CN102899087B - Deep processing method for medium and low temperature coal tar - Google Patents
Deep processing method for medium and low temperature coal tar Download PDFInfo
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Abstract
The invention discloses a deep processing method for medium and low temperature coal tar. The medium and low temperature coal tar raw material is pretreated and fractionated to obtain the light distillates, phenol oil, heavy distillates and heavy oil; the phenol oil is subjected to dephenolization to obtain phenol produces and dephenolized oil; bottom heavy oil and unconverted tail oil from a hydrocracking section are mixed and subjected to a coking reaction to obtain a variety of coking products; coking naphtha, coker diesel and coker gas oil from the coking products are mixed with light distillates, dephenolized oil and heavy distillates from raw material fractionation, and are subjected to hydrofining and hydrocracking reaction. Compared with the prior art, the method provided by the invention can produce clean gasoline and diesel fractions with stable performances. In addition, the method can produce a variety of chemical products with high additional value, realize the effective utilization of medium and low temperature coal tar, and greatly prolong operation cycle of the device.
Description
Technical field
What the present invention relates to is a kind of Coal Chemical Industry technique, specifically coalite tar deep processing technology method in one.
Background technology
The dry distillation of coal and gasification are the important component parts of Coal Chemical Industry technique, and raw material is main mainly with dross coal or weak caking coal.Dross coal or weak caking coal comprise brown coal, long-flame coal, bottle coal etc.Brown coal are a kind of incoherence or weak caking coal, and it is the coal that degree of coalification is minimum.The feature of brown coal is that moisture is high, proportion is little, volatile matter is high, non-caked, chemical reactivity strong, poor heat stability, thermal value are low, the humic acid containing different quantities.Be used as the raw material of fuel, gasification more, also can be used to extract montanin wax, humic acid, manufacture sulphonated coal or gac etc.The volatile content of long-flame coal is also very high, not or only have very little cohesiveness, easy firing, does not have very long flame during burning, therefore long-flame coal of gaining the name.Long-flame coal can be used as the raw material of gasification, also can make civilian and power fuel.Bottle coal volatile matter is high, and gelatinous layer is thicker, poor heat stability.The coking separately of long-flame coal energy, but the coke produced is elongated frangible, and shrinking percentage is large, and longitudinal crack is many, anti-crushing poor with wear resistance, therefore can only be used as coal-blending coking, also can be used to manufacture coal gas, produce nitrogenous fertilizer or the fuel that is used as power.
The dross coal such as above-mentioned brown coal, long-flame coal, bottle coal or weak caking coal all contain abundant organic matter, and when middle low-temperature pyrolysis, half afocal is produced in decapacitation, also can generate coal gas and coal tar, and the mass rate of production of coal tar is generally between 8% ~ 20%; This type of coal carries out gasification and manufactures coal gas (domestic fuel) or preparing synthetic gas (CO+H
2) when producing other Chemicals, also can produce coal tar, the mass rate of production of coal tar is generally between 4% ~ 12%.Due to coal directly burning can cause more serious dust pollution, therefore, be that raw material production town gas is more and more higher as the ratio of domestic fuel with coal, the middle coalite tar amount of simultaneously association also increases greatly.Because semicoke is the main raw material producing ferrosilicon and calcium carbide etc., the device therefore producing low-temperature pyrolysis in the coal of semicoke is also more and more, and the middle coalite tar amount of association simultaneously is also increasing greatly.At present, the treatment process that the factory of semicoke and the middle coalite tar of coal gasification plant by-product are produced in above-mentioned middle low-temperature pyrolysis is directly burnt as low-quality fuel oil after acid-alkali refining, or as emulsion fuel burns after direct emulsification.But wherein institute's impurity such as sulfur-bearing, nitrogen becomes SOx and NOx in combustion and discharges into the atmosphere and cause topsoil, and produces large amount of sewage again in acid-alkali refining process.
