropriate open loop.If the heavy constituent of deep hydrogenation modifying apparatus charging are less, then just can change whole heavy constituent into lightweight oil by a cracking, the technical process of deep hydrogenation modifying apparatus can once be passed through for single hop, Hydrobon catalyst and hydrocracking catalyst are seated in the reactor, also can be seated in two reactors; If heavy constituent are more in the charging, then once being difficult to whole heavy constituent crackings by flow process is gasoline, diesel oil, must be with deep hydrogenation upgrading tail oil circulation carrying out cracking, the deep hydrogenation device adopts two reactors to load Hydrobon catalyst and hydrocracking catalyst respectively, deep hydrogenation device tail oil is looped back cracking case process.
The used Hydrobon catalyst of deep hydrogenation modifying apparatus can be VIB and the VIII family non-precious metal catalyst that loads on unformed aluminum oxide or the silica-alumina supports, and hydrocracking catalyst is VIB and the VIII family non-precious metal catalyst that loads on the y-type zeolite molecular sieve.
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 method flow synoptic diagram from liquefied coal coil greatly preparing hihg-quality diesel oil or rocket engine fuel 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; after mixing from the hydrogen-rich gas of pipeline 5,6 successively; through interchanger 4 heat exchange; again after process furnace 7 heating; enter stable hydrogenation reactor 9, contact, remove impurity such as metal in the stock oil, sulphur and nitrogen with hydrogenation protecting agent, 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 stable hydrogenation reactor 9 through pipeline 8 after interchanger 4 heat exchange, enter high-pressure separator 10, in high-pressure separator, be separated into two bursts of logistics, one is a hydrogen-rich stream, wherein be mainly hydrogen, comprise partial vulcanization hydrogen, ammonia simultaneously, hydrogen-rich stream after pipeline 5 is through the recycle compressors compression with mix from the fresh hydrogen of pipeline 2, loop back reactor 9 through pipeline 6; Another burst logistics enters light pressure separator 12 through pipeline 11, the lighter hydrocarbons that remove are through pipeline 13 caterpillars, light pressure separator bottom effluent enters fractionating column system 15 through pipeline 14, the naphtha fraction that fractionates out is through pipeline 16 caterpillars, diesel oil distillate enters the deep hydrogenation modifying apparatus through pipeline 17, the tail oil cut is divided into two portions through pipeline 18, and wherein a part goes out the stable hydrogenation device as required, loops back coal liquefaction system and does hydrogen supply agent.
Remaining another part tail oil cut and diesel oil distillate advance surge tank 19, boost to reaction pressure by feedstock pump then, mix with the hydrogen-rich gas from pipeline 28,20 successively, after interchanger 21 heat exchange, after pipeline 22 enters process furnace 23 heating, enter the hydrofining reactor 24 of deep hydrogenation reforming reactor, again by contacting with the Hydrobon catalyst bed, further remove impurity such as sulphur and nitrogen, saturated 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 hydrofining reactor enters hydrocracking reactor 26 through pipeline 25, though hydrocracking is thermo-negative reaction, but the hydrogenation saturated reaction is thermopositive reaction, as a whole, the reaction that hydrocracking reactor carried out is thermopositive reaction, need in the middle of reactor, to introduce cold hydrogen, control reaction temperature.If degree of depth modifying apparatus is only established a reactor, hydrofining agent and hydrocracking agent will be seated in the reactor, reactor 24 and 26 be regarded as a reactor.Deep hydrogenation reforming reactor system effluent is after pipeline 27 enters interchanger 21 heat exchange, enter high-pressure separator 29, in high-pressure separator, be separated into two bursts of logistics, one is a hydrogen-rich stream, wherein be mainly hydrogen, comprise partial vulcanization hydrogen, ammonia simultaneously and because the light hydrocarbon that cracking produces, hydrogen-rich stream is after pipeline 28 is through the recycle compressors compression, with mix from the fresh hydrogen of pipeline 2, loop back reactor 24 through pipeline 20, interchanger 21, pipeline 22, process furnace 23 successively; Another burst logistics enters light pressure separator 31 through pipeline 30, the lighter hydrocarbons that remove are through pipeline 32 caterpillars, light pressure separator bottom effluent enters fractionating column system 34 through pipeline 33, and the naphtha fraction that fractionates out, rocket engine fuel cut or diesel oil distillate are respectively through pipeline 35,36 caterpillars.If the charging of deep hydrogenation modifying apparatus is heavier, can cut out more heavy-tailed oil distillate from separation column 34, the tail oil cut mixes charging as cracking case 26 through pipeline 37 with the effluent of hydrofining reactor.