Because middle coalite tar comes from the dry distillation of coal and gasification, be hot cracked product, so the composition of middle coalite tar is very complicated.Chemical constitution mainly aromatics and the alkene of middle coalite tar, Determination of Alkane Content is less, also contains oxygen, nitrogenous, sulfocompound containing a small amount of.Oxygenatedchemicals mainly has weakly acidic various phenols, and nitrogenous compound mainly has weakly alkaline pyridine, quinoline and their derivative, and sulfocompound is thiophene, mercaptan, thiophenol, thioether etc. mainly.Along with the deficiency of China's oil resource, the increase year by year of crude oil import ratio, with middle coalite tar for stock oil, adopts more suitable complete processing to produce the clean fuel suitable with petroleum products or petroleum products, not only there is significant economic benefit, also there is obvious social benefit simultaneously.
The deep processing method of middle coalite tar, once received much attention in twentieth century 50, the sixties and dropped into substantial contribution and manpower studies.But find along with the ground such as grand celebration, Xinjiang and exploited oil, oil instead of coal tar very soon as main energy sources and produces vehicle fuel.From twentieth century seventies, the research of China's centering coalite tar deep process technology is almost stagnated, until twentieth century end of the nineties, due to the growing tension of petroleum resources, the increasingly stringent of environmental regulation, the deep processing of coal tar starts to come into one's own again.Chinese patent CN1205302C proposes a kind of complete processing of middle coalite tar: first middle coalite tar carries out delayed coking, produce coke and coking distillate, coking distillate enters extraction tower afterwards, alkaline solution is added in extraction tower, extract phenols, the fraction oil of dephenolize enters separation column, then fractionates out the cut such as petroleum naphtha and diesel oil.But this technique patent has following shortcoming and defect:
1, dephenolize is put into delayed coking after phenols can corrode delayed coking unit, affect service life of equipment.
2, delayed coking scheme can reduce target product liquid and receive, and reduces economic benefit.Although and delayed coking can remove the impurity such as sulphur, nitrogen in part coal tar, very major part is still retained in coking distillate, can not be removed in a large number, still environmental pollution can be caused when burning.The more important thing is, the distillate after coking contains more alkene and colloid, and the heat that can affect oil product is stable qualitative, causes engine damage.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide coalite tar complete processing in one, make up the deficiency of above-mentioned prior art processes, not only can production high-quality oil product, and coalite tar in farthest utilizing.
In the present invention, coalite tar deep processing method comprises following processing step:
1, middle low temperature coal tar raw material carries out fractionation, obtains lighting end, carbolic oil, last running and heavy oil;
2, the carbolic oil that step 1 obtains carries out phenol removal, obtains phenol products and dephenolize oil;
3, the heavy oil obtained in step 1 carries out pyrogenic reaction, obtains the products such as coking dry gas, liquefied gas, coking naphtha, coker gas oil, wax tailings and refinery coke;
4, the dephenolize oil that the lighting end that step 3 obtains coking naphtha, coker gas oil and wax tailings obtain with step 1, last running and step 2 obtain mixes, carry out hydrofining and hydrocracking reaction, be obtained by reacting the products such as dry gas, liquefied gas, hydrotreated naphtha and hydrogenated diesel oil;
In the inventive method, the destructive distillation coal tar of low-temperature pyrolysis and/or the coal tar of gasification by-product in the preferred coal of middle coalite tar in step 1, middle coalite tar carries out pre-treatment before carrying out fractionation, pre-treatment mainly removes moisture and mechanical impurity, and the method such as centrifuging, electrodesalting and electrodehydrating specifically can be adopted to carry out pre-treatment.Fractionation adopts vacuum fractionation tower, tower top fractionates out lighting end, side line fractionates out carbolic oil and last running, heavy oil is obtained at the bottom of tower, the final boiling point of lighting end is generally and is not more than 180 DEG C, the final boiling point of carbolic oil is generally and is not more than 240 DEG C, and the final boiling point of last running is generally and is not more than 350 DEG C, and the initial boiling point of heavy oil is generally and is not less than 340 DEG C.
The inventive method, the phenol removal described in step 2 adopts soda acid method for extracting, and concrete operations mode is well known to those skilled in the art.Specifically can adopt conventional coal tar carbolic oil refining plant, what vacuum fractionation tower separated enters extraction tower containing phenol cut, in extraction tower, add alkaline solution, and the phenates extracted is through steaming stripping oil, sulfuric acid or CO
2obtain phenol products after decomposition, after extracting phenol products, obtain dephenolize oil.The phenol products obtained generally comprises phenol, industrial cresols, ortho-cresol and xylenol etc.Also may contain part aldehydes matter in the lighting end that step 1 obtains, also can carry out phenol removal, obtain phenol products and dephenolize oil.
The inventive method, pyrogenic reaction described in step 3 preferably adopts delayed coking, coking adopts method well known to those skilled in the art, but the delayed coking charging in this invention is heavy oil (initial boiling point is generally not less than 340 DEG C) at the bottom of tower in step 1 produces the mixing oil of unreacted tail oil with the hydrocracking section in this invention.In addition, other Suitable base can be added, as the sump oil etc. that various poor residuum, catalytically cracked oil, field of Environment Protection reclaim.A kind of typical pyrogenic reaction operational condition is as follows: temperature of reaction 400 DEG C ~ 550 DEG C, reaction pressure 0.15MPa ~ 0.5MPa; Preferable reaction temperature 400 DEG C ~ 535 DEG C, preferred reaction pressure 0.17MPa ~ 0.35MPa.
In the inventive method, hydrofining in step 4 and hydrocracking can adopt technological process well known to those skilled in the art, hydrofining effluent generally need carry out separating treatment, the water that the impurity removed in hydrofining reaction process particularly produces is separated, then carry out hydrocracking reaction, avoid having a negative impact to hydrocracking.A kind of typical method adopts two-stage hydrocracking technique, and hydrofining reaction product, before entering hydrocracking reactor, first enters separation column.Separation column is conventional atmospheric distillation plant, by hydrofining full distillate oil by can output gasoline fraction, diesel oil distillate and wax oil cut after fractionation, gasoline fraction and diesel oil distillate directly go out device, wax oil cut then carries out hydrocracking reaction, carry out hydrocracking further and produce gasoline fraction, diesel oil distillate and unconverted tail oil, gasoline fraction and diesel oil distillate directly go out device, and unconverted tail oil mixes the charging as delayed coking with heavy oil at the bottom of the tower in step 1 (initial boiling point is generally not less than 340 DEG C).If exist other source raw material, can as required with above-mentioned unifining process and hydrocracking process co-treatment.
In the inventive method, the hydrofining in step 4 and hydrocracking can adopt catalyzer well known to those skilled in the art and processing condition.Hydrofining reaction condition is generally: volume space velocity 0.15 ~ 1.5h when temperature of reaction 180 ~ 427 DEG C, pressure 10.0 ~ 17.0MPa, hydrogen to oil volume ratio 500: 1 ~ 3500: 1 and liquid
-1.The most preferred reaction conditions of hydrofining reaction is as follows: volume space velocity 0.2 ~ 1.2h when temperature of reaction 180 ~ 420 DEG C, pressure 10.0 ~ 16.0MPa, hydrogen to oil volume ratio 800: 1 ~ 3000: 1 and liquid
-1.Hydrocracking reaction condition is generally: volume space velocity 0.15 ~ 1.5h when temperature of reaction 360 ~ 427 DEG C, pressure 10.0 ~ 17.0MPa, hydrogen to oil volume ratio 500: 1 ~ 2000: 1 and liquid
-1.The most preferred reaction conditions of hydrocracking is as follows: volume space velocity 0.2 ~ 1.2h when temperature of reaction 380 ~ 420 DEG C, pressure 10.0 ~ 16.0MPa, hydrogen to oil volume ratio 800: 1 ~ 1500: 1 and liquid
-1.
In the inventive method, the hydrogen that in step 4, hydrofining and hydrocracking process need can derive from one or more in dry distillation of coal coal gas, gasification coal gas, natural gas hydrogen preparation, oil refinery dry gas hydrogen manufacturing and hydrogen from methyl alcohol, the concentrate of low-concentration hydrogen can adopt this area ordinary method, as pressure-changed adsorption concentrating method etc.