Method advantage provided by the invention is:
1, because the Hydrobon catalyst of stable hydrogenation halogen atom-containing not, the water of avoiding the contained oxygen hydrogenation of halogen atom and liquefied coal coil to generate reacts and the equipment corrosion that causes.
2, because the raw material of stable hydrogenation is removed solid particulate earlier after filtration, avoid the reactor bed pressure drop excessive, thereby prolonged the life-span of Hydrobon catalyst.
3, adopt the off-line stable hydrogenation can avoid that contained a large amount of water vapour reduce the hydrogen consumption, and can avoid the influence of gelatin liquefaction part unplanned shutdown to the stable hydrogenation device the influence of hydrogenation catalyst in the liquefied coal coil.
4, method provided by the invention can be produced fine-quality diesel oil or rocket engine fuel in maximum ground, provides hydrogen supply agent for coal liquefaction system simultaneously.If as the purpose product, then the yield of diesel oil is more than 70 weight % with diesel oil, the sulphur of diesel oil distillate and the content of nitrogen are very low, aromaticity content is lower, density is lower, and cetane value surpasses 45, can satisfy the requirement of " world's fuel oil standard " III class diesel oil to sulphur, nitrogen and aromaticity content; If as the purpose product, then the total recovery of rocket engine fuel has reached 50 weight % with rocket engine fuel, the sulphur of rocket engine fuel cut and the content of nitrogen are very low, and indexs such as freezing point, aromaticity content and smoke point have reached requirement.
The following examples will give further instruction to present method, but therefore not limit present method.
Liquefied coal coil A, B used among the embodiment are all through filtering, the used Hydrobon catalyst trade names of stable hydrogenation are RCT-1, hydrogenation protecting agent trade names are RG-10A/RG-10B, produce by Sinopec Chang Ling catalyst plant, the volume ratio of RG-10A/RG-10B and RCT-1 is 0.2; The used Hydrobon catalyst of deep hydrogenation upgrading, the trade names of hydrocracking catalyst are respectively RN-10, RT-5, produce by Sinopec Chang Ling catalyst plant.Test is carried out on medium-sized fixed bed hydrogenation device.
Liquefied coal coil A and hydrogen after the filtration enter the stable hydrogenation reactor, contact with hydrogenation protecting agent RG-10A/RG-10B, Hydrobon catalyst RCT-1, 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 that hydrofining agent RN-10 and hydrocracking agent RT-5 are housed, contact with RN-10, RT-5, separate the hydro-upgrading reactor effluent and obtain gas, naphtha fraction, diesel oil distillate and tail oil cut, the tail oil cut returns the deep hydrogenation reforming reactor and contacts with hydrocracking catalyst, and hydrogen rich stream returns the deep hydrogenation reforming reactor.
Stock oil character, processing condition and diesel product character are listed in table 1, table 2 and table 3 respectively.As seen from Table 3, the total recovery of diesel oil is 77 weight %, has realized maximum production diesel oil purpose.The sulphur of diesel oil distillate and the content of nitrogen are very low, and aromaticity content is lower, have reached the index request of " world's fuel oil standard " III class diesel oil, and its cetane value surpasses 45, is qualified diesel product.
The flow process of this embodiment is substantially the same manner as Example 1, and raw material still is liquefied coal coil A, and last purpose product is a rocket engine fuel.The processing condition of stable hydrogenation and deep hydrogenation upgrading and rocket engine fuel product property are listed in table 2 and table 3 respectively.As seen from Table 3, the total recovery of rocket engine fuel has reached 50%, and the content of the sulphur of rocket engine fuel cut and nitrogen is very low in the product, and indexs such as freezing point, aromaticity content and smoke point have reached requirement, are qualified rocket engine fuel products.
The flow process of this embodiment is substantially the same manner as Example 1, and raw material still is liquefied coal coil B, and last purpose product is a diesel oil, and deep hydrogenation upgrading flow process is for once passing through, and hydrofining agent RN-10 and hydrocracking agent RT-5 are seated in respectively in two reactors.Stock oil character, processing condition and diesel product character are listed in table 1, table 4 and table 5 respectively.As seen from Table 1, liquefied coal coil B is heavier; As seen from Table 5, the total recovery of diesel oil is 73%, has realized maximum production diesel oil purpose.The sulphur of diesel oil distillate and the content of nitrogen are very low, and aromaticity content is lower, can satisfy the requirement of " world's fuel oil standard " III class diesel oil to sulphur, nitrogen and aromaticity content, and cetane value surpasses 45, is qualified diesel product.