The gasoline fraction that the inventive method obtains and diesel oil distillate are clean, are also stable performances.In addition, the singularity of coal tar component is utilized also to produce the high value added products such as phenol, industrial cresols, ortho-cresol, xylenol, liquefied gas and refinery coke.Really achieve effective utilization of middle coalite tar, more substantially increase the work-ing life of appliance arrangement.
Specifically, the inventive method also has following attendant advantages:
1, phenols has deep-etching effect to equipment, and has high added value, therefore before to coal tar deep processing, first isolates phenol products, not only adds economic benefit, extends the work-ing life of coal tar deep processing appliance arrangement simultaneously.
2, because coal tar contains the material of more solid dust and easily coking, above-mentioned substance not easily adopts other technologies to be isolated out, adopt delay coking process can be solidificated in coke by the material of solid dust and easy coking, in addition, coal tar is different from oil, and the nitrogen content of coal tar is high, sulphur content is low, and oil is on the contrary, is therefore that low-sulfur is burnt with the coke that coal tar produces, has been widely used.
3, by the distillate after delayed coking again through hydrotreatment, greatly can improve the character of oil product, the petrol and diesel oil cut of maximum ground production high-quality, was becoming tight in oil supply day, when light-end products demand goes up, provide the source of supply of new light-end products.
4, coal gas is after purification, adopts pressure-variable adsorption (PSA) technology hydrogen to be proposed to be used for the hydrogenation process of destructive distillation coal tar, belongs to Matter Transfer and use, without exhaust emission.The more important thing is that the impurity such as the sulphur in raw coal, nitrogen are entered after in dry distillation gas and destructive distillation coal tar by destructive distillation, can be sulphur and ammoniacal liquor by sulphur, azepine cycling of elements easily, namely add economic benefit, additionally reduce the environmental pollution of burning dry distillation gas and coal tar production petrol and diesel oil cut.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of coalite tar processing in the present invention.
Embodiment
Press the citing of technical process shown in Fig. 1 below for a more detailed description to the present invention.
Table 1 is destructive distillation coal tar main character, and table 2 is product main character of the present invention.
Embodiment 1
The low-temperature pyrolysis coal tar of Shenmu County's brown coal, character is in table 1, send to after pretreatment unit removes mechanical impurity and water and enter vacuum fractionation tower 1, fractionate out benzoline (overhead oil), heavy distillate (side line), carbolic oil (side line) and heavy oil, carbolic oil enters carbolic oil extraction plant 2 and isolates phenol products and dephenolize oil, heavy oil at the bottom of tower and the unconverted tail oil of hydrocracking section are mixed into delayed coking unit 3 to carry out heat scission reaction and produces coking dry gas, liquefied gas, coking naphtha, coker gas oil, wax tailings and petroleum coke, temperature of reaction is 465 DEG C, reaction pressure 0.23MPa.Wherein coking naphtha, coker gas oil, the benzoline of wax tailings and separation column 1, enter hydro-refining unit 4 after the isolated dephenolize oil of carbolic oil extraction plant 2 and heavy distillate mix and carry out hydrofining reaction, the gasoline that hydrofining reaction obtains and diesel oil can go out device, the wax oil that hydrofining reaction obtains enters hydroeracking unit 5 and carries out hydrocracking reaction, hydrocracking reaction product separation is dry gas, liquefied gas, hydrotreated naphtha, hydrogenated diesel oil and unconverted tail oil, hydrorefined average reaction temperature is 320 DEG C, pressure 15.0MPa, volume space velocity 0.5h when hydrogen to oil volume ratio 1000: 1 and liquid
-1, volume space velocity 0.3h when the temperature of reaction 380 DEG C of hydrocracking, pressure 15.0MPa, hydrogen to oil volume ratio 800: 1 and liquid
-1.Hydrobon catalyst is with alumina supporter, and molybdenum oxide weight content is 15%, and Tungsten oxide 99.999 weight content is 12%, and nickel oxide weight content is 5%, and specific surface area is 185m
2/ g, pore volume is 0.35ml/g.(silica/alumina molecular ratio is for 12 with Y zeolite for hydrocracking catalyst, structure cell is often for 0.2426nm) and amorphous aluminum silicide (silica weight content is 27%, infrared acidity is 0.4mmol/g) be Cracking Component, Y zeolite weight content is 15%, amorphous aluminum silicide weight content is 35%, and Tungsten oxide 99.999 weight content is 28%, and nickel oxide weight content is 8%, surplus is aluminum oxide, and specific surface area is 270m
2/ g, pore volume is 0.42ml/g.Hydrobon catalyst and hydrocracking catalyst carry out conventional prevulcanized process before use.
Embodiment 2
The low-temperature pyrolysis coal tar of Shenmu County's brown coal, character is in table 1, send to after pretreatment unit removes mechanical impurity and water and enter vacuum fractionation tower 1, fractionate out benzoline (overhead oil), heavy distillate (side line), carbolic oil (side line) and heavy oil, carbolic oil enters carbolic oil extraction plant 2 and isolates phenol products and dephenolize oil, heavy oil at the bottom of tower and the unconverted tail oil of hydrocracking section are mixed into delayed coking unit 3 to carry out heat scission reaction and produces coking dry gas, liquefied gas, coking naphtha, coker gas oil, wax tailings and petroleum coke, temperature of reaction is 480 DEG C, reaction pressure 0.17MPa.Wherein coking naphtha, coker gas oil, the benzoline of wax tailings and separation column 1, enter hydro-refining unit 4 after the isolated dephenolize oil of carbolic oil extraction plant 2 and heavy distillate mix and carry out hydrofining reaction, the gasoline that hydrofining reaction obtains and diesel oil can go out device, the wax oil that hydrofining reaction obtains enters hydroeracking unit 5 and carries out hydrocracking reaction, hydrocracking reaction product separation is dry gas, liquefied gas, hydrotreated naphtha, hydrogenated diesel oil and unconverted tail oil, hydrorefined average reaction temperature is 340 DEG C, pressure 14.0MPa, volume space velocity 0.25h when hydrogen to oil volume ratio 1500: 1 and liquid
-1, volume space velocity 0.4h when the temperature of reaction 395 DEG C of hydrocracking, pressure 14.0MPa, hydrogen to oil volume ratio 1000: 1 and liquid
-1.Hydrobon catalyst is with alumina supporter, and molybdenum oxide weight content is 15%, and Tungsten oxide 99.999 weight content is 12%, and nickel oxide weight content is 5%, and specific surface area is 185m
2/ g, pore volume is 0.35ml/g.(silica/alumina molecular ratio is for 12 with Y zeolite for hydrocracking catalyst, structure cell is often for 0.2426nm) and amorphous aluminum silicide (silica weight content is 27%, infrared acidity is 0.4mmol/g) be Cracking Component, Y zeolite weight content is 15%, amorphous aluminum silicide weight content is 35%, and Tungsten oxide 99.999 weight content is 28%, and nickel oxide weight content is 8%, surplus is aluminum oxide, and specific surface area is 270m
2/ g, pore volume is 0.42ml/g.Hydrobon catalyst and hydrocracking catalyst carry out conventional prevulcanized process before use.