Embodiment 4
The flow process of this embodiment is substantially the same manner as Example 1, raw material still is liquefied coal coil B, last purpose product is a diesel oil, hydrofining agent RN-10 is seated in respectively in two different reactors with hydrocracking agent RT-5, the deep hydrogenation upgrading is the tail oil circulation process, in the deep hydrogenation device product＞and 390 ℃ of cuts loop back in the hydrocracking reactor.Stock oil character, processing condition and diesel product character are listed in table 1, table 4 and table 5 respectively.As seen from Table 5, the total recovery of diesel oil is 80%, has realized maximum production diesel oil purpose.The sulphur of diesel oil distillate and the content of nitrogen are very low, and aromaticity content is lower, can satisfy the requirement of " world's fuel oil standard " III class diesel oil to sulphur, nitrogen and aromaticity content, and cetane value surpasses 45, is qualified diesel product.
Table 1
| | | |
| The liquefied coal coil numbering | ????A | ????B |
| Density (20 ℃), g/cm 3 | ????0.9300 | ????0.9591 |
| S, weight % | ????0.19 | ????0.23 |
| N, weight % | ????0.41 | ????0.0.64 |
| The bromine valency, gBr/100g | ????20.4 | ????21.7 |
| Boiling range ASTM D-1160, ℃ | ||
| Initial boiling point | ????115 | ????64 |
| 10％ | ????178 | ????193 |
| 50％ | ????301 | ????335 |
| ?95％ | ????385 | ????436 |
Table 2
| | | |
| The stable hydrogenation processing condition | ||
| Temperature of reaction, ℃ | ????340 | ????355 |
| 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 |
| Deep hydrogenation modifying process condition | ||
| Temperature of reaction, ℃ | ????370 | ????375 |
| 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 |
| The diesel oil total recovery, weight % | ????77 | ?????- |
Table 3
| | | |
| Density (20 ℃), g/cm 3 | ????0.8821 | ????0.8012 |
| S，ppm | ????4 | ????3 |
| N，ppm | ????1 | ????0.6 |
| The bromine valency, gBr/100g | ????0.23 | ????＜0.1 |
| Cetane value | ????46.7 | ????- |
| Freezing point, ℃ | ????- | ????＜60 |
| Smoke point, mm | ????- | ????29.6 |
| Mercaptan sulfur, ppm | ????- | ????＜3 |
| Corrosion (100 ℃, 2h) | ????- | ????1 |
| Aromaticity content, weight % | ????- | ????12 |
| Boiling range ASTM D-86, ℃ | ||
| Initial boiling point | ????184 | ????143 |
| 50％ | ????277 | ????159 |
| 95％ | ????363 | ????210 |
Table 4
| | Embodiment 4 | |
| The stable hydrogenation processing condition | ||
| Temperature of reaction, ℃ | ????350 | ????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 |
| Deep hydrogenation modifying process condition | ||
| Temperature of reaction (anti-/ two are anti-), ℃ | ????350/375 | ????350/375 |
| 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 |
| The diesel oil total recovery, weight % | ????80 | ????80 |
Table 5
| | Embodiment 4 | |
| Density (20 ℃), g/cm 3 | ????0.8730 | ????0.861 |
| S，ppm | ????2 | ????2 |
| N，ppm | ????0.5 | ????0.5 |
| The bromine valency, gBr/100g | ????0.26 | ????0.26 |
| Cetane value | ????48 | ????46 |
| Aromaticity content, weight % | ????12.2 | ????14.8 |
| Boiling range ASTM D-86, ℃ | ||
| Initial boiling point | ????184 | ????189 |
| 50％ | ????267 | ????261 |
| 90％ | ????351 | ????322 |
Claims (11)
1, a kind of method from liquefied coal coil greatly preparing hihg-quality diesel oil or rocket engine fuel, liquefied coal coil after it is characterized in that filtering 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.
2, according to the method for claim 1, it is characterized in that described liquefied coal coil is the product liquid that coal obtains through direct liquefaction, its boiling range is C
5～540 ℃.
3, according to the method for claim 1, it is characterized in that the reaction conditions of stable hydrogenation is: hydrogen dividing potential drop 4.0MPa～20.0MPa, 280 ℃～450 ℃ of temperature of reaction, liquid hourly space velocity 0.1h
-1～10h
-1, hydrogen-oil ratio 300v/v～2800v/v.