Embodiment 3
The low-temperature pyrolysis coal tar of Shenmu County's brown coal, character is in table 1, send to after pretreatment unit removes mechanical impurity and water and enter vacuum fractionation tower 1, fractionate out benzoline (overhead oil), heavy distillate (side line), carbolic oil (side line) and heavy oil, carbolic oil enters carbolic oil extraction plant 2 and isolates phenol products and dephenolize oil, heavy oil at the bottom of tower and the unconverted tail oil of hydrocracking section are mixed into delayed coking unit 3 to carry out heat scission reaction and produces coking dry gas, liquefied gas, coking naphtha, coker gas oil, wax tailings and petroleum coke, temperature of reaction is 500 DEG C, reaction pressure 0.17MPa.Wherein coking naphtha, coker gas oil, the benzoline of wax tailings and separation column 1, enter hydro-refining unit 4 after the isolated dephenolize oil of carbolic oil extraction plant 2 and heavy distillate mix and carry out hydrofining reaction, the gasoline that hydrofining reaction obtains and diesel oil can go out device, the wax oil that hydrofining reaction obtains enters hydroeracking unit 5 and carries out hydrocracking reaction, hydrocracking reaction product separation is dry gas, liquefied gas, hydrotreated naphtha, hydrogenated diesel oil and unconverted tail oil, hydrorefined temperature of reaction is 410 DEG C, pressure 12.5MPa, volume space velocity 0.5h when hydrogen to oil volume ratio 2000: 1 and liquid
-1, volume space velocity 0.6h when the temperature of reaction 415 DEG C of hydrocracking, pressure 11.0MPa, hydrogen to oil volume ratio 1400: 1 and liquid
-1.Hydrobon catalyst is with alumina supporter, and molybdenum oxide weight content is 15%, and Tungsten oxide 99.999 weight content is 12%, and nickel oxide weight content is 5%, and specific surface area is 185m
2/ g, pore volume is 0.35ml/g.(silica/alumina molecular ratio is for 12 with Y zeolite for hydrocracking catalyst, structure cell is often for 0.2426nm) and amorphous aluminum silicide (silica weight content is 27%, infrared acidity is 0.4mmol/g) be Cracking Component, Y zeolite weight content is 15%, amorphous aluminum silicide weight content is 35%, and Tungsten oxide 99.999 weight content is 28%, and nickel oxide weight content is 8%, surplus is aluminum oxide, and specific surface area is 270m
2/ g, pore volume is 0.42ml/g.Hydrobon catalyst and hydrocracking catalyst carry out conventional prevulcanized process before use.
Table 1 destructive distillation coal tar main character
| Raw material | Middle coalite tar |
| Density (20 DEG C), g/cm 3 | 1.06 |
| Boiling range, DEG C | |
| IBP/10％ | 102.8/188.8 |
| 30％/50％ | 245.2/338.0 |
| 70％/90％ | 395.0/445.2 |
| 95％/FBP | 484.0/-- |
| S，wt％ | 0.39 |
| N，μg·g -1 | 7986 |
The hydrofining of table 2 the inventive method and hydrocracking mixing naphtha fraction main character
| Density (20 DEG C), gcm -3 | 0.7576 |
| Boiling range, DEG C | |
| IBP/10％ | 87/105 |
| 30％/50％ | 113/124 |
| 70％/90％ | 133/153 |
| EBP | 166 |
| S，μg·g -1 | ＜0.5 |
| N，μg·g -1 | ＜0.5 |
| Compositional analysis, wt% | |
| Alkane | 6.2 |
| C 4/C 5 | 0.2/0.9 |
| C 6/C 7 | 1.9/1.7 |
| C 8/C 9 | 0.9/0.5 |
| C 10 | 0.1 |
| Naphthenic hydrocarbon | 90.0 |
| C 5/C 6 | 0.2/19.0 |
| C 7/C 8 | 23.4/17.6 |
| C 9/C 10 | 14.3/13.5 |
| C 11 | 2.0 |
| Aromatic hydrocarbons | 3.8 |
| C 6/C 7 | 1.4/0.8 |
| C 8/C 9 | 0.6/0.9 |
| C 10 | 0.1 |
| Virtue is dived, % | 88.54 |
Continued 2 the inventive method hydrofining diesel oil and hydrocracking diesel fuel mixtures character
| Density (20 DEG C), gcm -3 | 0.8684 |
| Boiling range, DEG C | |
| IBP/10％ | 163/210 |
| 30％/50％ | 222/236 |
| 70％/90％ | 254/287 |
| 95％/EBP | 305/342 |
| Viscosity (20 DEG C), mm 2·s -1 | |
| Acidity, mgKOH (100mL) -1 | 1.57 |
| 10% steams excess carbon residue, % | ＜0.01 |
| Refractive power (20 DEG C) | |
| Flash-point, DEG C | 55 |
| Condensation point, DEG C | ＜-50 |
| Cold filter clogging temperature, DEG C | ＜-40 |
| Cetane value | 47.8 |
| S，μg·g -1 | ＜5 |
| N，μg·g -1 | ＜1.0 |
The physical properties of several main lower boiling phenol of continued 2 the inventive method
In phenol products of the present invention: industrial phenol ctystallizing point is no less than 31 DEG C of neutral oils and is not more than 0.5% moisture and is not more than 1.5% pyridine base 0.3%;
Ortho position cresols is not less than 96% phenol content and is not more than 2% xylenol and is not more than 2% moisture and is not more than 0.5%;
Flow out before discharge is not more than 3%210 DEG C before 3 mixed cresol 190 DEG C and be not less than 96%;
Between position cresols be not less than 41% neutral oil content and be not more than 1% moisture and be not more than 0.5%;
Be not less than 90% before discharge is not more than 0.5%225 DEG C before technical xylenol 205 DEG C, neutral oil is not more than 1.8% moisture and is not more than 1.2%.
Comparative example 1
The delayed coking unit charging of comparative example is the full cut of middle coalite tar, and the charging of the delayed coking unit of embodiment is the mixing oil of the heavy oil that obtains of middle coalite tar fractionation and hydrocracking section unconverted oil.The operational condition that delayed coking unit adopts, with embodiment 2, the results are shown in Table 3.
Table 3 delayed coking material balance
Claims (14)
1. a coalite tar deep processing method in, is characterized in that comprising following processing step:
(1) by the fractionation of middle coalite tar raw material, lighting end, carbolic oil, last running and heavy oil is obtained;
(2) carbolic oil that step (1) obtains carries out phenol removal, obtains phenol products and dephenolize oil;
(3) pyrogenic reaction is carried out in the hydrocracking tail oil mixing obtained in the heavy oil obtained in step (1) and step (4), obtains coking dry gas, liquefied gas, coking naphtha, coker gas oil, wax tailings and refinery coke product;
(4) at least one in the dephenolize oil in the lighting end that at least one in the coking naphtha, coker gas oil and the wax tailings that obtain of step (3) obtains with step (1), last running and step (2) mixes, carry out hydrofining and hydrocracking reaction, be obtained by reacting dry gas, liquefied gas, hydrotreated naphtha, hydrogenated diesel oil product and hydrocracking tail oil.
2. in accordance with the method for claim 1, it is characterized in that: carry out pre-treatment before coalite tar fractionation in step (1), pre-treatment removes moisture and mechanical impurity.
3. in accordance with the method for claim 2, it is characterized in that: described pre-treatment is centrifuging, electrodesalting and electrodehydrating.
4. in accordance with the method for claim 1, it is characterized in that: the middle low temperature coal tar raw material fractionation of step (1) adopts vacuum fractionation tower, tower top fractionates out lighting end, side line fractionates out carbolic oil, last running, obtain heavy oil at the bottom of tower, the final boiling point of lighting end is not more than 180 DEG C, and the final boiling point of carbolic oil is not more than 240 DEG C, the final boiling point of last running is not more than 350 DEG C, and the initial boiling point of heavy oil is not less than 340 DEG C.
5. in accordance with the method for claim 1, it is characterized in that: step (2) or the phenol removal described in step (4) adopt soda acid method for extracting.
6. in accordance with the method for claim 5, it is characterized in that: described phenol removal adopts coal tar carbolic oil refining plant, what separation column separated enters extraction tower containing phenol cut, in extraction tower, add alkaline solution, and the phenates extracted is through steaming stripping oil, sulfuric acid or CO
2obtain phenol products after decomposition, after extracting phenol products, obtain dephenolize oil.
7. in accordance with the method for claim 1, it is characterized in that: the pyrogenic reaction operational condition described in step (3) is temperature of reaction 400 DEG C ~ 550 DEG C, reaction pressure 0.15MPa ~ 0.5MPa.
8. in accordance with the method for claim 7, it is characterized in that: the pyrogenic reaction operational condition described in step (3) is temperature of reaction 400 DEG C ~ 535 DEG C, reaction pressure 0.17MPa ~ 0.35MPa.