4, according to the method for claim 1, it is characterized in that the used Hydrobon catalyst of stable hydrogenation is to load on the VIB on unformed aluminum oxide or the silica-alumina supports or the non-precious metal catalyst of VIII family, and halogen atom-containing not.
5,, it is characterized in that the used Hydrobon catalyst of stable hydrogenation is by 2.4～6.5 weight %NiO, 24～35 weight %WO according to the method for claim 4
3, 0.1～2.1 weight %MgO and surplus unformed aluminum oxide or silica-alumina supports constitute.
6,, it is characterized in that the used hydrogenation protecting agent of stable hydrogenation is by 1.0～5.0 heavy %NiO, 5.5～10.0 heavy %MoO according to the method for claim 1
3The γ-Al that diplopore distributes that has with surplus
2O
3Carrier is formed.
7, according to the method one of in the claim 1,4,5,6, the volume ratio that it is characterized in that described hydrogenation protecting agent and Hydrobon catalyst is 0.03～0.35.
8, reaction conditions is: hydrogen dividing potential drop 6.0MPa～20.0MPa, 280 ℃～450 ℃ of temperature of reaction, liquid hourly space velocity 0.1h
-1～20h
-1, hydrogen-oil ratio 400v/v～3000v/v.
9, according to the method for claim 1, it is characterized in that the used Hydrobon catalyst of deep hydrogenation upgrading can be VIB and the VIII family non-precious metal catalyst that loads on unformed aluminum oxide or the silica-alumina supports, hydrocracking catalyst is VIB and the VIII family non-precious metal catalyst that loads on the y-type zeolite molecular sieve.
10, according to the method for claim 1 or 9, it is characterized in that the deep hydrogenation upgrading used Hydrobon catalyst and hydrocracking catalyst are seated in the reactor or two reactors in
11,, it is characterized in that deep hydrogenation upgrading gained tail oil cut returns the deep hydrogenation reforming reactor and contacts with hydrocracking catalyst according to the method for claim 1.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100419044C (en) * | 2005-07-15 | 2008-09-17 | 中国石油化工股份有限公司 | Production of large-specific-weight aircraft liquid petroleum oil at maximum from coal liquefied oil |
| CN101928599A (en) * | 2009-06-25 | 2010-12-29 | 中国石油化工股份有限公司 | Method for producing jet fuel or jet fuel blending component |
| CN102051224A (en) * | 2010-06-24 | 2011-05-11 | 神华集团有限责任公司 | Production method of coal-based high-aromatic-hydrocarbon-potential-content naphtha for catalytic reforming, product and application thereof |
| CN102061191A (en) * | 2009-11-12 | 2011-05-18 | 中国石油化工股份有限公司 | Method for producing solvent oil or blended components thereof |
| CN103773489A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Hydrogenation method for treating high-nitrogen high-aromatic hydrocarbon inferior diesel oil raw materials |
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2002
- 2002-02-07 CN CNB02100594XA patent/CN1162516C/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100378204C (en) * | 2005-07-15 | 2008-04-02 | 中国石油化工股份有限公司 | Combined process for converting coal liquefied oil at maximum |
| CN100419044C (en) * | 2005-07-15 | 2008-09-17 | 中国石油化工股份有限公司 | Production of large-specific-weight aircraft liquid petroleum oil at maximum from coal liquefied oil |
| CN101928599A (en) * | 2009-06-25 | 2010-12-29 | 中国石油化工股份有限公司 | Method for producing jet fuel or jet fuel blending component |
| CN102061191A (en) * | 2009-11-12 | 2011-05-18 | 中国石油化工股份有限公司 | Method for producing solvent oil or blended components thereof |
| CN102051224A (en) * | 2010-06-24 | 2011-05-11 | 神华集团有限责任公司 | Production method of coal-based high-aromatic-hydrocarbon-potential-content naphtha for catalytic reforming, product and application thereof |
| CN102051224B (en) * | 2010-06-24 | 2013-09-25 | 神华集团有限责任公司 | Production method of coal-based high-aromatic-hydrocarbon-potential-content naphtha for catalytic reforming, product and application thereof |
| CN103773489A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Hydrogenation method for treating high-nitrogen high-aromatic hydrocarbon inferior diesel oil raw materials |
| CN103773489B (en) * | 2012-10-25 | 2016-03-02 | 中国石油化工股份有限公司 | A kind of method of hydrotreating processing high nitrogen, high aromatic hydrocarbons poor ignition quality fuel raw material |
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| Publication number | Publication date |
|---|---|
| CN1162516C (en) | 2004-08-18 |
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