9. in accordance with the method for claim 1, it is characterized in that: the hydrofining described in step (4) and hydrocracking adopt two-stage hydrocracking technique, hydrofining reaction product is before entering hydrocracking reactor, first separation column is entered, hydrofining full distillate oil is obtained gasoline fraction, diesel oil distillate and wax oil cut by fractionation, gasoline fraction and diesel oil distillate directly go out device, and wax oil cut then carries out hydrocracking reaction.
10. according to the method described in claim 1 or 9, it is characterized in that: the hydrofining reaction condition in step (4) is: volume space velocity 0.15 ~ 1.5h when temperature of reaction 180 ~ 427 DEG C, pressure 10.0 ~ 17.0MPa, hydrogen to oil volume ratio 500:1 ~ 3500:1 and liquid
-1.
11. in accordance with the method for claim 10, it is characterized in that: the hydrofining reaction condition in step (4) is as follows: volume space velocity 0.2 ~ 1.2h when temperature of reaction 180 ~ 420 DEG C, pressure 10.0 ~ 16.0MPa, hydrogen to oil volume ratio 800:1 ~ 3000:1 and liquid
-1.
12., according to the method described in claim 1 or 9, is characterized in that: the hydrocracking reaction condition in step (4) is: volume space velocity 0.15 ~ 1.5h when temperature of reaction 360 ~ 427 DEG C, pressure 10.0 ~ 17.0MPa, hydrogen to oil volume ratio 500:1 ~ 2000:1 and liquid
-1.
13. in accordance with the method for claim 12, it is characterized in that: the hydrocracking reaction condition in step (4) is as follows: volume space velocity 0.2 ~ 1.2h when temperature of reaction 380 ~ 420 DEG C, pressure 10.0 ~ 16.0MPa, hydrogen to oil volume ratio 800:1 ~ 1500:1 and liquid
-1.
14. according to the method described in claim 1 or 9, it is characterized in that: one or more in dry distillation of coal coal gas, gasification coal gas, natural gas hydrogen preparation, oil refinery dry gas hydrogen manufacturing and hydrogen from methyl alcohol of the hydrogen source of hydrofining and hydrocracking process needs in step (4), the concentrate of low-concentration hydrogen adopts pressure-changed adsorption concentrating method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210352692.7A CN102899087B (en) | 2012-09-19 | 2012-09-19 | Deep processing method for medium and low temperature coal tar |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN104178212B (en) * | 2013-05-20 | 2016-07-27 | 神华集团有限责任公司 | A kind of coal tar hydrogenating method for upgrading |
| CN103289718B (en) * | 2013-07-02 | 2015-09-09 | 西北大学 | A kind of middle coalite tar prepares the method for dephenolize oil and resol |
| US20150136652A1 (en) * | 2013-11-19 | 2015-05-21 | Uop Llc | Process for hydrotreating a coal tar stream |
| CN103695036B (en) * | 2013-12-31 | 2015-10-28 | 上海新佑能源科技有限公司 | Middle coalite tar processing and treating method |
| CN104004541B (en) * | 2014-06-13 | 2016-01-20 | 煤炭科学研究总院 | A kind of preparation method of coal-based high arene underwater content stock oil |
| CN105316034B (en) * | 2014-07-10 | 2018-05-15 | 神华集团有限责任公司 | The processing method of carbolic oil in a kind of coal tar |
| CN105694967A (en) * | 2014-11-25 | 2016-06-22 | 神华集团有限责任公司 | Processing method for coal tar and high-octane-number gasoline prepared by using same |
| CN108441250A (en) * | 2018-05-18 | 2018-08-24 | 上海优华系统集成技术股份有限公司 | A kind of processing system and its processing method of phenol tar |
| CN111704935B (en) * | 2020-08-03 | 2021-06-04 | 陕西延长石油（集团）有限责任公司 | Low-rank coal hydrogenation-pyrolysis-gasification coupling integrated poly-generation process method |
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| CN101538482B (en) * | 2009-04-01 | 2012-11-07 | 陕西煤业化工集团(上海)胜帮化工技术有限公司 | Medium and low temperature coal tar deep processing method |
| CN101580728B (en) * | 2009-06-10 | 2012-10-03 | 中煤能源黑龙江煤化工有限公司 | Process technology for non-caking coal or weak caking coal |
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